NEW STEREORETENTIVE RUTHENIUM COMPLEXES, METHOD OF THEIR PREPARATION, INTERMEDIATES USED IN THIS METHOD AND USE OF NEW STEREORETENTIVE RUTHENIUM COMPLEXES IN OLEFIN METATHESIS REACTIONS

Abstract

The subject matter of the invention is a stereoretentive ruthenium complex of the general formula 1a-Ru and/or 1b-Ru, in which all variables have the meanings defined in the description. The subject matter of the invention is also a method of preparing the ruthenium complex, an intermediate used in preparing the ruthenium complex, and the use of this ruthenium complex as a (pre) catalyst in olefin metathesis reactions such as ring-closing metathesis (RCM), homometathesis (self-CM), cross-metathesis (CM), and stereoretentive processes in olefin metathesis.

##STR00001##

Claims

1. Ruthenium complex of formula 1-Ru ##STR00137## in which: L.sup.1 is a neutral ligand selected from N-heterocyclic carbenes (NHCs), cyclic alkylaminocarbene (CAAC) or phosphines; R.sup.1 and R.sup.2 are independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.1 and R.sup.2 are independently alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups to form a quaternary ammonium group, a tertiary sulfonium group, or a quaternary phosphonium group; or R.sup.1 and R.sup.2, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system, which may be substituted by one and/or more substituents selected from hydrogen, halogen, C.sub.1-C.sub.25 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively, the two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus; R.sup.13 and R.sup.14 are independently hydrogen, halogen, optionally substituted C.sub.1-C.sub.25 alkyl, optionally substituted C.sub.3-C.sub.25 cycloalkyl, optionally substituted C.sub.1-C.sub.12 perfluoroalkyl, optionally substituted C.sub.2-C.sub.25 alkene, optionally substituted C.sub.2-C.sub.25 alkenyl, optionally substituted C.sub.3-C.sub.25 cycloalkenyl, optionally substituted C.sub.2-C.sub.25 alkynyl, optionally substituted C.sub.3-C.sub.25 cycloalkynyl, optionally substituted C.sub.1-C.sub.25 alkoxy, optionally substituted C.sub.5-C.sub.25 aryl, optionally substituted C.sub.5-C.sub.25 aryloxy, optionally substituted C.sub.6-C.sub.25 aralkyl, optionally substituted C.sub.5-C.sub.25 heteroaryl, optionally substituted C.sub.5-C.sub.25 heteroaryloxy, optionally substituted C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium or phosphorus, optionally substituted; wherein the R.sup.13 and R.sup.14 substituents, taken together, may form a ring selected from a group comprising C.sub.3-C.sub.25 cycloalkyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium or phosphorus, optionally substituted with one and/or more substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxy, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 aryloxy, C.sub.6-C.sub.25 arylalkyl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 heteroaryloxy, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle; wherein the R.sup.13 and R.sup.14 substituents are independently preferably hydrogen and/or C.sub.5-C.sub.25 aryl independently substituted with hydrogen, halogen, C.sub.1-C.sub.25 alkyl group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group independently is hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, the two R groups, taken together, may form either C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl ring containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, alternatively R is a ketone group (COR.sup.c) in which R.sup.c is C.sub.1-C.sub.12 perfluoroalkyl or alkoxy group (OR.sup.d) in which R.sup.d is C.sub.1-C.sub.12 alkyl or C.sub.3-C.sub.12 heterocycloalkyl containing nitrogen, oxygen or sulfur optionally additionally substituted with C.sub.1-C.sub.12 alkyl group; G is selected from such as L.sup.2 ligand ##STR00138## in which the R.sup.20 and R.sup.21 substituents are independently C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.5-C.sub.20 aryl group, or C.sub.5-C.sub.20 heteroaryl group, C.sub.5-C.sub.25 aralkyl group, which may be substituted independently by one and/or more substituents selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.5-C.sub.20 heteroaryl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy, alkoxy (OR), sulfide (SR), amine (NR.sub.2) group, in which the R group independently is hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, alternatively R.sup.20 and R.sup.21, taken together, form C.sub.5-C.sub.25 ring; each R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituent independently is hydrogen, halogen, hydroxyl group, C.sub.1-C.sub.12 alkoxy group, hydroxymethyl group (CH.sub.2OH), C.sub.1-C.sub.12 alkyl group optionally substituted with an amine group (NR.sup.a), in which each R.sup.a is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.a groups, taken together, may form either C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl, C.sub.3-C.sub.12 cycloalkyl group; C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 heteroaryl group, ester group (OCOR.sup.b), (COR.sup.d) group, methylester group (CH.sub.2OCOR.sup.b), in which R.sup.b is either C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group; amine group (NR.sup.c.sub.2), methylamine group (CH.sub.2NR.sup.c), in which each R.sup.c is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.c groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, which can be substituted independently by at least one substituent selected from a group comprising hydroxyl (OH), C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.3-C.sub.12 heterocycloalkyl optionally substituted with C.sub.1-C.sub.12 alkyl group, ester group (COOR.sup.d) or (COR.sup.d) group, in which R.sup.d is C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group, or amine group (NR.sup.e.sub.2) in which each R.sup.e is independently hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.e groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, and R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituents may optionally be interconnected to form cyclic C.sub.4-C.sub.10 system or polycyclic C.sub.4-C.sub.12 system; each R.sup.28, R.sup.29, and R.sup.30 substituent is independently C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.28, R.sup.29, R.sup.30, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system which may be substituted by one and/or more substituents selected from hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy and halogen; each R.sup.31, R.sup.32, R.sup.3, R.sup.34 and R.sup.35 substituent is independently C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.3-C.sub.20 aryl group or C.sub.5-C.sub.20 heteroaryl group, which may be substituted independently by one and/or more substituents selected from a group comprising hydrogen, C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, or halogen; or heteroatom 1 selected from a group comprising oxygen, sulfur, selenium, substituted by a group selected from such as hydrogen, halogen, oxygen, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, optionally substituted by acyl (COR), cyano (CN), carboxyl (COOH), ester (COOR), ester (CH.sub.2COOR), ester (CHRCOOR), ester (C(R).sub.2COOR), amide (CONR.sub.2), Weinreb-type amide (CON(R)(OR)), sulfonic (SO.sub.2R), formyl (COH), sulfonamide (SO.sub.2NR.sub.2), ketone (COR), thioamide (CSNR.sub.2), thioketone (CSR), thionoester (CSOR), thioester (COSR), dithioester (CS.sub.2R) group, in which R group is independently C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.3-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, C.sub.5-C.sub.24 heteroaryloxy and then the dashed line represents a direct binding of the heteroatom to the R.sup.14 substituent or represents the connection of the R.sup.14 substituent to the heteroatom via a CH.sub.2, CHR, or CR.sub.2 methylene bridge, wherein the R.sup.14 substituent is C.sub.5-C.sub.15 aryl optionally substituted by 1-4 substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl; or heteroatom 2 selected from a group comprising either nitrogen or phosphorus, substituted by a group selected from such as hydrogen, methylidene optionally substituted by an R substituent, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, acyl group (COR), ester group (COOR), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (CONR.sub.2), sulfonic group (SO.sub.2R), formyl group (COH), in which the R group is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy optionally substituted by acyl group (COR), cyano (CN), carboxyl (COOH), ester (COOR), ester (CH.sub.2COOR), ester (CHRCOOR), ester (C(R).sub.2COOR), amide (CONR.sub.2), sulfonic (SO.sub.2R), formyl (COH), sulfonamide (SO.sub.2NR.sub.2), ketone (COR), thioamide (CSNR.sub.2), thioketone (CSR), thionoester (CSOR), thioester (COSR), dithioester (CS.sub.2R) group, in which the R group is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy and then the dashed line represents a direct binding of the heteroatom to the R.sup.14 substituent or represents the connection of the R.sup.14 substituent to the heteroatom via a (CH.sub.2), (CHR), or (CR.sub.2) methylene bridge; wherein the R.sup.14 substituent is C.sub.5-C.sub.15 aryl optionally substituted by 1-4 substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, or heteroatom 3 selected from a group comprising a halogen, and then the dashed line represents a direct binding of the heteroatom to the R.sup.14 substituent, wherein the R.sup.14 substituent is C.sub.5-C.sub.15 aryl, or C.sub.5-C.sub.25 polyaryl optionally substituted by 1-4 substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl.

2. The ruthenium complex according to claim 1, in which the neutral L.sup.1 ligand has a structure represented by a general formula selected from 2a, 2b, 2c or 2d ##STR00139## in which: each R.sup.20 and R.sup.21 substituent is independently C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.5-C.sub.20 aryl group, or C.sub.5-C.sub.20 heteroaryl group, which may be substituted independently by one and/or more substituents selected from a group comprising hydrogen, C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 perfluoroaryl group, C.sub.5-C.sub.20 heteroaryl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, or halogen, alkoxy group (OR), sulfide group (SR), halogen, amino group (NR.sub.2), in which the R group independently is hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, alternatively R.sup.20 and R.sup.21, taken together, form ring C.sub.5-C.sub.25 group; each R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituent independently is hydrogen, halogen, hydroxyl group, C.sub.1-C.sub.12 alkoxy group, hydroxymethyl group (CH.sub.2OH), C.sub.1-C.sub.12 alkyl group optionally substituted with an amine group (NR.sup.a), in which each R.sup.a is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.a groups, taken together, may form either C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl, C.sub.3-C.sub.12 cycloalkyl group; C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 heteroaryl group, ester group (OCOR.sup.b), (COR.sup.d) group, methylester group (CH.sub.2OCOR.sup.b), in which R.sup.b is either C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group; amine group (NR), methylamine group (CH.sub.2NR.sup.c), in which each R.sup.c is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.c groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, which may be substituted independently by at least one substituent selected from a group comprising hydroxyl (OH), C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.3-C.sub.12 heterocycloalkyl optionally substituted with C.sub.1-C.sub.12 alkyl group, ester group (COOR.sup.d) or (COR.sup.d) group, in which R.sup.d is C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group, or amine group (NR.sup.e.sub.2) in which each R.sup.d is independently hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.e groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, and R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituents may optionally be interconnected to form cyclic C.sub.4-C.sub.10 system or polycyclic C.sub.4-C.sub.12 system; R.sup.28, R.sup.29 and R.sup.30 independently are C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.1 and R.sup.2, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system which can be substituted by one and/or more substituents selected from hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy and halogen.

3. The ruthenium complex according to claim 1 or 2 represented by the formula 1a-Ru ##STR00140## in which: L.sup.1 is a neutral ligand selected from N-heterocyclic carbenes (NHCs), cyclic alkylaminocarbene (CAAC), or phosphines; n is 1 or 0 Z is selected from a group comprising halogen, O, S, Se, or NR group, in which R is methylidene, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, acyl group (COR), ester group (COOR), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (CONR.sub.2), sulfonic group (SO.sub.2R), formyl group (COH), in which the R group is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy or halogen, wherein when Z is halogen, R.sup.15 does not exist; R.sup.1 and R.sup.2 are independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.1 and R.sup.2, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system, which may be substituted by one and/or more substituents selected from hydrogen, halogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy, C.sub.1-C.sub.25 alkyl group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl; R.sup.15 is independently hydrogen, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.24 aryloxy, COOR group, CH.sub.2COOR group, CONR.sub.2 group, CH.sub.2CONR.sub.2 group, COR group, CH.sub.2COR group, CON(OR)(R) group, CH.sub.2CON(OR)(R) group, or a halogen, wherein R is C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 aryl, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.6-C.sub.24 aryloxy, or halogen; R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl group, C.sub.2-C.sub.25 alkenyl group, C.sub.5-C.sub.25 aryl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, wherein R.sup.16, R.sup.17, R.sup.18, and R.sup.19 substituents, taken together, may form a substituted or unsubstituted cyclic C.sub.4-C.sub.10 or polycyclic C.sub.4-C.sub.12 system.

4. The ruthenium complex according to claim 1, 2 or 3 with the formula 1b-Ru ##STR00141## in which: L.sup.1 is a neutral ligand selected from N-heterocyclic carbenes (NHCs), cyclic alkylaminocarbene (CAAC) or PR.sub.3 phosphines; L.sup.2 is a neutral ligand selected from N-heterocyclic carbenes (NHCs), cyclic alkylaminocarbene (CAAC), PR.sub.3 phosphine derivatives or pyridine derivatives; R.sup.1 and R.sup.2, are independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.1 and R.sup.2, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system, which may be substituted by one and/or more substituents selected from hydrogen, halogen, C.sub.1-C.sub.25 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus; R.sup.13 and R.sup.14 are independently hydrogen, halogen, optionally substituted C.sub.1-C.sub.25 alkyl, optionally substituted C.sub.3-C.sub.25 cycloalkyl, optionally substituted C.sub.1-C.sub.12 perfluoroalkyl, optionally substituted C.sub.2-C.sub.25 alkene, optionally substituted C.sub.2-C.sub.25 alkenyl, optionally substituted C.sub.3-C.sub.25 cycloalkenyl, optionally substituted C.sub.2-C.sub.25 alkynyl, optionally substituted C.sub.3-C.sub.25 cycloalkynyl, optionally substituted C.sub.1-C.sub.25 alkoxy, optionally substituted C.sub.5-C.sub.25 aryl, optionally substituted C.sub.5-C.sub.25 aryloxy, optionally substituted C.sub.6-C.sub.25 arylalkyl, optionally substituted C.sub.5-C.sub.25 heteroaryl, optionally substituted C.sub.5-C.sub.25 heteroaryloxy, optionally substituted C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium or phosphorus, optionally substituted; wherein R.sup.13 and R.sup.14 substituents, taken together, may form a ring selected from a group comprising C.sub.3-C.sub.25 cycloalkyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium, or phosphorus which may be substituted independently with one and/or more substituents selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxy, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 aryloxy, C.sub.6-C.sub.25 arylalkyl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 heteroaryloxy, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle.

5. The ruthenium complex according to any of the claims 1 to 4 with the formula 1b-Ru ##STR00142## in which the L.sup.1 ligand is ##STR00143## in which: each R.sup.20 and R.sup.21 substituent is independently C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.5-C.sub.20 aryl group, or C.sub.5-C.sub.20 heteroaryl group, which may be substituted independently by one and/or more substituents selected from a group comprising hydrogen, C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 perfluoroaryl group, C.sub.5-C.sub.20 heteroaryl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, or halogen, alkoxy group (OR), sulfide group (SR), halogen, amino group (NR.sub.2), in which the R group independently is hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, alternatively R.sup.20 and R.sup.21, taken together, form ring C.sub.5-C.sub.25 group; each R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituent independently is hydrogen, halogen, hydroxyl group, C.sub.1-C.sub.12 alkoxy group, hydroxymethyl group (CH.sub.2OH), C.sub.1-C.sub.12 alkyl group optionally substituted with an amine group (NR.sup.a), in which each R.sup.a is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.a groups, taken together, may form either C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl, C.sub.3-C.sub.12 cycloalkyl group; C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 heteroaryl group, ester group (OCOR.sup.b), (COR.sup.d) group, methylester group (CH.sub.2OCOR.sup.b), in which R.sup.b is either C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group; amine group (NR), methylamine group (CH.sub.2NR.sup.c), in which each R.sup.c is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.e groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, which may be substituted independently by at least one substituent selected from a group comprising hydroxyl (OH), C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.3-C.sub.12 heterocycloalkyl optionally substituted with C.sub.1-C.sub.12 alkyl group, ester group (COOR.sup.d) or (COR.sup.d) group, in which R.sup.d is C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group, or amine group (NR.sup.e.sub.2) in which each R.sup.d is independently hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.e groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, and R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituents may optionally be interconnected to form cyclic C.sub.4-C.sub.10 system or polycyclic C.sub.4-C.sub.12 system; R.sup.28, R.sup.29, and R.sup.30 are independently C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.28, R.sup.29 and R.sup.30, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system which can be substituted by one and/or more substituents selected from hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy and halogen; in which L.sup.2 ligand is: ##STR00144## in which each R.sup.20 and R.sup.21 substituent is independently C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.5-C.sub.20 aryl group, or C.sub.5-C.sub.20 heteroaryl group, which may be substituted independently by one and/or more substituents selected from a group comprising hydrogen, C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 perfluoroaryl group, C.sub.5-C.sub.20 heteroaryl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, or halogen, alkoxy group (OR), sulfide group (SR), halogen, amino group (NR.sub.2), in which the R group independently is hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, alternatively R.sup.20 and R.sup.21, taken together, form ring C.sub.5-C.sub.25 group; each R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituent independently is hydrogen, halogen, hydroxyl group, C.sub.1-C.sub.12 alkoxy group, hydroxymethyl group (CH.sub.2OH), C.sub.1-C.sub.12 alkyl group optionally substituted with an amine group (NR.sup.a), in which each R.sup.a is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.a groups, taken together, may form either C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl, C.sub.3-C.sub.12 cycloalkyl group; C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 heteroaryl group, ester group (OCOR.sup.b), (COR.sup.d) group, methylester group (CH.sub.2OCOR.sup.b), in which R.sup.b is either C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group; amine group (NR), methylamine group (CH.sub.2NR.sup.c), in which each R.sup.c is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.e groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, which may be substituted independently by at least one substituent selected from a group comprising hydroxyl (OH), C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.3-C.sub.12 heterocycloalkyl optionally substituted with C.sub.1-C.sub.12 alkyl group, ester group (COOR.sup.d) or (COR.sup.d) group, in which R.sup.d is C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group, or amine group (NR.sup.e.sub.2) in which each R.sup.d is independently hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.e groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, and R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituents may optionally be interconnected to form C.sub.4-C.sub.10 cyclic system or C.sub.4-C.sub.12 polycyclic system; each R.sup.28, R.sup.29, and R.sup.30 substituent is independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.28, R.sup.29 and R.sup.30, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system, which may be substituted by one and/or more substituents selected from hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy, and halogen; each R.sup.31, R.sup.32, R.sup.33, R.sup.34 and R.sup.35 substituent is independently hydrogen, halogen, C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 heteroaryl group, which can be substituted independently by one and/or more substituents selected from a group comprising hydrogen, C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, or halogen; R.sup.13 and R.sup.14 are independently hydrogen, halogen, optionally substituted C.sub.1-C.sub.25 alkyl, optionally substituted C.sub.3-C.sub.25 cycloalkyl, optionally substituted C.sub.1-C.sub.12 perfluoroalkyl, optionally substituted C.sub.2-C.sub.25 alkene, optionally substituted C.sub.2-C.sub.25 alkenyl, optionally substituted C.sub.3-C.sub.25 cycloalkenyl, optionally substituted C.sub.2-C.sub.25 alkynyl, optionally substituted C.sub.3-C.sub.25 cycloalkynyl, optionally substituted C.sub.1-C.sub.25 alkoxy, optionally substituted C.sub.5-C.sub.25 aryl, optionally substituted C.sub.5-C.sub.25 aryloxy, optionally substituted C.sub.6-C.sub.25 arylalkyl, optionally substituted C.sub.5-C.sub.25 heteroaryl, optionally substituted C.sub.5-C.sub.25 heteroaryloxy, optionally substituted C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium or phosphorus, optionally substituted; wherein R.sup.13 and R.sup.14 substituents, taken together, may form a ring selected from a group comprising C.sub.3-C.sub.25 cycloalkyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium or phosphorus which may be substituted independently with one and/or more substituents selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxy, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 aryloxy, C.sub.6-C.sub.25 arylalkyl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 heteroaryloxy, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle.

6. The ruthenium complex according to any of the claims 1 to 5, characterized in that its structure is represented by a formula selected from such as ##STR00145## ##STR00146## ##STR00147## ##STR00148##

7. A compound with the structure defined by formula 3a or 3b ##STR00149## in which M is monovalent or divalent metal cation; n is 0, 1, 2 or 3; E is at least one heteroatom selected from a group comprising oxygen, sulfur, selenium, nitrogen, phosphorus, which are substituted with a group, or if the heteroatom is nitrogen or phosphorus, with groups: C.sub.1-C.sub.25 alkyl group, C.sub.1-C.sub.25 cycloalkyl group, C.sub.5-C.sub.20 alkoxy group, C.sub.5-C.sub.20 aryl group, C.sub.7-C.sub.20 aralkyl group, C.sub.5-C.sub.24 aryloxy group, C.sub.2-C.sub.12 alkenyl group, C.sub.6-C.sub.20 heteroaryl group, C.sub.5-C.sub.24 heteroaryloxy group, or hydrogen, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or if two identical or different heteroatoms constitute a chelating system then, taken together, they form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system, which may be substituted by one and/or more substituents selected from hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy, and halogen; R.sup.1 and R.sup.2 are independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.1 and R.sup.2 are independently alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, or R.sup.1 and R.sup.2, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10, polyaromatic C.sub.4-C.sub.10, and polyheteroaromatic C.sub.4-C.sub.10 system, which can be substituted by one and/or more substituents selected from hydrogen, halogen, C.sub.1-C.sub.25 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively, the two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus.

8. Compound 3c or 3d or 3e according to claim 7 ##STR00150## in which M.sup.2+ is Zn, Cu, Mg, Ca cation, M.sup.+ is Li, Na, K, Cs, Cu or Cu.sup.x(E).sub.n cation n is 1 or 2; R.sup.1 and R.sup.2 are independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.1 and R.sup.2 are independently alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group; or R.sup.1 and R.sup.2, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10, polyaromatic C.sub.4-C.sub.10, and polyheteroaromatic C.sub.4-C.sub.10 system, which can be substituted by one and/or more substituents selected from hydrogen, halogen, C.sub.1-C.sub.25 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively, the two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus; R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 independently are hydrogen, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or two selected R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 substituents, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, heterocyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system, which may be substituted by one and/or more substituents selected from hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.3-C.sub.20 heteroaryloxy, and halogen.

9. Compound 3f according to claim 7 or 8 ##STR00151## in which M.sup.2+ is Zn cation, R.sup.1 and R.sup.2 are independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.1 and R.sup.2 are independently alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group; or R.sup.1 and R.sup.2, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system, which may be substituted by one and/or more substituents selected from hydrogen, halogen, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, C.sub.1-C.sub.25 alkyl group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively, the two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus.

10. Compound according to claim 7, 8 or 9, characterized in that its structure is represented by a formula selected from such as 3-Zn1, 3-Zn2, 3-Zn3, 3-Zn4, 3-Zn5, 3-Zn6, 3-Zn7, 3-Zn8, 3-Zn9, 3-Zn10, 3-Zn11, 3-Zn12, 3-Zn13 and 3-K1: ##STR00152## ##STR00153##

11. A method of producing the ruthenium complex of formula 1-Ru, as defined in any of the claims 1 to 6: ##STR00154## in which: L.sup.1 is a neutral ligand selected from N-heterocyclic carbenes (NHCs), cyclic alkylaminocarbene (CAAC), or phosphines; R.sup.1 and R.sup.2, are independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.1 and R.sup.2 are independently alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group; or R.sup.1 and R.sup.2, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system, which can be substituted by one and/or more substituents selected from hydrogen, halogen, C.sub.1-C.sub.25 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively, the two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, R.sup.13 and R.sup.14 are independently hydrogen, halogen, optionally substituted C.sub.1-C.sub.25 alkyl, optionally substituted C.sub.3-C.sub.25 cycloalkyl, optionally substituted C.sub.1-C.sub.12 perfluoroalkyl, optionally substituted C.sub.2-C.sub.25 alkene, optionally substituted C.sub.2-C.sub.25 alkenyl, optionally substituted C.sub.3-C.sub.25 cycloalkenyl, optionally substituted C.sub.2-C.sub.25 alkynyl, optionally substituted C.sub.3-C.sub.25 cycloalkynyl, optionally substituted C.sub.1-C.sub.25 alkoxy, optionally substituted C.sub.5-C.sub.25 aryl, optionally substituted C.sub.5-C.sub.25 aryloxy, optionally substituted C.sub.6-C.sub.25 arylalkyl, optionally substituted C.sub.5-C.sub.25 heteroaryl, optionally substituted C.sub.5-C.sub.25 heteroaryloxy, optionally substituted C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium or phosphorus, optionally substituted; wherein R.sup.13 and R.sup.14 substituents, taken together, may form a ring selected from a group comprising C.sub.3-C.sub.25 cycloalkyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium or phosphorus which may be substituted independently with one and/or more substituents selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxy, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 aryloxy, C.sub.6-C.sub.25 arylalkyl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 heteroaryloxy, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle; wherein the R.sup.13 and R.sup.14 substituents are independently preferably hydrogen and/or an C.sub.5-C.sub.25 aryl independently substituted with hydrogen, halogen, C.sub.1-C.sub.25 alkyl group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.2), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group independently is hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, the two R groups, taken together, may form either C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl ring containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, alternatively R is a ketone group (COR.sup.c) in which R.sup.c is C.sub.1-C.sub.12 perfluoroalkyl or alkoxy group (OR.sup.d) in which R.sup.d is C.sub.1-C.sub.12 alkyl or C.sub.3-C.sub.12 heterocycloalkyl containing nitrogen, oxygen or sulfur optionally additionally substituted with C.sub.1-C.sub.12 alkyl group; G is selected from such as L.sup.2 ligand ##STR00155## in which the R.sup.20 and R.sup.21 substituents are independently C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 heteroaryl group, C.sub.5-C.sub.25 aralkyl group, which may be substituted independently by one and/or more substituents selected from a group comprising hydrogen, C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 perfluoroaryl group, C.sub.5-C.sub.20 heteroaryl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, or halogen, alkoxy group (OR), sulfide group (SR), halogen, amine group (NR.sub.2), in which the R group independently is hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, alternatively R.sup.20 and R.sup.21, taken together, form C.sub.5-C.sub.25 ring; each R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituent independently is hydrogen, halogen, hydroxyl group, C.sub.1-C.sub.12 alkoxy group, hydroxymethyl group (CH.sub.2OH), C.sub.1-C.sub.12 alkyl group optionally substituted with an amine group (NR.sup.a), in which each R.sup.a is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.a groups, taken together, may form either C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl, C.sub.3-C.sub.12 cycloalkyl group; C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 heteroaryl group, ester group (OCOR.sup.b), (COR.sup.d) group, methylester group (CH.sub.2OCOR.sup.b), in which R.sup.b is either C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group; amine group (NR), methylamine group (CH.sub.2NR.sup.c), in which each R.sup.c is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.c groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, which can be substituted independently by at least one substituent selected from a group comprising hydroxyl (OH), C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.3-C.sub.12 heterocycloalkyl optionally substituted with C.sub.1-C.sub.12 alkyl group, ester group (COOR.sup.d) or (COR.sup.d) group, in which R.sup.d is C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group, or an amino group (NR.sup.e.sub.2) in which each R.sup.d is independently hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.e groups may, taken together, form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, and R.sup.22, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituents may optionally be interconnected to form cyclic C.sub.4-C.sub.10 system or polycyclic C.sub.4-C.sub.12 system; each R.sup.28, R.sup.29, and R.sup.30 substituent is independently C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.28, R.sup.29, R.sup.30, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system which may be substituted by one and/or more substituents selected from hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy and halogen; each R.sup.31, R.sup.32, R.sup.33, R.sup.34 and R.sup.35 substituent is independently C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 heteroaryl group, which may be substituted independently by one and/or more substituents selected from a group comprising hydrogen, C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, or halogen; or heteroatom 1 selected from a group comprising oxygen, sulfur, selenium, substituted by a group selected from such as hydrogen, halogen, oxygen, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.2 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, optionally substituted by acyl group (COR), cyano (CN), carboxyl (COOH), ester (COOR), ester (CH.sub.2COOR), ester (CHRCOOR), ester (C(R).sub.2COOR), amide (CONR.sub.2), Weinreb-type amide (CON(R)(OR)), sulfonic (SO.sub.2R), formyl (COH), sulfonamide (SO.sub.2NR.sub.2), ketone (COR), thioamide (CSNR.sub.2), thioketone (CSR), thionoester (CSOR), thioester (COSR), dithioester (CS.sub.2R) group, in which R group is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.3-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy and then the dashed line represents a direct binding of the heteroatom to the R.sup.14 substituent or represents the connection of the R.sup.14 substituent to the heteroatom via (CH.sub.2), (CHR), or (CR.sub.2) methylene bridge, wherein the R.sup.14 substituent is C.sub.5-C.sub.15 aryl optionally substituted by 1-4 substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl; or heteroatom 2 selected from a group comprising nitrogen, or phosphorus, substituted by a group selected from such as hydrogen, methylidene optionally substituted by an R substituent, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, acyl group (COR), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (CONR.sub.2), sulfonic group (SO.sub.2R), formyl group (COH), in which R group is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy optionally substituted by acyl (COR), cyano (CN), carboxyl (COOH), ester (COOR), ester (CH.sub.2COOR), ester (CHRCOOR), ester (C(R).sub.2COOR), amide (CONR.sub.2), sulfonic (SO.sub.2R), formyl (COH), sulfonamide (SO.sub.2NR.sub.2), ketone (COR), thioamide (CSNR.sub.2), thioketone (CSR), thionoester (CSOR), thioester (COSR), dithioester (CS.sub.2R) group, in which the R group is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy and then the dashed line represents a direct binding of the heteroatom to the R.sup.14 substituent or represents the connection of the R.sup.14 substituent to the heteroatom via (CH.sub.2), (CHR), or (CR.sub.2) methylene bridge; wherein the R.sup.14 substituent is C.sub.5-C.sub.15 aryl optionally substituted by 1-4 substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, or heteroatom 3 selected from a group comprising halogen, and then the dashed line represents a direct binding of the heteroatom to the R.sup.14 substituent, wherein the R.sup.14 substituent is C.sub.5-C.sub.15 aryl, or C.sub.5-C.sub.25 polyaryl optionally substituted by 1-4 substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl; characterized in that the alkylidene ruthenium complex of formula 4-Ru: ##STR00156## in which: X.sup.1 and X.sup.2 independently are anionic ligands selected from a group comprising halogen anion, CN, SCN, OR.sup.a, SR.sup.a, O(CO)R.sup.a, O(SO.sub.2)R.sup.a, and OSi(R.sup.a); group, in which R.sup.a is C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl or C.sub.5-C.sub.20 aryl, which is optionally substituted by at least one C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy or halogen; L.sup.1 is a neutral ligand selected from N-heterocyclic carbenes (NHCs), cyclic alkylaminocarbene (CAAC) or phosphines; R.sup.13 and R.sup.14 are independently hydrogen, halogen, optionally substituted C.sub.1-C.sub.25 alkyl, optionally substituted C.sub.3-C.sub.25 cycloalkyl, optionally substituted C.sub.1-C.sub.12 perfluoroalkyl, optionally substituted C.sub.2-C.sub.25 alkene, optionally substituted C.sub.2-C.sub.25 alkenyl, optionally substituted C.sub.3-C.sub.25 cycloalkenyl, optionally substituted C.sub.2-C.sub.25 alkynyl, optionally substituted C.sub.3-C.sub.25 cycloalkynyl, optionally substituted C.sub.1-C.sub.25 alkoxy, optionally substituted C.sub.5-C.sub.25 aryl, optionally substituted C.sub.5-C.sub.25 aryloxy, optionally substituted C.sub.6-C.sub.25 arylalkyl, optionally substituted C.sub.5-C.sub.25 heteroaryl, optionally substituted C.sub.5-C.sub.25 heteroaryloxy, optionally substituted C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium or phosphorus, optionally substituted; wherein R.sup.13 and R.sup.14 substituents, taken together, may form a ring selected from a group comprising C.sub.3-C.sub.25 cycloalkyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle containing sulfur, oxygen, nitrogen, selenium or phosphorus which may be substituted independently with one and/or more substituents selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.2-C.sub.25 alkene, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 alkoxy, C.sub.5-C.sub.25 aryl, C.sub.5-C.sub.25 aryloxy, C.sub.6-C.sub.25 arylalkyl, C.sub.5-C.sub.25 heteroaryl, C.sub.5-C.sub.25 heteroaryloxy, C.sub.5-C.sub.25 perfluoroaryl, 3-12-membered heterocycle; wherein the R.sup.13 and R.sup.14 substituents independently preferably are hydrogen and/or C.sub.5-C.sub.25 aryl independently substituted with hydrogen, C.sub.1-C.sub.25 alkyl group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl; G is selected from such as L.sup.2 ligand ##STR00157## in which the R.sup.20 and R.sup.21 substituents are independently C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 heteroaryl group, C.sub.5-C.sub.25 aralkyl group which can be substituted independently by one and/or more substituents selected from a group comprising hydrogen, C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 perfluoroaryl group, C.sub.5-C.sub.20 heteroaryl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, or halogen, alkoxy group (OR), sulfide group (SR), halogen, amine group (NR.sub.2), in which the R group independently is hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, alternatively R.sup.20 and R.sup.21, taken together, form C.sub.5-C.sub.25 ring; each R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituent independently is hydrogen, halogen, hydroxyl group, C.sub.1-C.sub.12 alkoxy group, hydroxymethyl group (CH.sub.2OH), C.sub.1-C.sub.12 alkyl group optionally substituted with an amine group (NR.sup.a), in which each R.sup.a is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.a groups, taken together, may form either C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl, C.sub.3-C.sub.12 cycloalkyl group; C.sub.5-C.sub.20 aryl group, C.sub.5-C.sub.20 heteroaryl group, ester group (OCOR.sup.b), (COR.sup.d) group, methylester group (CH.sub.2OCOR.sup.b), in which R.sup.b is either C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group; amine group (NR), methylamine group (CH.sub.2NR.sup.c), in which each R.sup.c is independently either hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.c groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, which can be substituted independently by at least one substituent selected from a group comprising hydroxyl (OH), C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.3-C.sub.12 heterocycloalkyl optionally substituted with C.sub.1-C.sub.12 alkyl group, ester group (COOR.sup.d) or (COR.sup.d) group, in which R.sup.d is C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 perfluoroaryl group, or an amino group (NR.sup.e.sub.2) in which each R.sup.d is independently hydrogen or C.sub.1-C.sub.12 alkyl, the two R.sup.e groups, taken together, may form C.sub.3-C.sub.12 cycloalkyl ring or C.sub.3-C.sub.25 heterocycloalkyl containing nitrogen, oxygen or sulfur, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, and R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, and R.sup.27 substituents may optionally be interconnected to form cyclic C.sub.4-C.sub.10 system or polycyclic C.sub.4-C.sub.12 system; each R.sup.28, R.sup.29, and R.sup.30 substituent independently is C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.28, R.sup.29, R.sup.30, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system which can be substituted by one and/or more substituents selected from hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy, and halogen; each R.sup.31, R.sup.32, R.sup.33, R.sup.34 and R.sup.35 substituent is independently C.sub.1-C.sub.12 alkyl group, C.sub.3-C.sub.12 cycloalkyl group, C.sub.5-C.sub.20 aryl group or C.sub.5-C.sub.20 heteroaryl group, which may be substituted independently by one and/or more substituents selected from a group comprising hydrogen, C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, or halogen; or heteroatom 1 selected from a group comprising oxygen, sulfur, selenium, substituted by a group selected from such as hydrogen, halogen, oxygen, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.5-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, optionally substituted by acyl (COR), cyano (CN), carboxyl (COOH), ester (COOR), ester (CH.sub.2COOR), ester (CHRCOOR), ester (C(R).sub.2COOR), amide (CONR2), Weinreb-type amide (CON(R)(OR)), sulfonic (SO.sub.2R), formyl (COH), sulfonamide (SO.sub.2NR.sub.2), ketone (COR), thioamide (CSNR.sub.2), thioketone (CSR), thionoester (CSOR), thioester (COSR), dithioester (CS.sub.2R) group, in which the R group is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy and then the dashed line represents a direct binding of the heteroatom to the R.sup.14 substituent or represents the connection of the R.sup.14 substituent to the heteroatom via CH.sub.2, CHR, or CR.sub.2 methylene bridge, wherein the R.sup.14 substituent is C.sub.5-C.sub.15 aryl optionally substituted by 1-4 substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, or heteroatom 2 selected from a group comprising nitrogen, or phosphorus, substituted by a group selected from such as hydrogen, methylidene optionally substituted by an R substituent, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, acyl group (COR), tert-butyloxycarbonyl group (t-Boc) or 9-fluorenylmethoxycarbonyl group (Fmoc), carbamate group (CONR.sub.2), sulfonyl group (SO.sub.2R), formyl group (COH), in which R group is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy optionally substituted by acyl group (COR), cyano (CN), carboxyl (COOH), ester (COOR), ester (CH.sub.2COOR), ester (CHRCOOR), ester (C(R).sub.2COOR), amide (CONR.sub.2), sulfonic (SO.sub.2R), formyl (COH), sulfonamide (SO.sub.2NR.sub.2), ketone (COR), thioamide (CSNR.sub.2), thioketone (CSR), thionoester (CSOR), thioester (COSR), dithioester (CS.sub.2R) group, in which the R group is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy and then the dashed line represents a direct binding of the heteroatom to the R.sup.14 substituent or represents the connection of the R.sup.14 substituent to the heteroatom via (CH.sub.2), (CHR), or (CR.sub.2) methylene bridge; wherein the R.sup.14 substituent is C.sub.5-C.sub.15 aryl optionally substituted by 1-4 substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, or heteroatom 3 selected from a group comprising a halogen, and then the dashed line represents a direct binding of the heteroatom to the R.sup.14 substituent, wherein the R.sup.14 substituent is C.sub.5-C.sub.15 aryl, or C.sub.5-C.sub.25 polyaryl optionally substituted by 1-4 substituents independently selected from a group comprising hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.3-C.sub.25 cycloalkyl, C.sub.2-C.sub.25 alkenyl, C.sub.3-C.sub.25 cycloalkenyl, C.sub.2-C.sub.25 alkynyl, C.sub.3-C.sub.25 cycloalkynyl, C.sub.1-C.sub.25 perfluoroalkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.5-C.sub.20 perfluoroaryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.6-C.sub.20 heteroaryl or C.sub.5-C.sub.24 heteroaryloxy, 3-12-membered heterocycle, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl; is reacted with a compound of the structure defined by formula 3a or 3b ##STR00158## in which M is monovalent or divalent metal cation; n is 0, 1 or 2; E is at least one heteroatom selected from a group comprising oxygen, sulfur, selenium, nitrogen, phosphorus, which are substituted with a group, or if the heteroatom is nitrogen or phosphorus, with groups: C.sub.1-C.sub.25 alkyl group, C.sub.1-C.sub.25 cycloalkyl group, C.sub.5-C.sub.20 alkoxy group, C.sub.5-C.sub.20 aryl group, C.sub.7-C.sub.20 aralkyl group, C.sub.5-C.sub.24 aryloxy group, C.sub.2-C.sub.12 alkenyl group, C.sub.6-C.sub.20 heteroaryl group, C.sub.5-C.sub.24 heteroaryloxy group, or hydrogen, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or if two identical or different heteroatoms constitute a chelating system then, taken together, they form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10 system, which may be substituted by one and/or more substituents selected from hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 perfluoroalkyl, C.sub.1-C.sub.12 alkoxy, C.sub.5-C.sub.24 aryloxy, C.sub.5-C.sub.20 heteroaryloxy, and halogen; R.sup.1 and R.sup.2 are independently hydrogen, halogen, C.sub.1-C.sub.25 alkyl, C.sub.5-C.sub.20 alkoxy, C.sub.5-C.sub.20 aryl, C.sub.7-C.sub.20 aralkyl, C.sub.5-C.sub.24 aryloxy, C.sub.2-C.sub.12 alkenyl, C.sub.6-C.sub.20 heteroaryl, or C.sub.5-C.sub.24 heteroaryloxy, which are optionally substituted by at least one C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 perfluoroalkyl, or R.sup.1 and R.sup.2 are independently alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus, optionally additionally substituted with C.sub.1-C.sub.12 alkyl group, wherein the heteroatom present in the heterocyclic ring may be substituted by one or two C.sub.1-C.sub.12 alkyl groups which form a primary, secondary or tertiary amine, or a quaternary ammonium group, a tertiary sulfonium group or a quaternary phosphonium group, or R.sup.1 and R.sup.2, taken together, form a substituted or unsubstituted cyclic C.sub.4-C.sub.10, polycyclic C.sub.4-C.sub.12, aromatic C.sub.4-C.sub.10, heteroaromatic C.sub.4-C.sub.10, polyaromatic C.sub.4-C.sub.10, and polyheteroaromatic C.sub.4-C.sub.10 system, which can be substituted by one and/or more substituents selected from hydrogen, halogen, C.sub.1-C.sub.25 alkyl group, C.sub.1-C.sub.12 perfluoroalkyl group, C.sub.1-C.sub.12 alkoxy group, C.sub.5-C.sub.24 aryloxy group, C.sub.5-C.sub.20 heteroaryloxy group, C.sub.2-C.sub.25 alkenyl group, alkoxy group (OR), sulfide group (SR), sulfoxide group (S(O)R), sulfonium group (S.sup.+R.sub.2), sulfonyl group (SO.sub.2R), sulfonamide group (SO.sub.2NR.sub.2), amine group (NR.sub.2), ammonium group (N.sup.+R.sub.3), nitro group (NO.sub.2), cyano group (CN), phosphonate group (P(O)(OR).sub.2), phosphinate group (P(O)R(OR)), phosphonite group (P(OR).sub.2), phosphine group (PR.sub.2), phosphine oxide group (P(O)R.sub.2), phosphonium group (P.sup.+R.sub.3), carboxyl group (COOH), ester group (COOR), amide group (CONR.sub.2), amide group (NRC(O)R), formyl group (CHO), ketone group (COR), thioamide group (CSNR.sub.2), thioketone group (CSR), thionoester group (CSOR), thioester group (COSR), dithioester group (CS.sub.2R), in which the R group is C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 perfluoroalkyl, C.sub.6-C.sub.24 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.5-C.sub.24 perfluoroaryl, alternatively, the two R groups, taken together, form C.sub.5-C.sub.25 ring, which alternatively may contain at least one heteroatom selected from oxygen, sulfur, selenium, nitrogen, phosphorus.

12. Use of a compound of formula 1-Ru according to any of the claims 1 to 6 as a precatalyst and/or catalyst in olefin metathesis reactions, particularly in ring-closing metathesis (RCM), cross-metathesis (CM), homometathesis (cross-metathesis between two molecules of the same olefin), ethenolysis, isomerization, in diastereoselective ring rearrangement metathesis (DRRM) reaction, alkene-alkyne (ene-yne) metathesis or ROMP or ADMET polymerization reaction.

13. The use according to claim 12, wherein the olefin metathesis reactions are carried out with the catalyst and/or precatalyst 1-Ru defined in any of the claims 1 to 6 in the presence of a compound having a structure represented by a formula selected from such as 3-Zn1, 3-Zn2, 3-Zn3, 3-Zn4, 3-Zn5, 3-Zn6, 3-Zn7, 3-Zn8, 3-Zn9, 3-Zn10, 3-Zn11, 3-Zn12, 3-Zn13, 3-K1 in an amount ranging from 0.0001 mol % to 200 mol %.

14. The use according to claim 12 or 13, wherein the reaction is carried out in an organic solvent such as toluene, benzene, mesylene, hexane, dichloromethane, dichloroethane, chlorobenzene, perfluorobenzene, perfluorotoluene, ethyl acetate, methyl acetate, methyl carbonate, ethyl carbonate, methyl tert-butyl ether, cyclopentyl methyl ether, diethyl ether, THF, 2-ME-THF, 4-ME-THP, dioxane, DME, PAO, PEG, paraffin, esters of saturated fatty acids.

15. The use according to any of the claims 12 to 14, wherein the reaction is carried out in a solvent-free system.

16. The use according to any of the preceding claims, wherein the reaction is carried out at a temperature of 20 to 200 C.

17. The use according to any of the preceding claims, wherein the reaction is carried out over a period of 5 minutes to 48 hours.

18. The use according to any of the preceding claims, wherein the 1-Ru compound is used in an amount of not more than 10 mol %.

19. The use according to any of the preceding claims, wherein the 1-Ru compound is used in an amount of not more than 0.1 mol %.

20. The use according to any of the preceding claims, wherein the 1-Ru compound is added to the reaction mixture portionwise in a solid form and/or continuously, using a pump, as a solution in an organic solvent.

21. The use according to any of the preceding claims, wherein the gaseous by-product of the reaction, selected from ethylene, propylene, butylene, is actively removed from the reaction mixture using an inert gas barbotage or by vacuum.

Description

[0143] FIG. 1 shows the structure of stereoretentive ruthenium complex 1-Ru1a according to the invention, obtained from X-ray structural analysis, presented in two spatial projections.

[0144] FIG. 2 shows the structure of stereoretentive ruthenium complex 1-Ru1ar according to the invention, obtained from X-ray structural analysis, presented in two spatial projections.

[0145] In this description the terms used have the following meanings. Undefined terms herein have meanings which are given and understood by a person skilled in the art in light of the best knowledge possessed, the present disclosure and the context of the patent application specification. Unless stated otherwise, the following conventions of chemical terms are used in this description and have the meanings indicated as in the definitions below:

[0146] As used herein, the term halogen means an element selected from F, Cl, Br, I.

[0147] The term carbene means an electrically neutral molecule in which the carbon atom has two non-bonding electrons in the singlet or triplet state and is linked by a single covalent bond to two groups or linked by a double covalent bond to one group. The term carbene also includes carbene analogues in which the carbene carbon atom is replaced by another chemical element such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulfur, selenium or tellurium.

[0148] The term alkyl means a saturated, linear, or branched hydrocarbon substituent with the indicated number of carbon atoms. Examples of an alkyl substituent are -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, -n-hexyl, -n-heptyl, -n-octyl, -n-nonyl, and -n-decyl. Representative branched (C.sub.1-C.sub.10) alkyls include-isopropyl, -sec-butyl, -isobutyl, -tert-butyl, -isopentyl, -neopentyl, -1-methylbutyl, -2-methylbutyl, -3-methylbutyl, -1,1-dimethylpropyl, -1,2-dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -3-methylpentyl, -4-methylpentyl, -1-ethylbutyl, -2-ethylbutyl, -1,1-dimethylbutyl, -1,2-dimetylbutyl, -1,3-dimethylbutyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3,3-dimethylbutyl, -1-methylhexyl, -2-methylhexyl, -3-methylhexyl, -4-methylhexyl, -1,2-dimethylpentyl, -1,3-dimethylpentyl, -5-methylhexyl, -1,2-dimethylhexyl, -1,3-dimethylhexyl, -3,3-dimethylhexyl, -1,2-dimethylheptyl, -1,3-dimethylheptyl, -3,3-dimethylheptyl, and the like.

[0149] The term alkoxy means an alkyl substituent as defined above attached via an oxygen.

[0150] The term perfluoroalkyl means an alkyl group as defined above in which all hydrogens have been replaced by identical or different halogens.

[0151] The term cycloalkyl means a saturated mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms. Examples of a cycloalkyl substituent are -cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, -cyclooctyl, -cyclononyl, -cyclodecyl, and the like.

[0152] The term alkenyl means an unsaturated, linear, or branched non-cyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one carbon-carbon double bond. Examples of an alkenyl substituent are -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1-butenyl, -2-methyl-2-butenyl, -2,3-dimethyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-nonenyl, -1-decenyl, -2-decenyl, -3-decenyl, and the like.

[0153] The term cycloalkenyl means an unsaturated cyclic or branched cyclic hydrocarbon substituent with the indicated number of carbon atoms and containing at least one carbon-carbon double bond. Examples of cycloalkenyl substituent are -cyclopropene, -cyclobutene, -cyclopentene, -cyclohexene, -cycloheptene, -cyclooctene, cyclononene, -cyclodecene, -methylcyclopropene, -ethylcyclobutene, -isopropylcyclopentene, -methylcyclohexene, and the like.

[0154] The term aryl means an aromatic mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms. Examples of an aryl substituent are -phenyl, -tolyl, -xylyl, -naphthyl, -2,4,6-trimethylphenyl, -2-fluorophenyl, -4-fluorophenyl, -2,4,6-trifluorophenyl, -2,6-difluorophenyl, -4-nitrophenyl, and the like.

[0155] The term aralkyl means an alkyl substituent as defined above substituted with at least one aryl as defined above. Examples of an aralkyl substituent are -benzyl, -diphenylmethyl, -triphenylmethyl, and the like.

[0156] The term heteroaryl means an aromatic mono- or polycyclic hydrocarbon substituent with the indicated number of carbon atoms, in which at least one carbon atom has been replaced by a heteroatom selected from the O, N and S. Examples of a heteroaryl substituent are -furyl, -tienyl, -imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, -oxadiazolyl, -thiadiazolyl, -tetrazolyl, -pyridyl, -pyrimidyl, -triazinyl, -indolyl, -benzo[b]furyl, -benzo[b]thienyl, -indazolyl, -benzoimidazolyl, -azaindolyl, -quinolyl, -isoquinolyl, -carbazolyl, and the like.

[0157] The term heterocycle means a saturated, unsaturated or partially unsaturated, mono- or polycyclic hydrocarbon substituent, with the indicated number of carbon atoms, in which at least one carbon atom has been replaced by a heteroatom selected from O, N and S. Examples of a heterocyclic substituent are -furyl, -thiophenyl, -pirolyl, -oxazolyl, -imidazolyl, -thiazolyl, -isoxazolyl, -pirazolyl, -isothiazolyl, -triazinyl, -pirolidinonyl, -pirolidinyl, -hydantoinyl, -oxiranyl, -oxetanyl, -tetrahydrofuranyl, -tetrahydrothiophenyl, -quinolinyl, -isoquinolinyl, -chromonyl, -coumarinyl, -indolyl, -indolizinyl, -benzo[b]furanyl, -benzo[b]thiophenyl, -indazolyl, -purinyl, -4H-quinolysinyl, -isoquinolyl, -quinolyl, -phthalazinyl, -naphthyridinyl, -carbazolyl, --carbolinyl, and the like.

[0158] The term neutral ligand means an uncharged substituent capable of coordinating with a metallic center (transition metal atom). Examples of such ligands may be: N-heterocyclic carbenes (NHCs), cyclic alkylaminocarbenes (CAACs), amines, phosphines and their oxides, alkyl and aryl phosphites and phosphates, arsines and their oxides, ethers, alkyl and aryl sulfides, coordinated unsaturated or aromatic hydrocarbons, alkyl and aryl halides, nitriles, isonitriles, sulfides, sulfoxides, sulfones, thioketones, thioamides, thioesters, thionoesters and dithioesters.

[0159] The term anionic ligand means a substituent capable of coordinating with a metallic center (transition metal atom) and having a charge which is capable of partial or full metallic center charge compensation. Examples of such ligands may be fluoride anions, chloride anions, bromide anions, iodide anions, cyanide anions, cyanate anions and thiocyanate anions, anions of carboxylic acids, anions of alcohols, anions of phenols, anions of thiols and thiophenols, anions of hydrocarbons with delocalized charge (such as cyclopentadiene anion), anions of (organo) sulfuric and (organo)phosphoric acids and esters thereof (such as for example anions of alkyl and aryl sulfonic acids, anions of alkyl and aryl phosphoric acids, anions of alkyl and aryl esters of sulfuric acid, anions of alkyl and aryl esters of phosphoric acids, anions of alkyl and aryl esters of alkyl and aryl phosphoric acids). Alternatively, an anionic ligand may have L.sup.1, L.sup.2 and L.sup.3 groups, linked as the catechol anion, acetylacetone anion, salicylaldehyde anion. Anionic ligands (X.sup.1, X.sup.2) and neutral ligands (L.sup.1, L.sup.2, L.sup.3) can be linked together to form multidentate ligands, for example, a bidentate ligand (X.sup.1-X.sup.2), a tridentate ligand (X.sup.1-X.sup.2-L.sup.1), tetradentate ligand (X.sup.1-X.sup.2-L.sup.1-L.sup.2), bidentate ligand (X.sup.1-L.sup.1), tridentate ligand (X.sup.1-L.sup.1-L.sup.2), tetradentate ligand (X.sup.1-L.sup.1-L.sup.2-L.sup.3), bidentate ligand (L.sup.1-L.sup.2), tridentate ligand (L.sup.1-L.sup.2-L.sup.3). Examples of such ligands are catechol anion, dithiocatechol anion, acetylacetone anion, and salicylaldehyde anion.

[0160] The term heteroatom means an atom selected from a group comprising oxygen, sulfur, nitrogen, phosphorus, boron, silicon, arsenic, selenium, tellurium.

[0161] The term PAO means polyolefins, an abbreviation for Poly-Alpha-Olefins, in the case of the present invention it is an abbreviation used for low molecular weight polyolefins used as high boiling point solvents. It denotes also a class of solvents and/or lubricants that are the product of the polymerization of ethylene derivatives, leading to the formation of branched, saturated hydrocarbons, used here as heat-resistant, non-polar, high boiling point solvents.

EMBODIMENTS OF THE INVENTION

[0162] The following examples are included only to illustrate the invention and to clarify particular aspects of the invention, not to limit it, and should not be considered the entire scope of the invention as defined in the appended claims. In the following examples, unless stated otherwise, standard materials and methods used in the art were applied or manufacturers' recommendations for specific reactants and methods were followed.

[0163] When necessary, model compounds for the metathesis reaction were purified by fractional distillation and then stored in an inert gas atmosphere over activated inert aluminum oxide. Tetrahydrofuran was purified by distillation over sodium-potassium alloy in the presence of benzophenone and then stored over 4 molecular sieves. When appropriate, the selected reactions were carried out under an argon atmosphere using reaction vessels heated at 130 C.

[0164] Starting compounds for the synthesis of zinc complexes were commercially available.

[0165] The composition of the reaction mixtures of the metathesis reactions was studied by gas chromatography, using a PerkinElmer Clarus 680 GC equipped with a GL Sciences InertCap 5 MS/NP capillary column.

[0166] Individual components of the reaction mixtures were identified by comparing retention times with commercial standards or isolated from reaction mixtures for which the structure was confirmed by NMR.

Example I

Synthesis of New Dithiolate Ligands and Corresponding Metal Salts

[0167] The following Scheme 1 illustrates the synthesis of dithiolate ligand precursors and compounds (general formula VI and general formula VII) allowing the preparation of stereoretentive ruthenium catalysts (general formula 1-Ru1a to 1-Ru1ar and 1-Ru2a to 1-Ru2c, Scheme 10), which are the subject matter of the present invention.

##STR00037##

[0168] The reactions R1 to R4 shown in Scheme 1 were carried out using commercially available substrates based on procedures described in the literature with modifications developed by the authors. Unless stated otherwise, in the reactions described commercially available solvents were used and no attention was paid to the presence of oxygen and/or moisture.

[0169] The subsequent transformations described in Scheme 1 are shown below.

a. Reaction R1

[0170] In step R1 (Scheme 1), the synthesis of diamide of general formula II is carried out. For this purpose, diamine of general formula I and a dicarbonyl compound, preferably oxalic acid, dimethyl oxalate or oxalyl chloride, are used. The transformation is carried out in water or an organic solvent, using a catalytic amount of an organic or inorganic acid or using a stoichiometric amount of a base, preferably a non-nucleophilic base. The reaction mixture is heated under a reflux condenser or in a microwave reactor. The product is isolated by filtration from the reaction mixture. [(i) J. Lin, P. Wang, Z. Zhang, G. Xue, D. Zha, J. Wang, X. Xu, Z. Li, Synth. Commun. 2020, 50, 823-830; (ii) O. O. Ajani, C. A. Obafemi, C. O. Ikpo, K. O. Ogunniran, O. C. Nwinyi, Chem. Heterocycl. Compd. 2009, 45, 1370-1378].

Example of Reaction R1

##STR00038##

[0171] O-phenylenediamine (2.0 g, 18.4 mmol), oxalic acid dihydrate (1.66 g, 18.4 mmol), 15 ml of water and a catalytic amount of para-toluenesulfonic acid (pTsOH) were introduced into a reaction vessel equipped with a stirring element. The vessel was placed in a microwave reactor (MW), and the content of the vessel was heated for 10 min while maintaining a constant temperature of 100 C. After cooling the mixture to room temperature, the resulting red crystals of the product were filtered off, washed successively with a small amount of ethanol and diethyl ether, and then dried in air to obtain the expected product in 80% yield (2.4 g, 14.8 mmol).

[0172] .sup.1H NMR (400 MHZ, DMSO-d.sub.6) =11.90 (brs, 2H), 7.07 (ddt, J=18.1, 5.6, 3.5 Hz, 4H).

[0173] .sup.13C NMR (101 MHZ, DMSO-d.sub.6) =155.6, 126.0, 123.4, 115.6.

b. Reaction R2

[0174] In step R2 (Scheme 1), the resulting diamide of general formula II is converted to a 2,3-dichloroquinoxaline derivative of general formula III with dehydrating chlorinating agent, preferably phosphoryl chloride or thionyl chloride. The reaction is carried out in organic solvent or without solvent; preferably in the presence of dimethylformamide. The reaction mixture is heated under a reflux condenser or in a microwave reactor. The product is isolated by precipitation, followed by filtration of the resulting precipitate, or by extraction with an organic solvent [R. Beldi, K. F. Atta, S. Aboul-Ela, E. S. H. El Ashry, J. Heterocycl. Chem. 2011, 48, 50-56].

Example of Reaction R2

##STR00039##

[0175] The corresponding reaction product R1 (2.4 g, 14.8 mmol), POCl.sub.3 (5.5 mL, 59.2 mmol) and 15 mL of dry dimethylformamide were introduced into a reaction vessel equipped with a stirring element. The reaction mixture was heated in a microwave reactor for 20 min while maintaining a constant temperature of 50 C. After cooling the post-reaction mixture to the room temperature, the contents of the vessel were carefully poured onto ice. Thus obtained colorless precipitate was filtered off and washed successively with ethanol and diethyl ether. As a result, the expected product was obtained as a colorless solid in 71% yield (2.1 g, 10.6 mmol).

[0176] .sup.1H NMR (400 MHZ, CDCl.sub.3) =8.03 (dd, J=6.4, 3.4 Hz, 2H), 7.81 (dd, J=6.4, 3.4 Hz, 2H).

[0177] .sup.13C NMR (101 MHZ, CDCl.sub.3) =145.4, 140.6, 131.3, 128.2.

c. Functionalization of Substituents Forming Carboxylic or Sulfonic Acid Chlorides

[0178] When one of the substituents from R.sup.a to R.sup.d (Scheme 1.) contains functional groups that react with thionyl chloride or phosphoryl chloride (e.g. carboxylic acids, sulfonic acids), one obtains the compounds of the general formula:

##STR00040##

[0179] These compounds were used in an additional reaction with a nucleophile in the presence or absence of a base, and can form esters: acyl or sulfonic, or amides: acyl or sulfonic according to Scheme 4.

##STR00041##

Example of Reaction

##STR00042##

[0180] Dimethylamine hydrochloride (206 mg, 2.52 mmol), 2,3-dichloroquinoxalin-6-sulfonyl chloride (750 mg, 2.52 mmol) and 25 mL of dichloromethane were introduced into the reaction vessel. The vessel was placed in an acetone/dry ice cooling bath, after which triethylamine (0.7 mL, 5.04 mmol) was added dropwise into the reaction mixture. The vessel was then left to warm slowly overnight using the temperature inertia of the cooling bath. The next day, the reaction mixture was transferred to a separatory funnel and washed with water. The aqueous phase was extracted with two portions of dichloromethane. The combined organic phases were dried with anhydrous sodium sulfate, concentrated to about 10% of the initial volume, and then the product was precipitated by adding n-hexane. The resulting precipitate was filtered off under reduced pressure and dried to provide the product as a yellow solid in 65% yield (0.5 g, 1.63 mmol).

[0181] .sup.1H NMR (400 MHz, Chloroform-d) 8.49 (dd, J=2.0, 0.6 Hz, 1H), 8.22-8.17 (m, 1H), 8.14-8.10 (m, 1H), 2.81 (s, 6H).

d. Reaction R3

[0182] In step R3 (Scheme 1), the derivative of general formula III obtained in the previous steps is reacted with an alcoholic thiourea solution. The reaction is carried out at an elevated temperature, preferably 40 to 80 C. Depending on the water content in the solvent, and the substrate used in the reaction, a mixture of products of general formula IVa and IVb of different proportions can be obtained, which can be used in further reactions without much effect on their yields. In the example shown, the dominant compound was the one with the general formula IVa. [(iii) R. Beldi, K. F. Atta, S. Aboul-Ela, E. S. H. El Ashry, J. Heterocycl. Chem. 2011, 48, 50-56; (iv) Ya. Z. Voloshin, A. S. Belov, A. Yu. Lebedev, O. A. Varzatskii, M. Yu. Antipin, Z. A. Starikova, T. E. Kron, Russ. Chem. Bull. 2004, 53, 1218-1222]. The reaction product is isolated and purified by filtration.

Example of Reaction R3

##STR00043##

[0183] 2,3-dichloroquinoxaline (10.3 g, 52 mmol) and thiourea (8.7 g, 115 mmol) were introduced into a reaction vessel equipped with a stirring element. The contents of the vessel were suspended in 120 mL of ethanol and then heated under a reflux condenser for 6 h. After completion of the reaction, the resulting suspension was cooled to room temperature, then filtered off and washed with a small amount of ethanol and diethyl ether. After drying, the product was obtained as a yellow solid in 61% yield (11.0 g, 31.72 mmol).

[0184] .sup.1H NMR (400 MHZ, DMSO-d.sub.6) 15.14 (brs, 1H), 9.97 (brs, 2H), 9.83 (brs, 2H), 7.88 (dt, J=8.0, 1.0 Hz, 1H). 7.70-7.63 (m, 2H), 7.51 (ddd, J=8.4, 5.6, 2.9 Hz, 1H).

[0185] .sup.13C NMR (101 MHZ, DMSO-d.sub.6) 171.0, 164.9, 160.3, 135.1, 131.6, 131.5, 128.2, 127.0, 117.0.

e. Reaction R4

[0186] In step R4 (Scheme 1), a derivative of general formula III is treated with sodium bisulfide, in water or an organic solvent, preferably ethanol, at an elevated temperature or in a microwave reactor [(v) S. Henfling, R. Kempt, J. Klose, A. Kuc, B. Kersting, H. Krautscheid, Inorg. Chem. 2020, 59, 16441-16453]. The product after the reaction is isolated by filtration.

[0187] Alternatively, the derivative of general formula III is treated with thiourea, in water or an organic solvent, preferably ethanol, at elevated temperature or in a microwave reactor, and then hydrolysis of the resulting mixture under aqueous conditions is carried out using first a solution of an alkali, preferably sodium hydroxide, and then a solution of an organic or inorganic acid, preferably acetic acid.

Example of Reaction R4

##STR00044##

[0188] 1,2-dichloropyrazine (2.0 g, 13.2 mmol), hydrated sodium bisulfide (2.95 g, 52.6 mmol) and 15 mL of water were introduced into a reaction vessel equipped with a stirring element. The vessel was placed in a microwave reactor, and the contents were heated by maintaining temperature of 95 C. for 25 min. After cooling the reaction mixture to the room temperature, the precipitate formed was filtered off, washed with a small amount of water, ethanol and diethyl ether and then allowed to dry to give the expected product in the form of purple crystals in 84% yield (1.6 g, 11.1 mmol).

[0189] .sup.1H NMR (400 MHZ, DMSO-d.sub.6) =13.72 (s, 2H), 6.87 (s, 2H).

[0190] .sup.13C NMR (101 MHZ, DMSO-d.sub.6) =180.5, 118.0.

Alternative Example of Reaction R4

##STR00045##

[0191] 1,2-dichloroquinoxaline (2.1 g, 10.6 mmol), thiourea (2.1 g, 27.4 mmol) and 15 mL of water were introduced into a reaction vessel equipped with a stirring element. The vessel was placed in a microwave reactor, and the content of the vessel was heated by maintaining a temperature of 100 C. for 10 min. After cooling the reaction mixture to the room temperature, NaOH solution (4.22 g in 30 ml of water) was added. The content of the flask was then stirred for another 10 min, after which 9.1 mL of glacial acetic acid was added. The precipitate was filtered off, washed with water, ethanol and diethyl ether, and then allowed to dry. As a result, the expected product was obtained as a brown solid in 73% yield (1.5 g, 7.72 mmol).

[0192] .sup.1H NMR (400 MHZ, DMSO-d.sub.6) =14.25 (s, 2H), 7.45-7.35 (m, 2H), 7.32-7.21 (m, 2H).

[0193] .sup.13C NMR (101 MHZ, DMSO-d.sub.6) =179.7, 128.3, 126.0, 116.0.

f. Reactions R5 and R6

[0194] Compounds of general formula IVa, IVb and V can be directly converted to compound of general formula VI using similar reaction conditions. Each of these compounds (IVa, IVb and V) is treated with a metal complex, preferably zinc acetate or zinc chloride, in the presence of ethylenediamine, in water or an organic solvent. The reaction product is separated by filtration.

Example of Reaction R5

##STR00046##

[0195] Isothiourethane salt (5.6 g, 15.9 mmol), zinc acetate dihydrate (7.0 g, 31.9 mmol), ethylenediamine (6.5 mL, 95.7 mmol) and 100 ml of water were introduced into a reaction vessel equipped with a stirring element. The reaction was carried out for 2 hours at room temperature, and then the yellow precipitate formed was filtered off, washed with water, ethanol and diethyl ether, and allowed to dry. The expected product was obtained in 66% yield (4.5 g, 14.2 mmol).

[0196] By reaction R.sup.5 using zinc (II) acetate, or iron (II) chloride, or copper (II) chloride, respectively, the following compounds with the general formula

##STR00047##

were generated.

Example of Reaction R6

##STR00048##

[0197] Zinc acetate dihydrate (1.19 g, 5.4 mmol), ethylenediamine (1.46 mL, 21.6 mmol), 1.2 dithioquinoxaline (0.7 g, 3.6 mmol) and 10 mL of isopropanol were introduced into a reaction vessel equipped with a stirring element. The reaction was carried out for 24 hours at room temperature, and then the yellow precipitate formed was filtered off, washed with water, ethanol and diethyl ether and allowed to dry to obtain the expected product 3-Zn1 in 75% yield (0.7 g. 2.72 mmol).

[0198] By Reaction R6, the following list of compounds of general formula VI was obtained.

##STR00049## ##STR00050##

[0199] Zinc complexes 3-Zn1 to 3-Zn13 were characterized using ATR IR. The most characteristic absorption bands are shown below:

##STR00051## [0200] Code name: 3-Zn1 [0201] Molecular formula: C.sub.10H.sub.12N.sub.4S.sub.2Zn [0202] Molar mass: 315.98 g/mol [0203] IR (ATR IR): =3331.91, 3250.43, 3063.37, 2949.59, 2882.09, 1698.01, 1590.99, 1374.51, 1268.93, 1158.53, 1128.15, 1099.23, 1019.19, 999.43, 742.94 cm.sup.1

##STR00052## [0204] Code name: 3-Zn2 [0205] Molecular formula: C.sub.14H.sub.14N.sub.4S.sub.2Zn [0206] Molar mass: 366.00 g/mol [0207] IR (ATR IR): =3048.91, 1659.93, 1650.29, 1632.45, 1591.47, 1394.76, 1320.04, 1293.52, 1177.81, 1150.81, 1098.74, 1023.05, 863.95, 735.23 cm.sup.1

##STR00053## [0208] Code name: 3-Zn3 [0209] Molecular formula: C.sub.6H.sub.10N.sub.4S.sub.2Zn [0210] Molar mass: 265.96 g/mol [0211] IR (ATR IR): =3302.98, 3260.56, 3210.41, 3057.10, 2954.89, 2938.50, 2880.17, 1608.34, 1410.19, 1318.11, 1122.85, 1063.55, 1048.60, 1029.80 cm.sup.1

##STR00054## [0212] Code name: 3-Zn4 [0213] Molecular formula: C.sub.12H.sub.16N.sub.4S.sub.2Zn [0214] Molar mass: 344.01 g/mol [0215] IR (ATR IR): =3344.93, 3327.09, 3295.75, 3248.98, 2975.14, 2942.84, 2915.36, 2885.47, 1243.86, 1198.54, 1127.67, 1108.39, 998.46 cm.sup.1

##STR00055## [0216] Code name: 3-Zn5 [0217] Molecular formula: C.sub.10H.sub.11ClN.sub.4S.sub.2Zn [0218] Molar mass: 349.94 g/mol [0219] IR (ATR IR): =3297.68, 3225.36, 3130.87, 2936.09, 2883.54, 1588.09, 1574.59, 1369.21, 1270.38, 1134.42, 1105.98, 1024.98, 1008.59 cm.sup.1

##STR00056## [0220] Code name: 3-Zn6 [0221] Molecular formula: C.sub.10H.sub.10Cl.sub.2N.sub.4S.sub.2Zn [0222] Molar mass: 383.90 g/mol [0223] IR (ATR IR): =3326.12, 3139.54, 2947.18, 2884.99, 1698.50, 1585.68, 1432.37, 1378.85, 1261.22, 1116.58, 1022.57 cm.sup.1

##STR00057## [0224] Code name: 3-Zn7 [0225] Molecular formula: C.sub.10H.sub.11BrN.sub.4S.sub.2Zn [0226] Molar mass: 393.89 g/mol [0227] IR (ATR IR): =3057.58, 2963.57, 2883.06, 2734.08, 1657.52, 1544.22, 1401.51, 1360.53, 1256.88, 1154.19, 1110.80, 1015.34 cm.sup.1

##STR00058## [0228] Code name: 3-Zn8 [0229] Molecular formula: C.sub.10H.sub.11FN.sub.4S.sub.2Zn [0230] Molar mass: 333.97 g/mol [0231] IR (ATR IR): =3317.44, 3203.67, 3113.03, 3034.44, 2946.22, 2886.43, 1613.64, 1567.36, 1489.26, 1169.13, 1103.08, 1033.18, 1016.78 cm.sup.1

##STR00059## [0232] Code name: 3-Zn9 [0233] Molecular formula: C.sub.11H.sub.11F.sub.3N.sub.4S.sub.2Zn [0234] Molar mass: 383.97 g/mol [0235] IR (ATR IR): =3226.32, 2953.93, 2885.95, 2647.30, 1378.37, 1340.28, 1306.54, 1277.61, 1108.87, 1169.62, 1060.17, 1023.05 cm.sup.1

##STR00060## [0236] Code name: 3-Zn10 [0237] Molecular formula: C.sub.10H.sub.11N.sub.5O.sub.2S.sub.2Zn [0238] Molar mass: 360.96 g/mol [0239] IR (ATR IR): =3337.69, 3286.11, 3261.52, 3145.33, 2920.18, 2874.86, 1602.07, 1556.75, 1506.13, 1399.10, 1382.71, 1335.95, 1319.07, 1269.90, 1144.06, 1110.31, 1068.37, 1004.25, 988.82 cm.sup.1

##STR00061## [0240] Code name: 3-Zn11 [0241] Molecular formula: C.sub.12H.sub.14N.sub.4O.sub.2S.sub.2Zn [0242] Molar mass: 373.98 g/mol [0243] IR (ATR IR): =3261.04, 2946.70, 2884.50, 1698.98, 1607.86, 1378.85, 1294.48, 1266.04, 1229.40, 1137.31, 1107.90, 1013.89, 1433.82 cm.sup.1

##STR00062## [0244] Code name: 3-Zn12 [0245] Molecular formula: C.sub.12H.sub.17N.sub.5O.sub.2S.sub.3Zn [0246] Molar mass: 422.98 g/mol [0247] IR (ATR IR): =3329.98, 3254.29, 3166.54, 2939.95, 2882.58, 1590.99, 1458.40, 1374.03, 1315.70, 1243.86, 1138.76, 1106.94, 1065.96, 1003.28, 948.81, 728.00 cm.sup.1

##STR00063## [0248] Code name: 3-Zn13 [0249] Molecular formula: C.sub.14H.sub.19N.sub.5O.sub.3S.sub.3Zn [0250] Molar mass: 464.99 g/mol [0251] IR (ATR IR): =3544.52, 3319.37, 3249.47, 3139.06, 2945.73, 2888.84, 2865.70, 1704.28, 1698.50, 1581.34, 1456.47, 1378.85, 1260.74, 1141.65, 1110.31, 1017.27, 943.02, 738.12 cm.sup.1

f. Example of Reaction R7

[0252] In step R7 (Scheme 1), a derivative of general formula V is treated with one or more salts, or an organometallic compound, or a metal hydride, preferably lithium, sodium, potassium, magnesium, calcium or copper, respectively, in an organic solvent, preferably THF, at room temperature. The product VII does not have to be isolated, but can be used directly in the synthesis of suitable catalysts (Example IV). By reaction R7, the following compounds with the general formula VII were generated.

##STR00064## ##STR00065##

Example II

General Method for the Synthesis of Stereoretentive Ruthenium Complexes 1-Ru1a to 1-Ru1ar and 1-Ru2a to 1-Ru2c

[0253] The synthesis of stereoretentive ruthenium complexes, which are the subject matter of the present invention, consists in mixing together a metal complex of general structure VI or a reaction R7 product of general formula VII, which is formed in situ by reacting a compound of general formula V with a source of the previously mentioned metal cations and optionally neutral ligands, and an alkylidene ruthenium complex of general structure 4, 4a-Ru or 4b-Ru, according to Scheme 10. The reaction is carried out at room or elevated temperature, in organic solvents, preferably in tetrahydrofuran, while maintaining anhydrous and anaerobic conditions. The product is isolated by filtration of the reaction mixture, followed by evaporation of the resulting filtrate to obtain the expected products 1-Ru1a to 1-Ru1ar or 1-Ru2a to 1-Ru2c according to Scheme 10.

##STR00066##

Example III

Preparation of Stereoretentive Ruthenium Complexes Using 3-Zn1 Ligand

[0254] The transformations described below were performed, when necessary, using a glovebox and/or vacuum-argon line under an inert gas atmosphere, with deoxygenated and anhydrous reactants and solvents.

##STR00067##

[0255] Hoveyda-Grubbs II generation-type complex (50.0 mg, 0.07 mmol), a quinoxalino-2,3-dithiolate zinc 3-Zn1 complex (33.5 mg, 0.14 mmol), and 5 mL of tetrahydrofuran were introduced into a 10 mL vial equipped with a stirring element. The content of the vial was stirred at room temperature for 8 hours and the solvent was evaporated. The residue was suspended in dichloromethane and filtered, preferably through a syringe filter or a Celite pad. After evaporation of the solvent the product 1-Ru1a was obtained as a solid in 95% yield (0.067 mmol, 55.8 mg).

Example IV

Preparation of Stereoretentive Ruthenium Complexes Using 3-K1 Ligand (Obtained from Reaction R7, Scheme 1)

[0256] The transformations described below were performed when necessary using a glovebox and/or vacuum-argon line under an inert gas atmosphere, with deoxygenated and anhydrous reactants and solvents.

##STR00068##

[0257] Quinoxalino-2,3-dition (18.6 mg, 0.096 mmol), KHMDS (38.2 mg, 0.196 mmol) and 5 mL of THF were introduced into a 10 mL vial equipped with a stirring element. The content of the vial was stirred for 2 hours, then the Hoveyda-Grubbs II generation complex (Hov-II, 30.0 mg, 0.048 mmol) was added, and the mixture was stirred for another 22 hours, after which the solvent was evaporated. The residue was suspended in dichloromethane and filtered, preferably through a syringe filter or a Celite pad. The filtrate was concentrated to about 2 mL and then 15 mL of hexane was slowly added. The crystals formed were collected and washed with a small amount of hexane. After removal of residual solvent, the solid 1-Ru1b product was obtained in 70% yield (0.033 mmol, 25.0 mg).

[0258] Using the method presented in examples III and IV, a series of complexes 1-Ru1a to 1-Ru1ar or 1-Ru2a to 1-Ru2c were obtained, the structures of which are shown below.

##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076##

[0259] All of the above complexes were characterized using nuclear magnetic resonance spectroscopy. Table 1 summarizes the benzylidene proton shifts of each complex in the .sup.1H NMR spectrum in a given solvent.

TABLE-US-00001 TABLE 1 Summary of the obtained ruthenium complex structures according to the general procedure of example III and IV and the shift of their benzylidene proton in the .sup.1H NMR spectrum. .sup.1H NMR Compound Molar mass Ru = CH Item No. Structure Molecular formula [g/mol] (solvent) 1. 1-Ru1a [00077] C.sub.45H.sub.54N.sub.4ORuS.sub.2 832.14 15.02 ppm (CD.sub.2Cl.sub.2) 2. 1-Ru1b [00078] C.sub.39H.sub.42N.sub.4ORuS.sub.2 748.19 14.78 ppm (CD.sub.2Cl.sub.2) 3. 1-Ru1c [00079] C.sub.45H.sub.52N.sub.4ORuS.sub.2 830.27 15.15 ppm (CD.sub.2Cl.sub.2) 4. 1-Ru1d [00080] C.sub.41H.sub.44N.sub.4ORuS.sub.2 754.21 15.33 ppm (THF) 5. 1-Ru1e [00081] C.sub.38H.sub.42N.sub.4ORuS.sub.3 768.16 14.80 ppm (CD.sub.2Cl.sub.2) 6. 1-Ru1f [00082] C.sub.47H.sub.43F.sub.5N.sub.4O.sub.3RuS.sub.2 972.07 14.74 ppm (THF) 7. 1-Ru1g [00083] C.sub.40H.sub.44N.sub.4O.sub.2RuS.sub.2 778.20 15.03 ppm; 14.78 ppm (THF) 8. 1-Ru1h [00084] C.sub.47H.sub.48N.sub.4O.sub.3RuS.sub.2 882.23 14.82 ppm (THF) 9. 1-Ru1i [00085] C.sub.47H.sub.59ClN.sub.6ORuS.sub.2 924.67 14.73 ppm (THF) 10. 1-Ru1j [00086] C.sub.36H.sub.43N.sub.3ORuS.sub.2 699.20 14.45 ppm (THF) 11. 1-Ru1k [00087] C.sub.49H.sub.56N.sub.4ORuS.sub.2 882.30 14.97 ppm (CD.sub.2Cl.sub.2) 12. 1-Ru1l [00088] C.sub.41H.sub.52N.sub.4ORuS.sub.2 782.27 14.79 ppm (CD.sub.2Cl.sub.2) 13. 1-Ru1m [00089] C.sub.47H.sub.58N.sub.4ORuS.sub.2 860.32 14.94 ppm (CD.sub.2Cl.sub.2) 14. 1-Ru1n [00090] C.sub.45H.sub.53N.sub.4ClORuS.sub.2 866.25 14.97 ppm; 14.94 ppm (CD.sub.2Cl.sub.2) 15. 1-Ru1o [00091] C.sub.45H.sub.52N.sub.4Cl.sub.2ORuS.sub.2 900.24 14.98 ppm; 14.94 ppm (CD.sub.2Cl.sub.2) 16. 1-Ru1p [00092] C.sub.45H.sub.53N.sub.4BrORuS.sub.2 910.20 14.97 ppm (CD.sub.2Cl.sub.2) 17. 1-Ru1r [00093] C.sub.45H.sub.53FN.sub.4ORuS.sub.2 850.28 15.00 ppm 14.92 ppm (CD.sub.2Cl.sub.2) 18. 1-Ru1s [00094] C.sub.46H.sub.53F.sub.3N.sub.4ORuS.sub.2 900.27 14.98 ppm 14.94 ppm (CD.sub.2Cl.sub.2) 19. 1-Ru1t [00095] C.sub.45H.sub.53N.sub.5O.sub.3RuS.sub.2 877.27 15.00 ppm 14.89 ppm (CD.sub.2Cl.sub.2) 20. 1-Ru1u [00096] C.sub.47H.sub.56N.sub.4O.sub.3RuS.sub.2 890.29 15.00 ppm; 14.91 ppm (CD.sub.2Cl.sub.2) 21. 1-Ru1w [00097] C.sub.47H.sub.59N.sub.5O.sub.3RuS.sub.3 939.29 14.98 ppm 14.94 ppm (CD.sub.2Cl.sub.2) 22. 1-Ru1x [00098] C.sub.49H.sub.61N.sub.5O.sub.4RuS.sub.3 981.30 14.98 ppm 14.92 ppm (CD.sub.2Cl.sub.2) 23. 1-Ru1y [00099] C.sub.47H.sub.54F.sub.3N.sub.5O.sub.2RuS.sub.2 943.28 15.11 ppm (THF) 24. 1-Ru1z [00100] C.sub.45H.sub.53N.sub.5O.sub.3RuS.sub.2 877.27 15.14 ppm (THF) 25. 1-Ru1aa [00101] C.sub.44H.sub.51N.sub.5O.sub.3RuS.sub.2 863.26 14.95 ppm (THF) 26. 1-Ru1ab [00102] C.sub.41H.sub.47N.sub.5O.sub.3RuS.sub.3 855.20 14.88 ppm (THF) 27. 1-Ru1ac [00103] C.sub.46H.sub.46N.sub.4O.sub.2RuS.sub.2 852.22 14.94 ppm (THF) 28. 1-Ru1ad [00104] C.sub.43H.sub.51N.sub.5O.sub.2RuS.sub.2 835.26 14.74 ppm (THF) 29. 1-Ru1ae [00105] C.sub.43H.sub.51N.sub.5ORuS.sub.2 819.27 14.76 ppm (THF) 30. 1-Ru1af [00106] C.sub.39H.sub.41BrN.sub.4ORuS.sub.2 826.10 14.86 ppm (THF) 31. 1-Ru1ag [00107] C.sub.43H.sub.50N.sub.6O.sub.3RuS.sub.3 896.22 14.78 ppm (THF) 32. 1-Ru1ah [00108] C.sub.40H.sub.42N.sub.4O.sub.2RuS.sub.2 776.19 15.00 ppm (THF) 33. 1-Ru1ai [00109] C.sub.47H.sub.57N.sub.5O.sub.3RuS.sub.2 905.30 14.98 ppm (THF) 34. 1-Ru1aj [00110] C.sub.40H.sub.41N.sub.5O.sub.2RuS.sub.2 789.18 15.17 ppm 15.00 ppm (Dioxane) 35. 1-Ru1ak [00111] C.sub.39H.sub.40N.sub.4ORuS.sub.2 746.18 15.04 ppm (THF) 36. 1-Ru1al [00112] C.sub.40H.sub.42N.sub.4ORuS.sub.2 760.19 15.17 ppm (THF) 37. 1-Ru1am [00113] C.sub.41H.sub.44N.sub.4ORuS.sub.2 774.21 15.11 ppm (THF) 38. 1-Ru1an [00114] C.sub.39H.sub.42N.sub.4RuS.sub.2Se 812.11 15.36 ppm (THF) 39. 1-Ru1ao [00115] C.sub.36H.sub.35IN.sub.4RuS.sub.2 816.05 15.79 ppm (THF) 40. 1-Ru1ap [00116] C.sub.40H.sub.37IN.sub.4RuS.sub.2 866.06 16.34 ppm (THF) 41. 1-Ru1ar [00117] C.sub.39H.sub.43N.sub.5RuS.sub.2 747.21 16.14 ppm (CD.sub.2Cl.sub.2) 42. 1-Ru2a [00118] C.sub.51H.sub.76N.sub.2P.sub.2RuS.sub.2 944.40 18.43 ppm (THF) 43. 1-Ru2b [00119] C.sub.54H.sub.69N.sub.4PRuS.sub.2 970.38 19.02 ppm (THF) 44. 1-Ru2c [00120] C.sub.41H.sub.41N.sub.5RuS.sub.2 769.19 19.06 ppm (THF)

Example V

Application of New Stereoretentive Ruthenium Complexes

[0260] In the example applications of the new stereoretentive metathesis catalysts also the reference ruthenium catalysts 1-Ru0a, 1-Ru0b, 1-Ru0c and the reference molybdenum catalysts Mo1, Mo2, Mo3, shown below, were used for comparison. Reference values described in the literature are shown for some of the results. The % Z and % E values indicate the percentage of a given isomer relative to both present in the product. Unless stated otherwise, all manipulations were carried out under an inert gas atmosphere with anhydrous and deoxygenated solvents and reagents. Gas chromatograph analyses were performed using the internal standard method.

##STR00121## ##STR00122##

Example VI

Activity Study of the New Stereoretentive Ruthenium Complexes in the Cross-Metathesis Reaction of Methyl Oleate (OM)

[0261] A solution of methyl oleate (1.0 equiv.) in THF, a solution of tetradecane (0.1 equiv.) in THF and a solution of 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m, 1-Ruin, 1-Ru1x catalyst (0.001 equiv.) in THF were introduced into a vial equipped with a stirring element so that the concentration of methyl oleate in the mixture was 0.1 M. The reactions were carried out at room temperature (RT) for 18 hours. The conversion and composition of the mixture were determined by gas chromatography. The results of the model reaction are shown in Table 2, where OM is methyl oleate, 9-ODE is octadec-9-ene, 9-OKD in this example is dimethyl octadec-9-enodiate.

##STR00123##

TABLE-US-00002 TABLE 2 Comparison of model reaction results for selected ruthenium complexes Z/E ratio after reaction Catalyst Conversion [%] 9-ODE OM 9-OKD 1-Ru0a 50 >99/1 >99/1 >99/1 1-Ru1a 50 >99/1 >99/1 >99/1 1-Ru1c 50 98/2 >99/1 >99/1 1-Ru1m 50 >99/1 >99/1 >99/1 1-Ru1n 30 >99/1 >99/1 >99/1 1-Ru1x 50 >99/1 >99/1 >99/1

Example VII

Activity Study of the New Stereoretentive Ruthenium Complexes in the Cross-Metathesis Reaction of Methyl Oleate (OM) at Elevated Temperature

[0262] A solution of methyl oleate (1.0 equiv.) in THF, a solution of tetradecane (0.1 equiv.) in THF and a solution of 1-Ru1a, 1-Ru1c, 1-Ru1n, 1-Ru1x catalyst (0.0001 equiv.) in THF were introduced into a vial equipped with a stirring element so that the concentration of methyl oleate in the mixture was 0.1 M. The reactions were carried out at 60 C. for 18 hours. The conversion and composition of the mixture were determined by gas chromatography. The reaction results are shown in Table 3, where OM is methyl oleate, 9-ODE is octadec-9-ene, and 9-OKD is dimethyl octadec-9-enodiate.

##STR00124##

TABLE-US-00003 TABLE 3 Comparison of model reaction results for selected ruthenium complexes Z/E ratio after reaction Catalyst Conversion [%] 9-ODE OM 9-OKD 1-Ru1a 18 96/4 >99/1 >99/1 1-Ru1c 21 90/10 >99/1 >99/1 1-Ru1n 13 98/2 >99/1 >99/1 1-Ru1x 36 76/24 74/26 76/24

Example VIII

Study of the Effect of Addition of Zinc Derivative and Other Metals on the Activity and Selectivity of New Stereoretentive Ruthenium Complexes in the Cross-Metathesis Reaction of Methyl Oleate (OM)

[0263] A solution of methyl oleate (1.0 equiv.) in THF, a solution of tetradecane (0.1 equiv.) in THF, a solution of catalyst 1-Ru1c (0.0002 equiv.) in THF and 3-Zn1 (0.0-1.0 equiv.) was introduced into a vial equipped with a stirring element so that the concentration of methyl oleate in the reaction mixture was 0.1 M. The reactions were carried out at 60 C. for 18 hours. The conversion and composition of the mixture were determined by gas chromatography. The results of the reactions are shown in Table 4, where OM is methyl oleate, 9-ODE is octadec-9-ene, 9-OKD is dimethyl octadec-9-enodiate

##STR00125##

TABLE-US-00004 TABLE 4 Effect of zinc complex addition on the course of the model reaction Number of 3-Zn1 Conversion Z/E ratio after reaction equivalents per 1-Ru1c [%] 9-ODE OM 9-OKD 1 19 98/2 95/5 97/3 0.5 21 98/2 95/5 96/4 0.25 22 96/4 94/6 94/6 0 24 88/12 88/12 82/18

Example IX

Activity Study of the New Stereoretentive Ruthenium Complexes in the Cross-Metathesis Reaction of Allylbenzene with (Z)-1,4-Diacetoxybut-2-Ene

[0264] A solution of allylbenzene (1.0 equiv.) in THF, a solution of (Z)-1,4-diacetoxybut-2-ene (2.0 equiv.) in THF, a solution of tetradecane (0.1 equiv.) in THF, a solution of catalyst 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m or 1-Ru1x (0.05 equiv.) in THF were introduced into a vial equipped with a stirring element so that the concentration of allylbenzene in the mixture was 0.237 M. The reactions were carried out at room temperature for 4 hours. The conversion and composition of the mixture were determined by gas chromatography. The results of the reactions are shown in Table 5.

##STR00126##

TABLE-US-00005 TABLE 5 Comparison of model reaction results for selected ruthenium complexes Catalyst Conversion [%] Z/E ratio in the product 1-Ru0a 52 98/2 1-Ru1a 49 98/2 1-Ru1c 46 97/3 1-Ru1m 27 >99/1 1-Ru1x 32 >99/1 1-Ru0b.sup.a 55 97/3 .sup.aLiterature result [A. Dumas, D. S. Mller, I. Curbet, L. Toupet, M. Rouen, O. Basl, M. Mauduit, Organometallics 2018, 37, 829-834]

Example X

Activity Study of the New Stereoretentive Ruthenium Complexes in the Cross-Metathesis Reaction of Allylbenzene with (Z)-but-2-en-1,4-diol

[0265] A solution of allylbenzene (1.0 equiv.) in THF, a solution of (Z)-but-2-ene-1,4-diol (2.0 equiv.) in THF, a solution of tetradecane (0, 1 equiv.) in THF, a solution of catalyst 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m or 1-Ru1x (0.05 equiv.) in THF were introduced into a vial equipped with a stirring element so that the concentration of allylbenzene in the mixture was 0.237 M. The reactions were carried out at room temperature for 4 hours. The conversion and composition of the mixture were determined by gas chromatography (GC). The results of the model reaction are summarized in Table 6.

##STR00127##

TABLE-US-00006 TABLE 6 Comparison of model reaction results for selected ruthenium complexes Catalyst Conversion [%] Z/E ratio in the product 1-Ru0a 56 98/2 1-Ru1a 42 98/2 1-Ru1c 47 79/21 1-Ru1m 29 98/2 1-Ru1x 34 >99/1 1-Ru0b.sup.a 78 98/2 .sup.aLiterature result [A. Dumas, D. S. Mller, I. Curbet, L. Toupet, M. Rouen, O. Basl, M. Mauduit, Organometallics 2018, 37, 829-834]

[0266] .sup.[a] Literature result [A. Dumas, D. S. Mller, I. Curbet, L. Toupet, M. Rouen, O. Basl, M. Mauduit, Organometallics 2018, 37, 829-834]

Example XI

Activity Study of the New Stereoretentive Ruthenium Complexes in the Cross-Metathesis Reaction of Methyl Elaidinate (EM)

[0267] A solution of methyl elaidinate (1.0 equiv.) in THF, a solution of tetradecane (0.1 equiv.) in THF and a solution of catalyst 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m or 1-Ru1x (0.075 equiv.) in THF were introduced into a vial equipped with a stirring element so that the concentration of methyl elaidinate in the mixture was 0.42 M. The reactions were carried out at room temperature for 20 hours. The conversion and composition of the mixture were determined by gas chromatography. The results of the model reaction are shown in Table 7, where EM is methyl elaidinate, 9-ODE is octadec-9-ene, and 9-OKD is dimethyl octadec-9-enodiate.

##STR00128##

TABLE-US-00007 TABLE 7 Comparison of model reaction results for selected ruthenium complexes E/Z ratio after reaction Catalyst Conversion [%] 9-ODE OM 9-OKD 1-Ru0a 50 84/16 89/11 86/14 1-Ru1a 50 95/5 94/6 95/5 1-Ru1c 50 95/5 94/6 91/9 1-Ru1m 50 82/18 82/18 79/21 1-Ru1x 50 94/6 93/7 88/12

Example XII

Activity Study of the New Stereoretentive Ruthenium Complexes in the Cross-Metathesis Reaction of dec-9-en-1-ol acetate and (Z)-hex-3-ene. Synthesis of (Z)-dodec-9-en-1-ol acetate, the Insect Sex Pheromone of the Moth Eupoecilia ambiguella

[0268] A solution of dec-9-en-1-ol (1.0 equiv.) in THF, a solution of (Z)-hex-3-ene (2.0 equiv.) in THF, a solution of tetradecane (0, 1 equiv.) in THF, and a solution of catalyst 1-Ru0a, 1-Ru1a, 1-Ru1c, 1-Ru1m, 1-Ru1t or 1-Ru1x (0.05 equiv.) in THF were introduced into a vial equipped with a stirring element so that the concentration of dec-9-en-1-ol in the mixture was 0.237 M. The reactions were carried out at room temperature for 20 hours. The conversion and composition of the mixture were determined by gas chromatography. The results of the model reaction are shown in Table 8.

##STR00129##

TABLE-US-00008 TABLE 8 Comparison of model reaction results for selected ruthenium complexes Catalyst Conversion [%] Z/E ratio in the product 1-Ru0a 97 87/13 1-Ru1a 91 81/19 1-Ru1c 95 41/59 1-Ru1m 84 82/18 1-Ru1t 63 96/4 1-Ru1x 89 90/10

Example XIII

Activity Study of the New Stereoretentive Ruthenium Complexes in the Ring-Closing Metathesis Reaction of (Z)-6-nonenyl oleate

[0269] (Z)-6-nonenyl oleate (1.0 equiv.), 2.5 mL PAO6, and an appropriate amount of catalyst 1-Ru1a or 1-Ru0a were introduced into a reaction vessel equipped with a stirring element. The vessel was equipped with a Hickman distillation adapter, then connected to a diffusion pump (nominal pressure was 110.sup.6 mbar) and placed in a heating bath. The reaction was carried out for 8 hours at 110 C. After the reaction was completed, the distillate was purified on a column chromatography (SiO.sub.2, using n-hexane followed by ethyl acetate as eluents). The fractions collected with ethyl acetate were combined and then concentrated on a rotary evaporator. As a result, a pure product was obtained, in which the Z-isomer content was determined by gas chromatography. The results of the model reaction are shown in Table 9.

##STR00130##

TABLE-US-00009 TABLE 9 Effect of the amount of ruthenium complex on the course of the model reaction Catalyst amount Catalyst Yield [%] Z/E ratio in the product 10 mol % 1-Ru0a 52% 58/42 10 mol % 1-Ru1a 84% 93/7 1.0 mol % 1-Ru1a 76% 96/4 0.5 mol % 1-Ru1a 78% 98/2

Example XIV

Activity Study of the New Stereoretentive Ruthenium Complexes in the Reaction to Obtain Civetone by Ring-Closure Metathesis (RCM) Reaction

[0270] Substrate (1.0 equiv.), 2.5 mL PAO6, and the appropriate 1-Ru1a or 1-Ru0a catalyst amount were introduced into the reaction vessel. The vessel was equipped with a Hickman distillation adapter, then connected to a diffusion pump (nominal pressure was 110.sup.6 mbar) and placed in a heating bath. The reaction was carried out for 8 hours at 110 C. After the reaction was completed, the distillate was purified on a column chromatography (SiO.sub.2, using n-hexane followed by ethyl acetate as eluents). The fractions collected with ethyl acetate were combined and then concentrated on a rotary evaporator. As a result, a pure product was obtained, in which the content of the Z-isomer was determined by gas chromatography. The results of the model reaction are shown in Table 10.

##STR00131##

TABLE-US-00010 TABLE 10 Comparison of model reaction results for selected ruthenium complexes Z/E ratio in the Catalyst amount Temperature Catalyst Yield [%] product 1.0 mol % 110 C. 1-Ru1a 54% 96/4 0.5 mol % 110 C. 1-Ru1a 54% 98/2 0.5 mol % 110 C. 1-Ru0a 13% 83/17 0.5 mol % 130 C. 1-Ru1a 45% 96/4 0.5 mol % 150 C. 1-Ru1a 27% 96/4

[0271] The results shown in Example XIII and Example XIV indicate that the representative for the state of the art stereoretentive thiocatechol complex 1-Ru0a does not yield satisfactory results in the synthesis of macrocyclic lactones and ketones at elevated temperature, while the complexes that are the subject matter of the invention show much higher stereoselectivity and/or yield under the same conditions.

Example XV

Study of the Z-Selective Molybdenum Complex Activities in the Ring-Closure Metathesis Reaction of (Z)-6-nonenyl oleate

[0272] Substrate (1.0 equiv.), 2.5 mL PAO6, and catalyst Mo1, Mo2 or Mo3 in tablet form were introduced into the reaction vessel. The vessel was equipped with a Hickman distillation adapter, then connected to a diffusion pump (nominal pressure was 110.sup.6 mbar) and placed in a heating bath. The reactions were carried out for 8 hours at 110 C. After the reaction was completed, the distillate was purified on a column chromatography (SiO.sub.2, using n-hexane followed by ethyl acetate as eluents). The fractions collected with ethyl acetate were combined and then concentrated on a rotary evaporator. As a result, a pure product was obtained, in which the content of the Z-isomer was determined by gas chromatography. The results of the model reaction are shown in Table 11.

##STR00132##

TABLE-US-00011 TABLE 11 Comparison of model reaction results for selected ruthenium complexes Catalyst Catalyst amount Yield [%] Z/E ratio in the product Mo1 2.6 mol % 92% 18/82 Mo2 1.9 mol % 93% 30/70 Mo3 2.4 mol % 87% 26/74

[0273] As expected, the non-stereoselective Mo1 complex yielded the E/Z ratio typical of standard molybdenum complexes. In contrast, the Z-selective Mo2 complex unexpectedly did not show the expected Z-selectivity. Similarly, in the case of another representative for the state of the art Z-selective Mo3 complex, the obtaining of an excess Z-isomer also did not occur. The above results indicate that the cited method for the synthesis of macrocyclic lactones at elevated temperature is incompatible with representative Z-selective alkylidene molybdenum complexes, while the complexes that are the subject matter of the invention show high stereoselectivity under the same conditions.

Example XVI

Activity Study of the Z-Selective Ruthenium Complex in the Ring-Closure Metathesis Reaction of (Z)-6-nonenyl oleate

[0274] Substrate (1.0 equiv.), 2.5 mL PAO6, and catalyst were introduced into the reaction vessel. The vessel was equipped with a Hickman distillation adapter, then connected to a diffusion pump (nominal pressure was 110.sup.6 mbar) and placed in a heating bath. The reaction was carried out for 8 hours at 110 C. After the reaction was completed, the distillate was purified on a column chromatography (SiO.sub.2, hexane then ethyl acetate). The fractions collected with ethyl acetate were combined and then concentrated on a rotary evaporator. As a result, a pure product was obtained, in which the Z-isomer content was determined by gas chromatography. The results of the model reaction are shown in Table 12.

##STR00133##

TABLE-US-00012 TABLE 12 Comparison of results of model reaction carried out at different temperatures for different 1-Ru0c catalyst loadings 1-Ru0c catalyst Z/E ratio in the amount [mol %] Temperature Yield [%] product 0.5 110 0 0.5 40.fwdarw.110 0 10 110 0

[0275] The results shown in Example XVI indicate that the representative for the state of the art Z-selective 1-Ru0c complex does not give satisfactory results in the synthesis of macrocyclic lactones at elevated temperature.

Example XV

Activity Study of the New Stereoretentive Ruthenium Complexes in the Reaction to Obtain Macrocyclic Compounds by Ring-Closure Metathesis (RCM) Reaction

[0276] Substrate (1.0 equiv.), 2.5 mL PAO6, and the corresponding 1-Ru1a catalyst amount were introduced into the reaction vessel. The vessel was equipped with a Hickman distillation adapter, then connected to a diffusion pump (nominal pressure was 110.sup.6 mbar) and placed in a heating bath. The reaction was carried out for 8 hours at 110 C. After the reaction was completed, the distillate was purified on a column chromatography (SiO.sub.2, using n-hexane followed by ethyl acetate as eluents). The fractions collected with ethyl acetate were combined and then concentrated on a rotary evaporator. As a result, a pure product was obtained, in which the Z-isomer content was determined by gas chromatography. The results of the model reaction are shown in Scheme 24.

##STR00134##

Example XVI

Activity Study of the New Stereoretentive Ruthenium Complexes in the Cross-Metathesis Reaction of Terminal Olefins or Internal Olefins of Z-Configuration with Internal Symmetric Olefins of Z-Configuration

[0277] A solution of terminal olefin or internal olefin of Z-configuration (1.0 equiv.) in THF and a solution of symmetric internal olefin of Z-configuration (2.0 equiv.) in THF was introduced into a vial equipped with a stirring element so that the concentration of terminal olefin in the mixture was 0.2 M. A solution of 1-Ru0a, 1-Ru1a (0.02 equiv.) catalyst in THF was added to the mixture, or a solution of 1-Ru0a, 1-Ru1a (0.04 equiv.) catalyst in THF was added in two portions (the second portion was added one hour after the start of the reaction). The reactions were carried out at room temperature for 2 hours. The composition of the mixture was determined by NMR spectroscopy. The results of the model reaction are shown in Scheme 25.

##STR00135## ##STR00136##

LITERATURE

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