N-heterocyclic carbene complexes of metal imido alkylidenes and metal OXO alkylidenes, and the use of same

Abstract

The invention relates to an N-heterocyclic carbene complex of general formulas I to IV (I) (II) (III) (IV), according to which A1 stands for NR2 or PR2, A2 stands for CR2 R2, NR2, PR2, 0 or S, A3 stands for N or P, and C stands for a carbene carbon atom, ring B is an unsubstituted or a mono or poly-substituted 5 to 7-membered ring, substituents R2 and R2 stand, inter alia, for a linear or branched C1-Cw-alkyl group and, if N and N each stand for NR2 or PR2, are the same or different, M in formulas I, II, III or IV stands for Cr, Mo or W, X 1 or X2 in formulas I to IV are the same or different and represent, inter alia, C1-C1s carboxylates and C1-C1s-alkoxides, Y is inter alia oxygen or sulphur, Z is inter alia a linear or branched C1-Cw-alkylenoxy group, and R 1 and R1 in formulas I to IV are, inter alia, an aliphatic or aromatic group. These compounds are particularly suitable for use as catalysts for olefin metathesis reactions and have the advantage, compared to known Schrock carbene complexes, of displaying clearly increased tolerance to functional groups such as, in particular, aldehydes, secondary amines, nitriles, carboxylic acids and alcohols.

Claims

1. An N-heterocyclic carbene complex of one of the general formulae I-IV ##STR00024## wherein: A.sup.1 is NR.sup.2 or PR.sup.2, A.sup.2 is CR.sup.2R.sup.2, NR.sup.2, PR.sup.2, O or S, A.sup.3 is N or P, C is a carbene carbon atom, the ring B is an unsubstituted or a mono- or polysubstituted 5- to 7-membered ring which, as well as A.sup.1, A.sup.2 and/or A.sup.3, may contain further heteroatoms in the form of nitrogen, phosphorus, oxygen or sulfur and wherein the substituents may have the definition described for R.sup.2, the substituents R.sup.2 and R.sup.2 are independently H, a linear, partly cyclic or branched C.sub.1-C.sub.18-alkyl, a linear, partly cyclic or branched C.sub.2-C.sub.18-alkenyl, a C.sub.3-C.sub.12-cycloalkyl, a linear, partly cyclic or branched C.sub.6-C.sub.100-polyoxaalkyl, a C.sub.5-C.sub.14-aryl or -heteroaryl radical, a C.sub.5-C.sub.14-aryloxy, a linear, partly cyclic or branched C.sub.1-C.sub.18-perfluoroalkyl, a linear, partly cyclic or branched C.sub.1-C.sub.18-perchloroalkyl, a linear, partly cyclic or branched part-fluorinated C.sub.1-C.sub.18-alkyl, a linear, partly cyclic or branched part-chlorinated C.sub.1-C.sub.18-alkyl, a per- or part-fluorinated C.sub.6-C.sub.14-aryl, a per- or part-chlorinated C.sub.5-C.sub.14-aryl radical, and, when A.sup.1 and A.sup.2 are each NR.sup.2 or PR.sup.2, R.sup.2 may be the same or different, or R.sup.2 and R.sup.2 together are a linear or branched C.sub.1-C.sub.18-alkylene, M in the formulae I, II, III and IV is Cr, Mo or W, X.sup.1 and X.sup.2 in formulae I to IV are the same or different and are selected from the group consisting of halogen, C.sub.1-C.sub.18 carboxylates, C.sub.1-C.sub.18-alkoxides, fluorinated C.sub.1-C.sub.18 alkoxides, C.sub.1-C.sub.18 mono- or polyhalogenated carboxylates, unsubstituted or mono- or polysubstituted C.sub.6-C.sub.18 mono-, bi- or terphenoxides, trifluoromethanesulfonate, and non-coordinating anions, where the substituents on the mono-, bi- or terphenoxides, can be halogen or may have the same definition as R.sup.2, Y is oxygen, sulfur, an N-adamantyl, an N-tert-butyl, a C.sub.6-C.sub.14N-aryl radical, where the aryl radical may be mono- or polysubstituted by halogen, a linear or branched C.sub.1-C.sub.18 alkyl, a linear or branched C.sub.1-C.sub.18 alkyloxy or an unsubstituted or substituted phenyl radical wherein the substituents have the same definition as R.sup.2, Z is a linear, partly cyclic or branched C.sub.1-C.sub.10-alkyleneoxy, a linear, partly cyclic or branched C.sub.1-C.sub.10-alkylenethio, a linear, partly cyclic or branched C.sub.1-C.sub.10-alkylene-NR.sup.2, a C.sub.6-C.sub.10-aryleneoxy, a per- or part-fluorinated C.sub.6-C.sub.14-aryleneoxy, a per- or part-chlorinated C.sub.6-C.sub.14-aryleneoxy, a per- or part-brominated C.sub.6-C.sub.14-aryleneoxy, a C.sub.6-C.sub.14-arylenethio, a per- or part-fluorinated C.sub.6-C.sub.14-arylenethio, a per- or part-chlorinated C.sub.6-C.sub.14-arylenethio, a per- or part-brominated C.sub.6-C.sub.14-arylenethio, C.sub.6-C.sub.14-arylene-NR.sup.2, a per- or part-fluorinated C.sub.6-C.sub.14-arylene-NR.sup.2, a per- or part-chlorinated C.sub.6-C.sub.14-arylene-NR.sup.2, a per- or part-brominated C.sub.6-C.sub.14-arylene-NR.sup.2, a C.sub.6-C.sub.14-arylene-PR.sup.2, a per- or part-fluorinated C.sub.6-C.sub.14-arylene-PR.sup.2, a per- or part-chlorinated C.sub.6-C.sub.14-arylene-PR.sup.2, a per- or part-brominated C.sub.6-C.sub.14-arylene-PR.sup.2, a carboxyl, a thiocarboxyl or a dithiocarboxyl group, and R.sup.1 and R.sup.1 in the formulae I to IV are independently H, aliphatic, aromatic radical, linear or branched C.sub.1-C.sub.18 alkyl group, tert-butyl, CMe.sub.2Ph group, unsubstituted or mono- or polysubstituted C.sub.6-C.sub.14-aryl group, where the substituents have the definitions given for R.sup.2, 2-(2-propoxy)phen-1-yl; 2-methoxyphen-1-yl; 2,4,5-trimethoxyphenyl; or ferrocenyl.

2. An N-heterocyclic carbene complex as claimed in claim 1, wherein the ring B is a heterocycle selected from the group comprising 1,3-disubstituted imidazol-2-ylidenes, 1,3-disubstituted imidazolin-2-ylidenes, 1,3-disubstituted tetrahydro-pyrimidin-2-ylidenes, 1,3-disubstituted diazepin-2-ylidenes, 1,3-disubstituted dihydrodiazepin-2-ylidenes, 1,3-disubstituted tetrahydrodiazepin-2-ylidenes, N-substituted thiazol-2-ylidenes, N-substituted thiazolin-2-ylidenes, N-substituted triazol-2-ylidenes, mono- or polysubstituted dihydrotriazol-2-ylidenes, mono- or polysubstituted triazolin-2-ylidenes, N-substituted thiadiazol-2-ylidenes, mono- or polysubstituted thiadiazolin-2-ylidenes and mono- or polysubstituted tetrahydrotriazol-2-ylidenes.

3. An N-heterocyclic carbene complex as claimed in claim 1, wherein the ring B is bonded covalently via a spacer group to a solid support.

4. An N-heterocyclic carbene complex as claimed in claim 3, wherein the solid support is a polymeric support, and the spacer group is a C.sub.1-C.sub.20-,-dioxaalkylene or a C.sub.1-C.sub.20-alkyleneoxy group.

5. An N-heterocyclic carbene complex as claimed in claim 3, wherein the solid support is an inorganic support, and the spacer group is an alkyl-Si(O).sub.3 or an alkyl-SiR(O).sub.2 group in which R has the same definition as R.sup.2.

6. An N-heterocyclic carbene complex as claimed in claim 1, wherein R.sup.1 in formulae I, II, III or IV is t-butyl, an unsubstituted or substituted phenyl, ferrocenyl or CMe.sub.2Ph, R.sup.1 in addition to H may have all the definitions mentioned for R.sup.1 and substituents on the phenyl may have the same definition as R.sup.2.

7. An N-heterocyclic carbene complex as claimed in claim 1, wherein the non-coordinating anions as X.sup.1 and X.sup.2 are selected from tetrakis(3,5-bis-(trifluoromethyl)phenyl)borate, tetrakis(penta-fluorophenyl)borate, tetrakis(nonafluoro-t-butoxy)-aluminate, tetrafluoroborate, hexafluorophosphate or hexafluoroantimonate.

8. A method of conducting an olefin metathesis reaction, the method including: contacting a substrate for the olefin methathesis reaction with a catalyst, wherein the catalyst is an N-heterocyclic carbene complex according to claim 1.

9. The method as claimed in claim 8, wherein the olefin metathesis reaction is an asymmetric or desymmetrizing ring-closing metathesis, a cross-metathesis, a ring-opening cross-metathesis, a (cross-)ene-yne metathesis, a ring-closing ene-yne metathesis, a cross-ene-diyne metathesis, a tandem ring-opening-ring-closing metathesis, a ring-opening metathesis polymerization (ROMP), a 1-alkyne polymerization, an acyclic diene metathesis polymerization (ADMET) or a cyclopolymerization of ,-diynes.

10. The method as claimed in claim 8, wherein the olefin metathesis reaction is an olefinolysis of fatty acid esters.

11. The method as claimed in claim 10, wherein the olefinolysis of fatty acid esters comprises the olefinolysis of vegetable oils and fats.

12. The method as claimed in claim 11, wherein the vegetable oils are selected from the group consisting of castor oil, palm oil, and coconut oil.

13. The method as claimed in claim 12, wherein the vegetable oils are combined with at least one of ethylene and butene.

14. The method as claimed in claim 8, wherein the catalyst is a compound of formula II or IV and the method further comprises: dissolving the compound of formula II or IV in an organic solvent (I) or in an ionic liquid to form a solution, applying the solution in the form of a thin film to a support material, introducing the support material including the thin film into a reaction vessel, and introducing a substrate into the reaction vessel, wherein the substrate is dissolved in a solvent (II) that is immiscible with the organic solvent (I) or the ionic liquid.

15. The method as claimed in claim 14, wherein the ionic liquid used is 1,3-dimethyl-imidazolium salt, 1,2,3-trimethylimidazolium salt, 1-butyl-3-methylimidazolium salt, 1-butyl-2,3-dimethylimidazolium salt, and the solvent (II) immiscible with the ionic liquid employed is toluene, pentane, hexane, heptane, octane, or a combination thereof.

16. The method as claimed in claim 14, wherein the substrate is charged continuously into the reaction vessel and resulting reaction products are discharged continuously therefrom.

17. The method as claimed in claim 14, wherein the support material is an inorganic support material or a polymer-organic support material.

18. The method as claimed in claim 17, wherein the inorganic support material comprises silicon dioxide.

19. The method as claimed in claim 17, wherein the polymer-organic support material is a polymer-organic monolithic support material.

Description

EXAMPLES

(1) ##STR00004## ##STR00005## ##STR00006## ##STR00007##

(2) Structure of selected Mo catalysts. DIPP=2,6-di(2-propyl)phen-1-yl.

Example 1 (Preparation of Mo(N-2,6-Me2-C6H3)(IMesH2)(CH-tBu)(OTf)2) (1)

(3) Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(CH-tBu)(OTf).sub.2 (DME) (0.300 g, 0.445 mmol) were dissolved in 8 mL of benzene, and a solution of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolinylidene (0.136 g, 0.445 mmol) in 5 mL of benzene was added. The reaction solution was stirred for three hours, the benzene was decanted off, and the residue was washed with benzene. Yield: 0.32 g (81%, yellow powder). It was possible to obtain crystalline material by recrystallization from CH.sub.2Cl.sub.2. .sup.1H NMR (CD.sub.2Cl.sub.2): (syn isomer, 99.9%) 12.76 (s, 1, CHCMe.sub.3, J.sub.CH=118 Hz), 7.06-6.61 (7H, ArH), 3.98 (4H, CH.sub.2NC), 2.69-1.71 (24H, Me), 0.93 (s, 9H, CH.sub.2CMe.sub.3); .sup.19F NMR (CD.sub.2Cl.sub.2): 74.65 (SO.sub.3CF.sub.3), 76.7 (SO.sub.3CF.sub.3). .sup.13C NMR (CD.sub.2Cl.sub.2): 320.9 (CH-tBu), 208.7 (CN.sub.carbene), 154.6 (C.sub.ipso), 140.4 (C.sub.ortho), 137.1 (C.sub.aryl), 136.8 (C.sub.aryl), 135.7 (C.sub.aryl), 131.1 (CH.sub.aryl), 130.5 (CH.sub.aryl), 130.1 (CH.sub.aryl), 128.2 (C.sub.aryl), 120.2 (q, CF.sub.3, J=319 Hz), 119.8 (q, CF.sub.3, J=320 Hz), 53.1 (CMe.sub.3), 50.7 (CH.sub.2-imidazolylene), 30.5 (CMe.sub.3), 21.3 (CH.sub.3), 19.0 (CH.sub.3), 18.9 (CH.sub.3); anal. calc. for C.sub.36H.sub.45F.sub.6MoN.sub.3O.sub.6S.sub.2.CH.sub.2Cl.sub.2: C, 45.54; H, 4.96; N, 4.31. Found: C, 45.52; H, 4.75; N, 4.37.

Example 2 (Preparation of Mo(N-2,6-Me2-C6H3)(I-tBu)(CH-tBu)(OTf)2) (2)

(4) Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(CH-tBu)(OTf).sub.2 (DME) (0.100 g, 0.148 mmol) were dissolved in 3 mL of benzene. 1,3-Di-t-butylimidazol-2-ylidene (0.027 g, 0.15 mmol), likewise dissolved in benzene, was added while stirring. After stirring for three hours, the liquid was decanted from the precipitate and the residue was washed with benzene. Yield: 0.060 g (65%, yellow powder). It was possible to obtain crystalline material by recrystallization from CH.sub.2Cl.sub.2. .sup.1H NMR (CD.sub.2Cl.sub.2): 14.60 (s, 1H, CHCMe.sub.3, J.sub.CH=121 Hz, syn isomer), 7.12-6.95 (3H, ArH), 2.60 (2H, CHNC), 1.80-1.67 (24H, Me), 1.32 (s, 9H, CH.sub.2CMe.sub.3); .sup.19F NMR (CD.sub.2Cl.sub.2): 77.68, 77.69, 77.70, 77.71 (CF.sub.3SO.sub.3), 78.06, 78.07, 78.08, 78.09 (CF.sub.3SO.sub.3); .sup.13C NMR (CD.sub.2Cl.sub.2): 329.6 (CH-tBu), 175.4 (CN.sub.carbene), 154.3 (C.sub.ipso), 142.2 (C.sub.aryl), 136.9 (C.sub.aryl), 129.7 (CH.sub.aryl), 129.6 (CH.sub.aryl), 128.9 (CH.sub.aryl), 121.7 (C.sub.CC), 120.6 (C.sub.CC), 119.8 (q, CF.sub.3, J=318 Hz), 119.7 (q, CF.sub.3, J=319 Hz), 61.7 (NCMe.sub.3), 61.3 (CMe.sub.3), 32.8 (CMe.sub.3), 30.5 (CMe.sub.3), 30.1 (CMe.sub.3), 21.1 (CH.sub.3), 18.4 (CH.sub.3). Anal. calc. for C.sub.26H.sub.39F.sub.6MoN.sub.3O.sub.6S.sub.2: C, 40.84; H, 5.27; N, 5.50. Found: C, 40.88; H, 5.20; N, 5.56.

Example 3 (Preparation of N-2,6-Me2-C6H3)(IMesH2)(CHCMe3)(OTf)(OEt)) (3)

(5) Sodium ethoxide (0.0120 g, 0.1842 mmol) was dissolved in 5 mL of diethyl ether:THF, 1:1. Then Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (0.080 g, 0.090 mmol) was added. After stirring for two hours, the solvent was removed, and the residue was dissolved in 5 mL of dichloromethane and filtered through Celite. Recrystallization from dichloromethane gave yellow crystalline material in 40% yield. .sup.1H NMR (CD.sub.2Cl.sub.2): 12.30 (s, 1H, CHCMe.sub.3), 6.94-6.65 (7H, ArH), 4.15 (4H, CH.sub.2NC), 3.69 (2H, OCH.sub.2CH.sub.3), 2.53-2.24 (24H, Me), 1.82 (3H, OCH.sub.2CH.sub.3), 1.14 (s, 9H, CH.sub.2CMe.sub.3); 19F NMR (CD.sub.2Cl.sub.2): 79.05 (CF.sub.3SO.sub.3).

Example 4 (Preparation of Mo(N-2,6-Cl2C6H3)(CHCMe3)-(OTf)2(IMes)) (4)

(6) In a glovebox, Mo(N-2,6-ClC.sub.6H.sub.3)(CHCMe.sub.3)(OTf).sub.2(DME) (0.432 g, 0.605 mmol) was initially charged in a 25 mL Schlenk flask. The complex was dissolved in 15 mL of toluene and cooled at 40 C. for 30 min. 1,3-Dimesitylimidazol-2-ylidene (0.184 g, 0.605 mmol, 1 equiv.) was dissolved in 3 mL of toluene and likewise cooled. While stirring, the cold NHC solution was added dropwise to the metal complex. The color changed gradually to dark orange. The reaction mixture was stirred at room temperature for 2 h. After a few minutes, cloudiness set in and a precipitate formed. Subsequently, the solvent was concentrated to about and the suspension was frozen for 30 min. The precipitated solids were filtered off and washed with a little cold toluene. The crude product is obtained as a yellow solid and can be recrystallized from dichloromethane (0.450 g, 80%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =1.12 (s, 9H, tBu), 2.10 (s, 6H, o-Mes-Me), 2.11 (s, 6H, o-Mes-Me), 2.24 (s, 6H, p-Mes-Me), 6.68 (s, br, 2H, Mes-Ar), 6.98 (s, br, 2H, Mes-Ar), 7.14 (m, 3H, Ar), 7.22 (s, 2H, NCHCHN), 12.94 (s, 1H, MoCH); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2): =18.9 (o-Mes-Me), 19.0 (o-Mes-Me), 21.3 (p-Mes-Me), 31.4 (CMe.sub.3), 50.6 (CMe.sub.3), 124.4, 126.4, 128.3, 129.5, 130.3, 130.9, 134.7, 135.9, 136.3, 136.5, 141.0 (ipso-Mes), 149.9 (ipso-imido), 185.2 (NCN), 327.4 (MoCH, J.sub.CH=119.5 Hz); .sup.19F NMR (375 MHz, CD.sub.2Cl.sub.2) =75.07, 76.56.

Example 5 ((Preparation of Mo(N-2,6-Cl2C6H3)(CHCMe3)-(OTf)2(IMesH2)) (5)

(7) In a glovebox, Mo(N-2,6-ClC.sub.6H.sub.3)(CHCMe.sub.3)(OTf).sub.2(DME) (0.198 g, 0.277 mmol) was initially charged in a 25 mL Schlenk flask. The complex was dissolved in 15 mL of toluene and cooled at 40 C. for 30 min. 1,3-Dimesitylimidazol-2-ylidene (0.085 g, 0.277 mmol, 1 equiv.) was dissolved in 3 mL of toluene and likewise cooled. While stirring, the cold NHC solution was added dropwise to the metal complex. The color changed gradually to dark orange. The reaction mixture was stirred at room temperature for 2 h. After a few minutes, cloudiness set in and a precipitate formed. Subsequently, the solvent was concentrated to about and the suspension was frozen for 30 min. The precipitated solids were filtered off and washed with a little cold toluene. The crude product is obtained as a yellow solid and can be recrystallized from dichloromethane (0.185 g, 72%).

Example 6 (Preparation of Mo(N-2,6-Me2-C6H3)(IMesH2)(CHCMe2Ph)(OTf)2) (6)

(8) Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(CHCMe.sub.2Ph)(OTf).sub.2(DME) (0.20 g, 0.2720 mmol) was initially charged in 8 mL of benzene: 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidin-2-ylidene (0.0830 g, 0.2720 mmol) was dissolved in 1 mL of benzene and added dropwise. In the course of this, a rapid color change from a yellow to dark red was observed with simultaneous formation of a precipitate.

(9) After stirring for three hours, the benzene was then decanted off, and the residue was washed with benzene and dried under reduced pressure. The product was isolated as a yellow solid (0.15 g, 81%). Alternatively, the yellow solid can be dissolved in a minimal amount of dichloromethane and crystallized at 30 C. for 24 h, giving a crystalline yellow material with 69% yield. .sup.1H NMR (CD.sub.2Cl.sub.2): =13.11 (s, 1H, CHCMe.sub.2Ph, J.sub.CH=114 Hz), 7.19-6.95 (m, 9H, ArH), 6.51 (s, 2H, ArH), 3.97 (s, 4H, CHNC), 2.69-1.71 (s, 27H, Me), 1.25 (s, 3H, CHCMe.sub.2Ph) ppm; .sup.19F NMR (CD.sub.2Cl.sub.2): =74.59 (s, CF.sub.3SO.sub.3, trans to the NHC ligand), 76.53 (s, CF.sub.3SO.sub.3); .sup.13C NMR (CD.sub.2Cl.sub.2): =317.4 (CHCMe.sub.3), 208.7 (CN.sub.carbene), 154.6 (C.sub.ipso), 149.0, 140.4 (C.sub.ortho), 137.0 (C.sub.aryl), 136.4 (C.sub.aryl), 135.6 (C.sub.aryl), 130.9 (C.sub.aryl), 130.5 (C.sub.aryl), 130.2 (C.sub.aryl), 128.4 (C.sub.aryl), 128.2 (C.sub.aryl), 126.9 (C.sub.aryl), 125.9 (C.sub.aryl), 121.6 (q, CF.sub.3, J=319 Hz), 118.5 (q, CF3, J=320 Hz), 56.8 (CMe.sub.2Ph), 53.1 (CH.sub.2 imidazolylidene), 32.9 (CMe.sub.2Ph), 29.6 (CMe.sub.2Ph), 21.3 (CH.sub.3), 19.0 (CH.sub.3), 18.9 (CH.sub.3); elemental analysis: C.sub.41H.sub.47F.sub.6MoN.sub.3O.sub.6S.sub.2; calculated: C, 51.68; H, 5.02; N, 4.41. found: C, 51.81; H, 4.88; N, 4.35.

Example 7 (Preparation of Mo(N-2,6-Me2-C6H3)(IMes)-(CHCMe2Ph)(OTf)2) (7)

(10) Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(CHCMe.sub.2Ph)(OTf).sub.2(DME) (0.1500 g, 0.204 mmol) was dissolved in 6 mL of benzene, adding to the initially charged solution of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazol-2-ylidene (0.0620 g, 0.2040 mmol) in a 1 mL of benzene. The color changed immediately from yellow to dark red with simultaneous formation of a precipitate. The reaction mixture was stirred for three hours and then the solvent was decanted. The residue was washed with benzene and dried under reduced pressure. A yellow solid was obtained (0.13 g, 85%). The yellow product can be recrystallized from a minimal amount of dichloromethane at 30 C. (65%). .sup.1H NMR (CD.sub.2Cl.sub.2): =13.18 (s, 1H, CHCMe.sub.2Ph, J.sub.CH=118 Hz), 7.21-6.95 (m, 9H, ArH), 6.56 (s, 2H), 4.29 (s, 2H, CHNC), 2.60-1.97 (s, 27H, Me), 1.29 (s, 3H, CHCMe.sub.2Ph) ppm; .sup.19F NMR (CD.sub.2Cl.sub.2): =74.92 (s, CF.sub.3SO.sub.3, trans to the NHC ligand), 76.53 (s, CF.sub.3SO.sub.3); .sup.13C NMR (CD.sub.2Cl.sub.2): =317.0 (CHCMe.sub.3), 184.3 (CN.sub.carbene), 154.8 (C.sub.ipso), 149.0, 141.3 (C.sub.ortho), 136.4 (C.sub.aryl), 135.9 (C.sub.aryl), 135.5 (C.sub.aryl), 130.6 (C.sub.aryl), 130.1 (C.sub.aryl), 130.0 (C.sub.aryl), 128.6 (C.sub.aryl), 128.2 (C.sub.aryl), 126.9 (C.sub.aryl), 126.4 (C.sub.aryl), 125.9 (C.sub.aryl), 121.6 (C.sub.CC), 121.4 (C.sub.CC), 118.4 (q, CF.sub.3, J=318 Hz), 118.3 (q, CF.sub.3, J=319 Hz), 56.8 (CMe.sub.2Ph), 33.2 (CMe.sub.2Ph), 29.8 (CMe.sub.2Ph), 21.4 (CH.sub.3), 20.6 (CH.sub.3), 18.7 (CH.sub.3); elemental analysis: C.sub.41H.sub.45F.sub.6MoN.sub.3O.sub.6S.sub.2; calculated: C, 51.79; H, 4.88; N, 4.42. found: C, 51.73; H, 4.80; N, 4.39.

(11) The catalyst Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMeS)(CH-tBu)(OTf).sub.2) (8) was prepared analogously to example 2, except using a corresponding amount of 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene rather than 1,3-di-t-butylimidazol-2-ylidene.

Example 8 (Preparation of Mo(N-2,6-Me2-C6H3)(IMesH2)(CHCMe2Ph)(OTf)(OCH(CF3)2)) (9)

(12) Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(CHCMe.sub.2Ph)(OTf).sub.2(DME) (0.0400 g, 0.0420 mmol) was dissolved in a minimal amount (2 mL) of C.sub.2H.sub.4Cl.sub.2, the solution was cooled to 30 C. and then LiOCH(CF.sub.3).sub.2 (0.0050 g, 0.0420 mmol) was added. The reaction mixture was stirred at room temperature for two hours and then filtered through Celite. After the solvent had been removed under reduced pressure, a yellow solid was obtained. The residue was dissolved in a minimal amount of dichloromethane and crystallized at 30 C. for several days, in order to obtain yellow crystals (63%). .sup.1H NMR (CD.sub.2Cl.sub.2): =13.49 (s, 1H, CHCMe.sub.2Ph, J.sub.CH=114 Hz), 7.28-6.41 (m, 14H, ArH), 3.97-3.82 (m, 4H, CH.sub.2NC), 2.32-1.79 (s, 30H, Me); .sup.13C NMR (CD.sub.2Cl.sub.2): 323.8 (CHCMe.sub.3), 210.0 (CN.sub.carbene), 155.2 (C.sub.ipso), 150.7, 139.5 (C.sub.ortho) r, 136.9 (C.sub.aryl), 135.8 (C.sub.aryl), 135.2 (C.sub.aryl), 130.1 (C.sub.aryl), 129.9 (C.sub.aryl), 129.1 (C.sub.aryl), 128.6 (C.sub.aryl), 127.8 (C.sub.aryl), 126.6 (C.sub.aryl), 125.8 (C.sub.aryl), 121.6 (CF.sub.3), 118.4 (q, CF.sub.3), 76.07-75.11 (q, OCH(CF.sub.3).sub.2), 56.1 (CMe.sub.2Ph), 51.9 (CH.sub.2-imidazolylidene), 37.2 (CMe.sub.2Ph), 29.3 (CMe.sub.2Ph), 21.5 (CH.sub.3), 21.3 (CH.sub.3), 19.0 (CH.sub.3), 18.9 (CH.sub.3); .sup.19F NMR (CD.sub.2Cl.sub.2): =73.07-73.14 (q, CF.sub.3), 77.33-73.40 (q, CF.sub.3), 78.07 (s, CF.sub.3SO.sub.3, trans to the NHC ligand). Elemental analysis: C.sub.44H.sub.50Cl.sub.2F.sub.9MoN.sub.3O.sub.4S; calculated: C, 50.05; H, 4.87; N, 3.98. found: C, 50.51; H, 4.85; N, 4.07.

Example 9 ((Preparation of [Mo(N-2,6-Me2-C6H3)(CHCMe2Ph)(OTf)(IMesH2)+ B(3,5-(CF3)2C6H3)4]) (10)

(13) [Ag.sup.+ B(3,5-(CF.sub.3).sub.2C.sub.6H.sub.3).sub.4] (0.0874 g, 0.0879 mmol) was dissolved in 1 mL of C.sub.2H.sub.4Cl.sub.2 and added at 30 C. to a solution of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(CHCMe.sub.2Ph)(OTf)(DME) (0.08370 g, 0.0879 mmol) in 2 mL of C.sub.2H.sub.4Cl.sub.2. The reaction mixture was stirred overnight, then filtered through Celite, and the solvent was removed under reduced pressure. The yellow residue was taken up in a minimal amount of dichloromethane and stored at 30 C. for several days in order to isolate the product in the form of yellow crystals in a 60% yield. .sup.1H NMR (CD.sub.2Cl.sub.2): =12.90 (s, 1H, CHCMe.sub.2Ph, J.sub.CH=127 Hz), 7.72-6.97 (m, 20H, ArH), 4.06 (s, 4H, CH.sub.2NC), 2.37-0.92 (s, 33H, Me); .sup.13C NMR (CD.sub.2Cl.sub.2): =325.0 (CHCMe.sub.3), 206.7 (CN.sub.carbene), 163.1-162.59 (q, .sup.1J.sub.BC=50 Hz), 154.0 (C.sub.ipso), 144.3, 143.2, 142.4, 141.3 (C.sub.ortho), 137.1 (C.sub.aryl), 135.4 (C.sub.aryl), 132.5 (C.sub.aryl), 131.6 (C.sub.aryl), 130.6 (C.sub.aryl), 130.0 (C.sub.aryl), 129.6 (C.sub.aryl), 129.2 (C.sub.aryl), 129.0 (C.sub.aryl), 128.8 (C.sub.aryl), 128.6 (C.sub.aryl), 127.8 (C.sub.aryl), 126.7 (C.sub.aryl), 126.3 (C.sub.aryl), 123.8, 121.1, 118.1, 57.5 (CMe.sub.2Ph), 52.8 (CH.sub.2-imidazolylidene), 28.8 (CMe.sub.2Ph), 21.4 (CH.sub.3), 21.3 (CH.sub.3), 20.7 (CH.sub.3), 19.8 (CH.sub.3), 18.7 (CH.sub.3), 18.0 (CH.sub.3). .sup.19F NMR (CD.sub.2Cl.sub.2): =62.89 (s, 3F), 75.66 (s, CF.sub.3SO.sub.3, trans to the imido ligand).

Example 10 (Preparation of Mo(N-2,6-Me2-C6H3)(3-mesityl-1-(1-phenylethyl)imidazolin-2-ylidene)(CHCMe2Ph)(OTf2)) (11)

(14) 3-Mesityl-1-(1-phenylethyl)-4,5-dihydrol-H-imidazol-3-ium tetrafluoroborate (0.0820 g, 0.2160 mmol) was suspended in 2 mL of benzene. KHMDS (0.0430 g, 0.2160 mmol) was added to the suspension while stirring. After a reaction time of one hour, the clear benzene solution was filtered through Celite. Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3) (CHCMe.sub.2Ph)(OTf.sub.2)(DME) (0.1580 g, 0.2160 mmol; J. Organomet. Chem. 1993, 459, 185) was dissolved in 8 mL of benzene and the solution was stirred for 15 minutes. The previously filtered benzene solution of the free NHC was then added thereto, with observation of an immediate color change from yellow to dark red. After stirring for three hours, the benzene was removed, and the yellow residue was washed with n-pentane and dried under reduced pressure (0.0110 g, 85%). The residue was dissolved in a minimal amount of dichloromethane and stored at 30 C. for several days in order to obtain yellow crystals (60%). .sup.1H NMR (CD.sub.2Cl.sub.2): =14.73 (s, 1H, CHCMe.sub.2Ph), 7.36-6.99 (m, 14H, ArH), 6.29 (s, 1H, Ar-Mes), 4.08-3.80 (m, 4H, CH.sub.2NC), 2.46-1.39 (s, 24H, Me); .sup.19F NMR (CD.sub.2Cl.sub.2): =77.06 (s, CF.sub.3SO.sub.3), 77.77 (s, CF.sub.3SO.sub.3, trans to the NHC ligand); elemental analysis calculated for C.sub.41H.sub.47Cl.sub.2F.sub.6MoN.sub.3O.sub.6S.sub.2; C, 48.14; H, 4.73; N, 4.10. found: C, 48.17; H, 4.68; N, 4.06.

Example 11 (Preparation of Mo(N-2,6-Me2-C6H3)(IMesH2)(CHCMe3)(OTf)(OCH(CH3)2)) (13)

(15) Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.3)(OTf).sub.2 (0.080 g, 0.0900 mmol) was dissolved in a minimal amount (2 mL) of C.sub.2H.sub.4Cl.sub.2, the solution was cooled to 30 C. and then LiOCH(CH.sub.3).sub.2 (0.0050 g, 0.0900 mmol) was added. The reaction mixture was stirred at room temperature for two hours, then filtered through Celite, and the solvent was removed under reduced pressure. The yellow residue was taken up in a minimal amount of dichloromethane and stored at 30 C. for several days in order to isolate the product in the form of yellow crystals in 63% yield.

(16) The catalyst Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.3)(OTf)-(OOCCF.sub.3) (14) was prepared analogously to example 11, except using a corresponding amount of lithium trifluoroacetate instead of LiOCH(CH.sub.3).sub.2.

Example 12 (Preparation of Mo(N-2,6-Me2-C6H3)(IMesH2)(CHCMe3)(OTf)(OC6H5)) (15)

(17) Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.3)(OTf).sub.2 (0.0300 g, 0.0315 mmol) was dissolved in a minimal amount (2 mL) of C.sub.2H.sub.4Cl.sub.2, the solution was cooled to 30 C. and then LiOC.sub.6F.sub.5 (0.0050 g, 0.0315 mmol) was added. The reaction mixture was stirred at room temperature for two hours and then filtered through Celite. After the solvent had been removed under reduced pressure, a yellow solid was obtained. The residue was dissolved in a minimal amount of dichloromethane and stored at 30 C. for several days in order to obtain yellow crystals.

Example 13 (Preparation of Mo(N-2-tBu-C6H4)(IMesH2)(CHCMe2Ph)(OTf)2) (12)

(18) Mo(N-2-.sup.tBu-C.sub.6H.sub.4)(CHCMe.sub.2Ph)(OTf).sub.2(DME) (0.0320 g, 0.0430 mmol) was first dissolved in 2 mL of toluene. 1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidin-2-ylidene (0.0130 g, 0.0430 mmol) was dissolved 1 mL of toluene. A color change from yellow to light orange was observed here. After stirring for three hours, the toluene was then removed and the residue was dried under reduced pressure. The product was isolated as a yellow solid.

Example 14 (Preparation of Mo(NtBu)(Cl)2(1,3-iPr2-4,5-Cl2-imidazol-2-ylidene)(pyridine)(CHCMe3)) (16)

(19) Mo(NtBu)(Cl).sub.2(pyridine).sub.2(CHCMe.sub.3) (0.036 g, 0.078 mmol) was dissolved in 5 mL of dichloromethane. 1,3-Me.sub.2-4,5-Cl.sub.2-imidazol-2-ylidene-AgI (0.036 g, 0.36 mmol, 1.0 equiv.) was added in solid form. The suspension was stirred at room temperature for 1 hour. Subsequently, the suspension was filtered through Celite and the solvent was removed. The pale yellow solids were taken up in 4 mL of dichloromethane and filtered once more. The solvent was removed and the solids were washed with n-pentane. The product was obtained as a pale orange solid. Yield: 0.039 g (82%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =1.55 (s, br, 9H, tBu), 1.67 (s, br, 9H, tBu), 1.71 (d, br, 12H, iPr-Me), 4.98 (m, br, 2H, iPr-CH), 7.56 (m, br, 2H, pyr), 8.02 (m, br, 1H, pyr), 9.21 (m, br, 1H, pyr), 9.86 (m, br, 1H, pyr), 14.38 (s, br, 1H, MoCH).

Example 15 (Synthesis of Cat. 17)

(20) 31.1 mg (0.076 mmol of 1-(2,6-diisopropylphenyl)-3-(2-hydroxyphenyl)-4,5-dihydroimidazolium tetrafluoroborate and 25.4 mg (0.152 mmol) of LiHMDS were suspended in benzene. After the mixture had been stirred at room temperature for 1 h, the solids were filtered off and the filtrate was added dropwise to a solution of 60 mg (0.076 mmol) of Mo(N-2,6-C.sub.6H.sub.3.sup.iPr.sub.2)(CH.sub.2CMe.sub.2Ph)(OSO.sub.2CF.sub.3).sub.2(DME). The yellow solution darkened somewhat and became slightly cloudy. The mixture was stirred at room temperature for 3 h and then filtered through Celite. The solvent was removed under reduced pressure and the yellow solids obtained were dissolved in a little dichloromethane. Yellow crystals were obtained at 35 C. .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz) =13.64 (s, 1H, CHCMe.sub.2Ph, J.sub.CH=119 Hz); 7.50-7.41 (m, 2H, CH); 7.28-7.18 (m, 5H, CH); 7.17-7.01 (m, 7H, CH); 6.95 (dd, J=7.79, 1.32 Hz; 1H, CH); 4.60-4.47 (m, 1H, CH); 4.38-4.26 (m, 1H, CH); 4.07-3.94 (m, 1H, CH); 3.93-3.80 (m, 1H, CH); 3.72-3.56 (m, 2H, CH); 2.68 (hept, J=6.88 Hz; 1H, CH); 2.51 (hept, J=6.51 Hz; 1H, CH); 1.14 (d, J=6.81 Hz; 6H, CH.sub.3); 1.03 (s, 3H, CH.sub.3); 0.98 (d, J=6.84 Hz; 3H, CH.sub.3); 0.5 (d, J=6.81 Hz; 3H, CH.sub.3); 0.84 (d, J=6.86 Hz; 6H, CH.sub.3); 0.3 (d, J=6.74 Hz; 3H, CH.sub.3); 0.6 (d, J=6.80 Hz; 3H, CH.sub.3); 9F NMR (CD.sub.2Cl.sub.2) =77.94 (SO.sub.3CF.sub.3); .sup.13C NMR (CD.sub.2Cl.sub.2, 100 MHz) =316.9 (CH-Me.sub.2Ph), 205.9 (CN.sub.carbene), 152.2 (C.sub.ar.), 151.9 (C.sub.ar.), 149.3 (C.sub.ar.), 147.4 (C.sub.ar.), 146.5 (C.sub.ar.), 145.7 (C.sub.ar.), 137.2 (C.sub.ar.), 130.3 (C.sub.ar.), 129.7 (C.sub.ar.), 128.5 (C.sub.ar.), 128.4 (C.sub.ar.), 126.9 (C.sub.ar.), 126.7 (C.sub.ar.), 126.6 (C.sub.ar.), 126.4 (C.sub.ar.), 125.3 (C.sub.ar.), 123.2 (C.sub.ar.), 120.9 (C.sub.ar.), 120.6 (C.sub.ar.), 119.9 (q, CF.sub.3, J=319 Hz), 117.5 (C.sub.ar.), 55.6 (CH.sub.2-imidazolylidene), 54.9 (CH.sub.2-imidazolylidene), 49.4 (CMe.sub.2Ph), 34.8, 29.7, 28.7, 28.5, 26.6, 26.1, 25.9, 24.3, 23.4, 22.7, 21.5.

Example 16 (Synthesis of Cat. 18)

(21) 30.03 mg (0.086 mmol) of 1-(mesityl)-3-(2-hydroxyphenyl)-4,5-dihydroimidazolium tetrafluoroborate and 27.30 mg (0.163 mmol) of LiHMDS were suspended in benzene and stirred at room temperature for 2 h. The LiBF.sub.4 formed was filtered off and the filtrate was slowly added dropwise to a solution of 60 mg (0.086 mmol) of Mo(N-2,6-C.sub.6H.sub.3Me.sub.2)(CH.sub.2CMe.sub.2Ph)(OSO.sub.2CF.sub.3).sub.2-(DME) in benzene. The reaction mixture was stirred at room temperature for 3 h and then filtered through Celite. The solvent was removed under reduced pressure and the residue was dissolved in a little dichloromethane. A couple of drops of n-pentane were added and the product was obtained at 35 C. as dark yellow crystals. .sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz) =(anti/syn 2:3) 14.46; 12.81 (s, 1H, CHCMe.sub.2Ph, J.sub.CH=147 Hz (anti), 116 Hz (syn)); 7.31-7.13 (m, 7H, CH); 7.11-7.02 (m, 2H, CH); 7.01-6.76 (m, 3H, CH); 6.70; 6.63 (s, br, 1H, CH); 6.14; 6.02 (s, br, 1H, CH); 4.44-4.15 (m, 2H, CH.sub.2); 2.30 (s, CH.sub.3); 2.22 (s, 3H, CH.sub.3); 2.07 (s, CH.sub.3); 2.05 (s, 3H, CH.sub.3); 1.98 (s, CH.sub.3); 1.84 (s, CH.sub.3); 1.70 (s, CH.sub.3); 1.69 (s, CH.sub.3); 1.57 (s, CH.sub.3); 1.44 (s, CH.sub.3); 1.38 (s, CH.sub.3); 1.30 (s, CH.sub.3); .sup.19F NMR (CD.sub.2Cl.sub.2) =78.13 (SO.sub.3CF.sub.3); 78.21 (SO.sub.3CF.sub.3); .sup.13C NMR (CD.sub.2Cl.sub.2, 100 MHz) =330.2 (CH-Me.sub.2Ph), 309.3 (CH-Me.sub.2Ph), 210.4 (CN.sub.carbene), 208.1 (CN.sub.carbene), 154.8 (C.sub.ar.), 154.6 (C.sub.ar.), 153.6 (C.sub.ar.), 151.8 (C.sub.ar.), 147.8 (C.sub.ar.), 147.7 (C.sub.ar.), 140.3 (C.sub.ar.), 138.9 (C.sub.ar.), 136.4 (C.sub.ar.), 136.1 (C.sub.ar.), 136.0 (C.sub.ar.), 135.6 (C.sub.ar.), 135.5 (C.sub.ar.), 135.3 (C.sub.ar.), 134.6 (C.sub.ar.), 130.1 (C.sub.ar.), 130.1 (C.sub.ar.), 130.0 (C.sub.ar.), 129.7 (C.sub.ar.), 129.4 (C.sub.ar.), 129.3 (C.sub.ar.), 128.2 (C.sub.ar.), 127.8 (C.sub.ar.), 127.7 (C.sub.ar.), 127.3 (C.sub.ar.), 126.7 (C.sub.ar.), 126.7 (C.sub.ar.), 126.6 (C.sub.ar.), 126.5 (C.sub.ar.), 126.1 (C.sub.ar.), 126.0 (C.sub.ar.), 121.0 (C.sub.ar.), 120.7 (C.sub.ar.), 120.4 (C.sub.ar.), 120.1 (C.sub.ar.), 120.0 (q, CF.sub.3, J=319 Hz), 120.0 (q, CF.sub.3, J=320 Hz), 117.8 (C.sub.ar.), 117.3 (C.sub.ar.), 54.7 (CH.sub.2-imidazolylidene), 54.2 (CH.sub.2-imidazolylidene), 51.7 (CH.sub.2-imidazolylidene), 51.3 (CH.sub.2-imidazolylidene), 49.7 (CMe.sub.2Ph), 49.5 (CMe.sub.2Ph), 32.4 (CH.sub.3), 29.2 (CH.sub.3), 29.2 (CH.sub.3), 27.3 (CH.sub.3), 21.1 (CH.sub.3), 21.0 (CH.sub.3), 20.5 (CH.sub.3), 19.0 (CH.sub.3), 18.5 (CH.sub.3), 18.0 (CH.sub.3), 17.8 (CH.sub.3), 17.3 (CH.sub.3).

Example 17 (ROMP of 5,6-bis((pentyloxy)methyl)bicyclo-[2.2.1]hept-2-ene)

(22) To an initially charged solution of the monomer (0.05 g, 0.167 mmol) in 2 mL of dichloromethane was added at room temperature, all at once, a catalyst solution of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf).sub.2 (6) (0.0032 g, 0.0033 mmol) in 0.5 mL of dichloromethane. The mixture was stirred for four hours and then the polymer was precipitated in n-pentane. The wash phase was concentrated and precipitated again. The colorless polymer was washed with n-pentane and dried (0.045 g, 90%). .sup.1H NMR (400 MHz, CDCl.sub.3): =5.27-5.15 (m, 2H), 3.34 (brs, 10H), 2.70 (brs, 1H), 2.31 (brs, 1H), 1.93 (brs, 2H), 1.54 (brs, 4H), 1.32 (brs, 8H), 0.89 (brs, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3): =134, 133.7, 71.25-70.25 (m), 50.9-39.91 (m), 29.7, 29.6, 28.7, 22.7, 14.2; FT-IR (ATR, cm.sup.1): 2928 (s), 2854 (s), 1460 (m), 1369 (m), 1104 (s), 967 (w), 734 (w); M.sub.n=4000 g/mol, PDI=1.03, .sub.trans=88%.

(23) With Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMes)(CHCMe.sub.2Ph)(OTf).sub.2 (7) (0.0032 g, 0.0033 mmol) in dichloromethane (0.5 mL) and the monomer (0.05 g, 0.167 mmol) in dichloromethane (2 mL), the polymer was isolated with a yield of 84% (0.042 g). .sup.1H NMR (400 MHz, CDCl.sub.3): =5.27-5.17 (m, 2H), 3.34 (brs, 10H), 2.70 (brs, 1H), 2.31 (brs, 1H), 1.93 (brs, 2H), 1.54 (brs, 4H), 1.32 (brs, 8H), 0.89 (brs, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3): =134, 133.7, 71.12-70.63 (m), 47.60-39.92 (m), 29.7, 28.7, 22.7, 14.2; FT-IR (ATR, cm.sup.1): 2928 (s), 2854 (s), 1460 (m), 1369 (m), 1104 (s), 967 (w), 733 (w); M.sub.n=8200 g/mol, PDI=1.06, .sub.trans=93%.

(24) With Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf)(OCH(CF.sub.3).sub.2) (9) (0.0026 g, 0.00271 mmol) in dichloromethane (0.5 mL) and the monomer (0.04 g, 0.1358 mmol) in dichloromethane (2 mL), the polymer was prepared with a yield of 28% (0.012 g). .sup.1H NMR (400 MHz, CDCl.sub.3): =5.27-5.17 (m, 2H), 3.34 (brs, 10H), 2.70 (brs, 1H), 2.31 (brs, 1H), 1.93 (brs, 2H), 1.54 (brs, 4H), 1.32 (brs, 8H), 0.89 (brs, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3): =134, 133.6, 71.11-70.11 (m), 47.60-39.78 (m), 29.6, 29.5, 28.5, 22.6, 22.5, 14.2; FT-IR (ATR, cm.sup.1); 2928 (s), 2854 (s), 1460 (m), 1369 (m), 1104 (s), 966 (w), 737 (w); M.sub.n=11 400 g/mol, PDI=1.22, .sub.trans=64%.

Example 18

(25) The polymerization of the same monomer with Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(I-tBu)(CH-tBu)(OTf).sub.2 (2) (0.050 g of monomer, 2.6 mg of catalyst) affords the polymer in 60% isolated yield (M.sub.n=8500 g/mol), PDI=1.1, .sub.trans=50%).

Example 19 (ROMP of 7-oxabicyclo[2.2.1]hept-5-ene-2,3-diylbis(methylene) diacetate)

(26) A cooled solution (35 C.) of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(I-tBu)-(CH-tBu)(OTf).sub.2 (2) (0.0045 g, 0.0050 mmol) in CH.sub.2Cl.sub.2 (0.5 mL) was added to a solution of the monomer (0.0600 g, 0.2520 mmol) in CH.sub.2Cl.sub.2 (2 mL) at 30 C. After 24 hours, the polymer was precipitated by adding pentane, washed with pentane and dried. Yield: 0.058 g (97%). FT-IR (ATR, cm.sup.1): 2902 (m), 1732 (s), 1431 (w), 1366 (s), 1220 (s), 1104 (w), 1029 (s), 968 (s), 728 (m). .sup.1H NMR (400 MHz, CDCl.sub.3): 5.72-5.58 (m, 2H), 4.49 (brs, 1H), 4.18 (m, 5H), 2.40 (brs, 2H), 2.03 (brs, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3): 170.8, 133.1, 81.4, 61.9, 45.8, 20.9. M.sub.n=13 000 g/mol, PDI=1.7, .sub.trans=85%.

Example 20

(27) The polymerization of 0.050 g of the same monomer with 0.0032 g of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(I-tBu)-(CH-tBu)(OTf).sub.2 (2) affords the polymer in 35% yield (M.sub.n=1800 g/mol, PDI=1.2, .sub.trans=33%).

Example 21 (ROMP of 2-(N-cyclohexylmethyl)norborn-5-ene)

(28) To a cooled solution (30 C.) of 2-(N-cyclohexylmethyl)-norborn-5-ene (57.7 mg) in CH.sub.2Cl.sub.2 (2 mL) was added a solution of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) (40 mg) in CH.sub.2Cl.sub.2 (0.5 mL). The reaction mixture was stirred at 80 C. for 24 h; then the polymer was precipitated by adding pentane, filtered off and dried (44.5 mg, 90%). FT-IR (ATR, cm.sup.1): 3270 (m), 2935 (s), 2860 (m), 2450 (m), 2075 (s), 1681 (m), 1454 (s), 1225 (m), 1159 (s), 1030 (s), 807 (s), 636 (s); .sup.1H NMR (400 MHz, D.sub.2O, hydrochloride salt): =6.40-5.86 (m), NH.sub.2.sup.+ part of the D.sub.2O signal at 4.7, 3.17 (b), 3.03-2.96 (m), 2.60-2.0 (b, m), 1.93 (b), 1.74 (b), 1.40 (b), 1.28 (b); M.sub.n=13 100 g/mol, PDI=1.10.

(29) With Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf).sub.2 (6) (0.0074 g, 0.0078 mmol) and monomer (0.0400 g, 0.1951 mmol) in CH.sub.2Cl.sub.2 (3 mL), the polymer was obtained in 70% yield (0.028 g). FT-IR (ATR, cm.sup.1): 3421 (m), 2935 (s), 2858 (m), 2424 (m), 1630 (m), 1454 (s), 1222 (s), 1155 (s), 1030 (s), 724 (s), 637 (s); .sup.1H NMR (400 MHz, CDCl.sub.3): =8.69, 8.02, 7.04, 6.92, 6.19, 5.79, 5.77, 5.36, 5.28, 4.52, 3.83, 3.10, 2.96, 2.80, 2.36, 2.14, 2.00, 1.25, 0.86; .sup.13C NMR (101 MHz, CDCl.sub.3): =141.2, 138.8, 134.9, 132.0, 130.3, 129.3, 58.1, 49.8, 48.6, 44.5, 42.3, 35.7, 34.3, 24.8, 22.2, 17.8, 14.12.

(30) With Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMes)(CHCMe.sub.2Ph)(OTf).sub.2 (7) (0.0075 g, 0.0078 mmol) in dichloromethane (0.5 mL) and the monomer (0.04 g, 0.1951 mmol) in chloroform (2 mL), the polymer was obtained with 65% yield (0.026 g). FT-IR (ATR, cm.sup.1): 3425 (m), 2920 (s), 2858 (m), 2424 (m), 1630 (m), 1454 (s), 1222 (s), 1155 (s), 1030 (s), 724 (s), 637 (s); .sup.1H NMR (400 MHz, CDCl.sub.3): =8.64, 7.06, 6.22, 6.21, 5.69, 5.34, 3.09, 2.85, 2.34, 2.17, 1.84, 1.82, 1.24, 0.88; .sup.13C NMR (101 MHz, CDCl.sub.3): =142.0, 138.8, 134.0, 131.7, 129.8, 50.10, 42.68, 34.4, 24.1, 22.8, 14.

(31) With Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf)(OCH(CF.sub.3).sub.2) (9) (0.0082 g, 0.0078 mmol) in dichloromethane (0.5 mL) and the monomer (0.04 g, 0.1951 mmol) in dichloromethane (2 mL), the polymer was isolated with a yield of 54% (0.022 g). .sup.1H NMR (400 MHz, CDCl.sub.3): =6.97, 6.17, 6.07, 5.79, 5.77, 5.35, 5.33, 4.54, 3.45, 3.18, 2.96, 2.82, 2.64, 2.36, 2.31, 1.81, 1.60, 1.24; .sup.13C NMR (101 MHz, CDCl.sub.3): =140.7, 138.5, 137.1, 136.6, 135.2, 132.3, 130.3, 58.2, 48.7, 45.0, 42.8, 42.6, 36.2, 31.5, 29.0, 24.8, 21.0, 17.5, 14.4; FT-IR (ATR, cm.sup.1): 3421 (m), 2935 (s), 2858 (m), 2424 (m), 1630 (m), 1454 (s), 1222 (s), 1155 (s), 1030 (s), 724 (s), 637 (s).

Example 22 (ROMP of 2-(N,N-dimethylaminomethyl)-norborn-5-ene)

(32) To a cooled solution (30 C.) of 2-(N,N-dimethylaminomethyl)norborn-5-ene (79.7 mg) in CH.sub.2Cl.sub.2 (2 mL) was added a solution of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) (10.5 mg) in CH.sub.2Cl.sub.2 (0.5 mL). After stirring for 24 hours, the polymer was precipitated by adding pentane and filtered off and dried. Yield: 27 mg (34%). FT-IR (ATR, cm.sup.1): 2955 (s), 1629 (s), 1464 (s), 1259 (s), 1151 (s), 1029 (s), 636 (s); .sup.1H NMR (400 MHz, DMSO-d.sup.6): =6.98, 5.42, 3.14, 2.66, 2.32, 2.20, 2.17, 2.05, 0.85; M.sub.n=10 500 g/mol, PDI=1.21.

Example 23 (ROMP of norborn-5-ene-2,3-dimethanol)

(33) A solution of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) (0.0173 g, 0.0194 mmol) in CHCl.sub.3 (1.5 mL) was added to a solution of the monomer (0.0300 g, 0.1940 mmol) in CHCl.sub.3 (2 mL) at room temperature. The reaction mixture was then stirred at 55 C. for 5 hours. Subsequently, the polymer is precipitated from pentane, washed with pentane and dried. Yield 80% (0.024 g). FT-IR (ATR, cm.sup.1): 3373 (s), 2930 (s), 2884 (s), 1477 (m), 1261 (s), 1109 (s), 1023 (s), 921 (w), 632 (s); .sup.1H NMR (400 MHz, DMSO-d.sup.6): 5.48-5.40 (m, 2H), 3.86 (brs, 2H), 3.44 (brs, 4H), 2.45 (brs, 1H), 2.10 (brs, 1H), 1.83 (brs, 1H), 1.57 (brs, 1H), 1.33 (brs, 1H). .sup.13C NMR (101 MHz, CDCl.sub.3): =134.8, 129.5, 69.4, 59.3, 47.8, 47.0, 43.8, 43.4, 37.5 (b), 32.3; M.sub.n=2800 g/mol, PDI=1.12.

Example 24 (ROMP of bicyclo[2.2.1]hept-5-ene-2-carbaldehyde)

(34) A solution of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) (0.006 g, 0.0068 mmol) in CH.sub.2Cl.sub.2 (1.0 mL) was added to a solution of the monomer (0.0400 g, 0.3438 mmol) in CH.sub.2Cl.sub.2 (1.0 mL) at room temperature. The reaction mixture was then stirred at room temperature for 20 hours. Subsequently, the reaction was quenched with MeOH:HCl (90:10 vol./vol.). The polymer thus precipitated was washed with pentane and dried. Yield: 55% (0.022 g). FT-IR (ATR, cm.sup.1): 2942 (s), 2830 (m), 1720 (s), 1630 (s), 1470 (s), 1255 (s), 1158 (s), 1026 (s), 719 (s), 636 (s); .sup.1H NMR (400 MHz, THF-d8): =9.53 (CHO), 6.13 (b), 5.95 (b), 4.62 (b), 2.75 (b); .sup.13C NMR (101 MHz, THF-ds): =204.6 (CHO), 141.2, 136.9, 131.9, 130.7, 128.7, 43.2, 30.4, 21.2, 19.0, 17.9; M.sub.n=5000 g/mol, PDI=2.1 (M.sub.n, theor.=6100 g/mol).

Example 25 (General Method for the Cyclopolymerization of Diynes)

(35) The catalyst was dissolved in the solvent specified and this solution was added rapidly to one of the monomer in the same solvent. After 2 hours, the polyreactions were terminated by addition of wet methanol. After a further 10 min, the polymer was precipitated by adding methanol or pentane and dried.

Example 26 (Preparation of poly(4,4,5,5-tetrakis-(ethoxycarbonyl)-1,7-octadiyne))

(36) The polymer was obtained according to example 25 using Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) (3.6 mg, 0.004 mmol) and the monomer (80 mg, 0.203 mmol) in 81% isolated yield (64 mg). IR (cm.sup.1): 2901 (m), 1730 (s), 1461 (m), 1444 (m), 1387 (m), 1363 (m), 1265 (s), 1198 (m), 1122 (w), 1095 (m), 1052 (m), 1027 (s), 941 (m), 856 (m), 781 (w), 703 (w); .sup.1H NMR (400 MHz, CDCl.sub.3): =6.71 (s, 2H, CH), 4.41-4.25 (bs, 8H, CH.sub.2), 3.25-3.18 (bs, 4H, CH.sub.2), 1.38-1.23 (bs, 12H, CH.sub.3); .sup.13C NMR (101 MHz, CDCl.sub.3): =169.7, 130.8, 124.7, 61.7, 56.9, 32.5, 13.7; UV/Vis (CHCl.sub.3): .sub.max=484 nm. M.sub.n=13 200 g/mol, PDI=1.9 (M.sub.n, theor.=19 700 g/mol).

(37) It was possible to isolate the polymer through the use of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf).sub.2 (6) (0.0036 g, 0.004 mmol) and the monomer (0.0800 g, 0.203 mmol) with 81% yield (64 mg). The polymerization was initiated at 30 C., and stirring was continued at 80 C. for one hour. .sup.1H NMR (CDCl.sub.3): =7.01 (br, m, 2H), 4.21 (br, m, 8H), 3.18 (br, m, 4H), 1.28 (br, m, 12H); .sup.13C NMR (CDCl.sub.3): =169.9, 131.0, 125.0, 61.9, 57.1, 32.7, 14.0; FT-IR (ATR, cm.sup.1): 2981 (m), 1729 (s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s), 1027 (w), 945 (s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl.sub.3): .sub.max=483 nm, M.sub.n=15 000 g/mol, PDI=2.2, insertion: 96%.

(38) With the monomer (0.0400 g, 0.1014 mmol) and Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMes)(CHCMe.sub.2Ph)(OTf).sub.2 (7) (0.0019 g, 0.0020 mmol), the polymer was prepared with a yield of 75% (0.03 g). .sup.1H NMR (CDCl.sub.3): =7.02 (br, m, 2H), 4.21 (br, m, 8H), 3.18 (br, m, 4H), 1.27 (br, m, 12H); .sup.13C NMR (CDCl.sub.3): =169.9, 131.0, 125.0, 61.9, 57.1, 32.7, 14.0; FT-IR (ATR, cm.sup.1): 2981 (m), 1729 (s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s), 1027 (w), 945 (s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl.sub.3): .sub.max=481 nm, M.sub.n=14 000 g/mol, PDI=1.8, insertion: 96%.

(39) With Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf)(OCH(CF.sub.3).sub.2) (9) (0.0022 g, 0.0020 mmol) and the monomer (0.0400 g, 0.1014 mmol), the polymer was likewise isolated with a yield of 75% (0.03 g). .sup.1H NMR (CDCl.sub.3): =7.02 (br, m, 2H), 4.22 (br, m, 8H), 3.19 (br, m, 4H), 1.27 (br, m, 12H); .sup.13C NMR (CDCl.sub.3): =169.9, 131.0, 125.0, 61.9, 57.1, 32.7, 14.0; FT-IR (ATR, cm.sup.1): 2981 (m), 1729 (s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s), 1027 (w), 945 (s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl.sub.3): .sub.max=482 nm, M.sub.n=22 000 g/mol, PDI=2.1, insertion: 96%.

Example 27 (Preparation of poly(2-(prop-2-yn-1-yl)-pent-4-ynoic Acid))

(40) The polymer was prepared from Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf).sub.2 (6) (0.0055 g, 0.0059 mmol) and the monomer (0.004 g, 0.294 mmol) with a yield of 65% (0.0260 g). The polymerization was initiated at 30 C. and stirring was continued at 80 C. for one hour. .sup.1H NMR (400 MHz, d.sub.6-DMSO): =12.25, 7.07-6.84, 3.23, 2.34; .sup.13C NMR (400 MHz, d.sub.6-DMSO): =177.0, 135.4, 129.5, 71.1, 58.1; FT-IR (ATR, cm.sup.1): 2981 (m), 1729 (s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s), 1027 (w), 945 (s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl.sub.3): .sub.max=587, 547 nm.

(41) With Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMes)(CHCMe.sub.2Ph)(OTf).sub.2 (7) (0.0055 g, 0.0059 mmol) and the monomer (0.0400 g, 0.294 mmol), the polymer was isolated with 55% yield (0.022 g). .sup.1H NMR (400 MHz, d.sub.6-DMSO): =12.27, 6.68-6.76, 3.23, 2.34; .sup.13C NMR (400 MHz, d.sub.6-DMSO): =177.0, 135.4, 129.5, 71.1, 58.1; FT-IR (ATR, cm.sup.1: 2981 (m), 1729 (s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s), 1027 (w), 945 (s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl.sub.3): .sub.max=587, 547 nm.

(42) With the monomer (0.0400 g, 0.294 mmol) and Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf)(OCH(CF.sub.3).sub.2) (9) (0.0062 g, 0.0059 mmol), it was likewise possible to obtain the polymer with a yield of 55% (0.022 g). .sup.1H NMR (400 MHz, d.sub.6-DMSO): =12.27, 6.68-6.76, 3.23, 2.34; .sup.13C NMR (400 MHz, d.sub.6-DMSO): =177.0, 135.4, 129.5, 71.1, 58.1; FT-IR (ATR, cm.sup.1): 2981 (m), 1729 (s), 1444 (w), 1368 (s), 1262 (s), 1199 (w), 1092 (s), 1027 (w), 945 (s), 862 (w), 700 (w), 636 (w), 579 (w). UV/Vis (CHCl.sub.3): .sub.max=587, 547 nm.

Example 28 (Preparation of poly(2,2-di(prop-2-yn-1-yl)propane-1,3-diol))

(43) The polymer was obtained using Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) in 80% isolated yield (0.030 g). .sup.1H NMR (400 MHz, d.sub.6-DMSO): =7.09-6.66 (m, 2H), 4.60 (brs, 2H), 3.17 (s, 2H), 2.08 (s, 2H). UV-vis: .sub.max=593, 554 nm (DMSO).

(44) With Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf).sub.2 (6) (0.010 g, 0.0105 mmol) and the monomer (0.04 g, 0.2628 mmol), the polymer was prepared with a yield of 70% (0.027 g). The polymerization was initiated at 30 C., and stirring was continued at room temperature for one hour. .sup.1H NMR (400 MHz, d.sub.6-DMSO): =7.27-6.66, 4.42, 2.34, 2.29, 1.9; .sup.13C NMR (101 MHz, d.sub.6-DMSO): 5=139.7, 135.4, 130.9, 129.4, 50.9, 20.5, 17.6, 17.2; IR (ATR mode, cm.sup.1): 3400 (w), 2977 (w), 1444 (w), 1367 (w), 1247 (m), 1159 (m), 1065 (m), 946 (w), 856 (w), 629 (w). UV-vis: .sub.max=593, 554 nm (DMSO); M.sub.n=5000 g/mol, PDI=2.1.

(45) In the case of use of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMes) (CHCMe.sub.2Ph)(OTf).sub.2 (7) (0.010 g, 0.0105 mmol) and the monomer (0.0400 g, 0.2628 mmol), it was possible to prepare the polymer with a yield of 65% (0.026 g). .sup.1H NMR (400 MHz, d.sub.6-DMSO): =7.19-6.72, 2.86, 2.34, 2.26, 2.1, 1.82; .sup.13C NMR (101 MHz, d.sub.6-DMSO); =139.7, 135.4, 130.9, 129.4, 50.9, 20.5, 17.6, 17.2; IR (ATR mode, cm.sup.1): 3420 (w), 2963 (w), 1465 (w), 1353 (w), 1233 (m), 1122 (m), 1072 (m), 920 (w), 863 (w), 640 (w). UV-vis: .sub.max=595, 554 nm (DMSO); M.sub.n=3900 g/mol, PDI=1.8.

(46) In the case of use of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf)(OCH(CF.sub.3).sub.2) (9) (0.0011 g, 0.0052 mmol) and the monomer (0.0400 g, 0.212 mmol), the polymer was isolated with 54% yield (0.022 g). IR (ATR mode, cm.sup.1): 3400 (w), 2977 (w), 1444 (w), 1367 (w), 1247 (m), 1159 (m), 1065 (m), 946 (w), 856 (w), 629 (w). UV-vis: .sub.max=593, 554 nm (DMSO); M.sub.n=3000 g/mol, PDI=1.3.

Example 29 (poly(dipropargylmalonitrile))

(47) A solution of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) (0.016 g, 0.0211 mmol) in CH.sub.2Cl.sub.2 (0.5 mL) was added to a solution of the monomer (0.0300 g, 0.211 mmol) in CH.sub.2Cl.sub.2 (2 mL) at 30 C. The mixture was stirred at room temperature for 90 min, then quenched with MeOHHCl (90:10, vol./vol.). The precipitated polymer was washed with pentane and dried. Yield: 60% (0.018 g). IR (cm.sup.1): 2960 (m), 2252 (w), 1588 (w), 1484 (m), 1267 (s), 1232 (s), 1027 (s), 810 (w), 636 (s); .sup.1H NMR (DMSO-d.sub.6): =7.5-6.5 (b), 53.8 (b); .sup.13C NMR (DMSO-d.sub.6): =160.2, 139.6, 135.4, 130.8, 129.4, 50.9, 30.2, 20.6, 17.6; UV/Vis (DMSO): .sub.max=530 nm. M.sub.n=1100 g/mol, PDI=1.15 (M.sub.n, theor.=1420 g/mol).

Example 30 (poly(1,7-octadiyne-4,5-dicarboxylic Acid)

(48) A solution of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) (0.0137 g, 0.0154 mmol) in CH.sub.2Cl.sub.2 (1.0 mL) was added to a solution of the monomer (0.0300 g, 0.1956 mmol) in THF (2 mL) at 30 C. The reaction mixture was stirred at room temperature for 1 hour, then the polymer was precipitated with pentane, washed with pentane and dried. Yield: 90% (0.034 g). IR (cm.sup.1): 3288 (m), 2918 (m), 1702 (s), 1431 (m), 1213 (s), 1168 (s), 1026 (s), 946 (m), 634 (s); .sup.13C NMR (CDCl.sub.3): =174.8, 128-140 (b), 40.4, 30.1; .sup.13C NMR (LiOD/D.sub.2O): =184.5, 132-128, 44.4, 30.5; UV/Vis (THF): .sub.max=432 nm. M.sub.n=2600 g/mol, PDI=1.3 (M.sub.n, theor.=2500 g/mol).

Example 31 (poly(4,4-bis(ethoxycarbonyl)-1,6-heptadiyne; poly(DEDPM))

(49) The polymer was prepared using Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) (4.5 mg, 0.0051 mmol) and the monomer (60 mg, 0.2540 mmol) in 89% yield (53 mg). The polymerization was initiated at 30 C. and then conducted at room temperature for a further hour. .sup.1H NMR (CDCl.sub.3): =6.95-6.83 (s, 1H, CH), 6.45 (s, 1H, CH), 4.10-3.37 (bm, 6H, CH.sub.2), 2.82 (s, 1H, CH), 2.05-1.80 (m, 2H, CH.sub.2), 1.17 (s, 3H); .sup.13C NMR (CDCl.sub.3): =170.9, 170.8, 169.0, 137.0, 123.2, 61.9, 58.2, 58.0, 57.3, 57.1, 54.3, 54.1, 41.5, 29.7, 14.1; IR (ATR, cm.sup.1): 3367 (m), 2969 (s), 2929 (s), 2864 (s), 1673 (s), 1519 (m), 1453 (m), 1366 (s), 1337 (w), 1258 (w), 1190 (w), 1125 (s), 1077 (s), 947 (m), 770 (s), 690 (w); UV/Vis (CHCl.sub.3): .sub.max=548, 584 nm, insertion: 81%, k.sub.p/k.sub.i=7.

(50) With Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf).sub.2 (6) (0.004 g, 0.0042 mmol) and monomer (0.05 g, 0.213 mmol), the polymer was obtained in 84% yield. .sup.1H NMR (400 MHz, CDCl.sub.3): =6.68 (br m, 2H), 4.27 (br m, 4H), 3.43 (br m, 4H), 1.30 (br m, 6H) ppm; .sup.13C NMR (101 MHz, CDCl.sub.3): =172.1, 137.1, 128.4, 126.3, 123.3, 62.1, 57.4, 41.6, 14.2 ppm; IR (ATR mode, cm.sup.1): 2977 (w), 1720 (s), 1444 (w), 1367 (w), 1247 (m), 1159 (m), 1065 (m), 946 (w), 856 (w), 629 (w). UV/Vis (CHCl.sub.3): .sub.max25=586, 546 nm. M.sub.n=8500 g/mol, PDI=2.1, insertion: 95%.

(51) In the case of use of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMes) (CHCMe.sub.2Ph)(OTf).sub.2 (7) (0.0040 g, 0.0042 mmol) and the monomer (0.0500 g, 0.212 mmol), it was possible to isolate poly(DEDPM) with a yield of 86% (0.043 g). .sup.1H NMR (CDCl.sub.3): =6.68 (br m, 2H), 4.27 (br m, 4H), 3.43 (br m, 4H), 1.31 (br m, 6H); .sup.13C NMR (CDCl.sub.3): =172.1, 138.7, 128.0, 125.8, 122.9, 62.1, 57.4, 41.5, 14.2; FT-IR (ATR, cm.sup.1): 2979 (m), 1722 (s), 1446 (w), 1367 (s), 1248 (s), 1158 (w), 1067 (s), 947 (s), 631 (m). UV/Vis (CHCl.sub.3): .sub.max=587, 546 nm. M.sub.n=84 000 g/mol, PDI=2.8, insertion: 99%.

(52) In the case of use of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf)(OCH(CF.sub.3).sub.2) (9) (0.0040 g, 0.0042 mmol) with the monomer (0.0500 g, 0.212 mmol), it was possible to isolate poly(DEDPM) with a yield of 54% (0.043 g). .sup.1H NMR (CDCl.sub.3): =6.68 (br m, 2H), 4.27 (br m, 4H), 3.43 (br m, 4H), 1.31 (br m, 6H); .sup.13C NMR (CDCl.sub.3): =172.1, 137.1, 128.2, 126.4, 123.3, 62.1, 57.4, 41.6, 14.2; FT-IR (ATR, cm.sup.1): 2977 (m), 1721 (s), 1444 (w), 1367 (s), 1248 (s), 1158 (w), 1067 (s), 947 (s), 631 (m). UV/Vis (CHCl.sub.3): .sub.max=581, 546 nm, M.sub.n=67 400 g/mol, PDI=2.7, insertion: 96%.

Example 32 (poly(4,4-bis[(3,5-diethoxybenzoyloxy)-methyl]-1,6-heptadiyne))

(53) The polymer was prepared using Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CH-tBu)(OTf).sub.2 (1) (1.9 mg, 0.0022 mmol) and the monomer (60 mg, 0.1120 mmol) in 94% yield (57 mg). The polymerization was initiated at 30 C. and then conducted at room temperature for a further hour. .sup.1H NMR (CDCl.sub.3): =7.04-6.92 (m, 4H), 6.71-6.60 (m, 2H), 6.45-6.31 (m, 2H), 4.44-4.31 (m, 4H), 3.90-3.81 (m, 8H), 2.89-2.82 (m, 4H), 1.40-1.25 (m, 12H); .sup.13C NMR (CDCl.sub.3): =168.3, 159.3, 138.2, 131.2, 107.7, 107.6, 106.3, 63.6, 40.7, 27.1, 14.7; IR (ATR, cm.sup.1): 3367 (m), 2969 (s), 2929 (s), 2864 (s), 1673 (s), 1519 (m), 1453 (m), 1366 (s), 1337 (w), 1258 (w), 1190 (w), 1125 (s), 1077 (s), 947 (m), 770 (s), 690 (w); UV/Vis (CHCl.sub.3): .sub.max=550, 590 nm, insertion: >91%; k.sub.p/k.sub.i=33.

(54) It was possible to isolate the polymer through the use of Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf).sub.2 (6) (0.0014 g, 0.0015 mmol) and the monomer (0.04 g, 0.0745 mmol) in quantitative yield (0.0392 g). The polymerization was initiated at 30 C. and stirring was continued at 80 C. for one hour. .sup.1H NMR (CDCl.sub.3): =6.90 (br, m, 4H), 6.36 (br, m, 4H), 4.30 (brs, 4H), 3.85 (brs, 8H), 2.81 (brs, 4H), 1.29 (brs, 12H); .sup.13C NMR (CDCl.sub.3): =168.5, 159.9, 138.3, 131.1, 123.4, 107.7, 106.4, 69.6, 63.7, 43.4, 40.8, 14.8; FT-IR (ATR, cm.sup.1): 2978 (w), 1788 (w), 1716 (s), 1592 (s), 1446 (m), 1385 (w), 1296 (m), 1216 (s), 1166 (s), 1101 (m), 1051 (m), 990 (w), 817 (w), 757 (m), 675 (w), 619 (m); UV/Vis (CHCl.sub.3): .sub.max=591, 550 nm, insertion: 93%.

(55) With the monomer (0.0400 g, 0.754 mmol) and Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMes)(CHCMe.sub.2Ph)(OTf).sub.2 (7) (0.0014 g, 0.0015 mmol), the polymer was prepared with a yield of 60% (0.0255 g). .sup.1H NMR (CDCl.sub.3): =6.90 (br, m, 4H), 6.36 (br, m, 4H), 4.30 (br, s, 4H), 3.84 (br, S, 8H), 2.81 (br, s, 4H), 1.28 (br, s, 12H); .sup.13C NMR (CDCl.sub.3): =166.5, 159.9, 138.5, 131.2, 123.4, 107.7, 106.4, 69.6, 63.8, 43.4, 40.8, 14.5; FT-IR (ATR, cm.sup.1): 2978 (w), 1787 (w), 1716 (s), 1591 (s), 1446 (m), 1385 (w), 1297 (m), 1216 (s), 1166 (s), 1101 (m), 1051 (m), 990 (w), 817 (w), 757 (m), 674 (w), 618 (m), UV/Vis (CHCl.sub.3): .sub.max=590, 550 nm, insertion: 93%.

(56) The polymer was prepared with Mo(N-2,6-Me.sub.2-C.sub.6H.sub.3)(IMesH.sub.2)(CHCMe.sub.2Ph)(OTf)(OCH(CF.sub.3).sub.2) (9) (0.0015 g, 0.0015 mmol) and the monomer (0.0400 g, 0.0745 mmol) with a yield of only 50% (0.020 g). .sup.1H NMR (CDCl.sub.3): 5=6.90 (br, m, 4H), 6.36 (br, m, 4H), 4.30 (br, s, 4H), 3.84 (br, s, 8H), 2.81 (br, s, 4H), 1.28 (br, s, 12H); .sup.13C NMR (CDCl.sub.3): =166.4, 159.9, 138.3, 131.2, 123.4, 107.6, 106.4, 69.5, 63.6, 43.4, 40.8, 14.8; FT-IR (ATR, cm.sup.1): 2978 (w), 1787 (w), 1716 (s), 1591 (s), 1446 (m), 1385 (w), 1297 (m), 1216 (s), 1166 (s), 1101 (m), 1051 (m), 990 (w), 817 (w), 757 (m), 674 (w), 618 (m), UV/Vis (CHCl.sub.3): .sub.max=591, 550 nm, insertion: 95%.

Example 33 (General Procedure for the Reactions with the Catalysts 1-18)

(57) Homo-Metathesis and Ring-Closing Metathesis (RCM):

(58) The reactions are conducted in 1,2-dichloroethane (5 mL) and the appropriate substrates (see table 1). T=80 C.; catalyst:substrate (unless stated otherwise)=1:1000. The conversion was determined by GC-MS after a reaction time of four hours. Internal standard: dodecane. The results of these studies are shown in table 1 below.

(59) Ring-Opening Metathesis Polymerization (ROMP):

(60) All reactions were conducted at 80 C. in 1,2-dichloroethane over a period of 4 hours. Monomer/catalyst=50:1. The results of these studies are shown in table 2 below.

(61) Cyclopolymerization of ,-diynes:

(62) All reactions were conducted at 30 C. to room temperature in dichloromethane at a monomer/catalyst ratio of 50:1 and, unless stated otherwise, over a period of 1 hour. The results of these studies are shown in tables 3 to 7 below. The monomers used within the context of the ROMP and cyclopolymerizations are shown below:

(63) ##STR00008## ##STR00009##

(64) TABLE-US-00001 TABLE 1 Turnover numbers of catalysts 9-14 in various olefin metathesis reactions. 9 10 11 12 13 14 Substrate Homo-metathesis (HM), (values in brackets indicate the E fraction in %) Allyltrimethyl- 520 435 460 350 silane (60) (55) (60) (60) 1-Hexene 340 490 790 85 000.sup.[c] 660 540 (100) (100) (100) (100) (100) (100) 140 000.sup.[d] (100) Styrene 60 80 200 45 000.sup.[d] 30 (100) (100) (100) (100) 1-Octene 680 560 210 000.sup.[d] 400 480 (85) (85) 150 000 (100) (100) (86) Ring-closing metathesis (RCM) Diethyl diallyl 175 90 .sup.3200.sup.[b] 150 350 malonate Diallyldi- 620 490 390 660 520 phenylsilane 1,7-Octadiene 140 920 .sup.4100.sup.[b] 80 000.sup.[c] 830 650 100 000.sup.[d] N,N-Diallyl-t- 390 50 270 0 butylcarbamide N,N-Diallyl-p- 180 160 420 250 350 tosylamide N,N-Diallyltri- 62 15 0 fluoroacetamide Diallylmalo- 190 70 360 100 150 nitrile Diallyl ether 220 245 690 0 0 .sup.[a]ClCH.sub.2CH.sub.2Cl, 80 C., 4 h, cat:substrate = 1:1000, .sup.[b]ClCH.sub.2CH.sub.2Cl, 80 C., 4 h, cat:substrate = 1:5000, .sup.[c]ClCH.sub.2CH.sub.2Cl, RT, overnight, cat:substrate = 1:100 000, .sup.[d]ClCH.sub.2CH.sub.2Cl, RT, 1 h, cat:substrate = 1:500 000.

(65) TABLE-US-00002 TABLE 2 Summary of the polymerization results with catalysts 9-11. Monomer:catalyst = 50:1. All reactions were conducted in CH.sub.2Cl.sub.2 at room temperature. Yield Selectivity M.sub.n Monomer Catalyst (%) (cis/trans) (g/mol) PDI I 9 84 95% 4000 1.03 I 10 86 99% 8200 1.06 I 11 28 64% 11 400 1.22

(66) TABLE-US-00003 TABLE 3 Reactivity of catalysts 8, 9 and 11 in the cyclopolymerization of ,-diynes. Monomer:catalyst = 50:1 Mono- Solv./T Yield M.sub.n mer Cat. ( C.)/t (%) Selectivity (g/mol) PDI II 9 CH.sub.2Cl.sub.2, 84 95% 8500 2.1 30 C.-RT, 1 h II 10 CH.sub.2Cl.sub.2, 86 99% 84 000 2.3 30 C.-RT, 1 h II 11 CH.sub.2Cl.sub.2, 54 96% 67 000 2.7 30 C.-RT, 1 h III 9 CH.sub.2Cl.sub.2, 70 5000 2.1 30 C.-RT, 1 h III 10 CH.sub.2Cl.sub.2, 56 3900 1.8 30 C.-RT, 1 h III 11 CH.sub.2Cl.sub.2, 54 3000 1.3 30 C.-RT, 1 h IV 9 CHCl.sub.3, 81 96 15 000 2.2 30 C.-80 C., 1 h IV 10 CHCl.sub.3, 75 96 14 000 1.8 30 C.-80 C., 1 h IV 11 CHCl.sub.3, 75 96 2200 2.1 30 C.-80 C., 1 h V 9 CHCl.sub.3, 65 3300 1.9 30 C.-80 C., 1 h V 10 CHCl.sub.3, 55 2900 1.4 30 C.-80 C., 1 h V 11 CHCl.sub.3, 55 6000 1.5 30 C.-80 C., 1 h

(67) TABLE-US-00004 TABLE 4 Cyclopolymerization of VI with initiator 6. Initiator M:I M.sub.n,exp.sup.a) Yield Selectivity trans st (I) ratio [g/mol] [%].sup.b) PDI [%] [%] [%] 6 50:1 19 800 47 1.3 96 100 72 CH.sub.2Cl.sub.2, 30 C. to 20 C., 3 h. .sub.max = 469 nm, poly-VI: M.sub.n,theo = 27 900 g/mol. .sup.a)GPC in CHCl.sub.3, UV-vis detector, calibration against poly(styrene) standards; .sup.b)isolated, gravimetrically determined yields. st = syndiotactic.

(68) TABLE-US-00005 TABLE 5 Cyclopolymerization of VII with initiator 6. Initiator M:I M.sub.n,exp.sup.a) Yield Selectivity trans it (I) ratio [g/mol] [%].sup.b) PDI [%] [%] [%] 6 50:1 24 800 24 1.5 95 34 CH.sub.2Cl.sub.2, 30 C. to 20 C., 2 h. .sub.max = 463 nm, poly-VII: M.sub.n,theo = 27 900 g/mol. .sup.a)GPC in CHCl.sub.3, UV-vis detector, calibration against poly(styrene) standards; .sup.b)isolated, gravimetrically determined yields. it = isotactic.

(69) TABLE-US-00006 TABLE 6 Cyclopolymerization of monomer III with initiator 6. Initiator (I) M:I ratio M.sub.n, exp.sup.a) [g/mol] Yield [%].sup.b) PDI 6 50:1 9000 90 1.1 CH.sub.2Cl.sub.2, 30 C. to 20 C., 2 h. Poly-III: M.sub.n, theo = 8300 g/mol. .sup.a)GPC in DMSO, UV-vis detector, calibration against poly(styrene) standards; .sup.b)isolated, gravimetrically determined yields.

(70) TABLE-US-00007 TABLE 7 Cyclopolymerization of monomer VIII with initiators 1 and 4. Initiator M:I M.sub.n,exp.sup.a) .sub.max Yield Selectivity trans st (I) ratio [g/mol] [nm] [%].sup.b) PDI [%] [%] [%] 1 50:1 32 300 550; 83 2.1 >90 100 100 591 4 50:1 27 500 547; 77 1.8 >71 100 74 585 CH.sub.2Cl.sub.2, 30 C. to 20 C., 2 h. Poly-VIII: M.sub.n,theo = 17 300 g/mol. .sup.a)GPC in CHCl.sub.3, UV-vis detector, calibration against poly(styrene) standards; .sup.b)isolated, gravimetrically determined yields.

Example 34 (Immobilization of 4-(hydroxymethyl)-1,3-dimesityl-4,5-dihydro-1H-imidazol-3-ium chloride (I1))

(71) G60 silica gel (350 mg) were suspended in 10 mL of chloroform. A few drops of concentrated sulfuric acid were added thereto. 4-(Hydroxymethyl)-1,3-dimesityl-4,5-dihydro-1H-imidazol-3-ium chloride (500 mg, 1.34 mmol) was dissolved in 10 mL of chloroform and added to the reaction mixture. The reaction mixture was stirred at 60 C. overnight in order then to be cooled to room temperature and filtered. The solids obtained were washed repeatedly with CH.sub.2Cl.sub.2 and demineralized water. In order to remove residues of water, the solids were suspended in dry THF and stirred for one hour. The solids were filtered off and washed with diethyl ether. All volatile constituents were removed under reduced pressure. The solids were suspended in 20 mL of CH.sub.2Cl.sub.2, 1 mL of trimethylsilyl chloride (8.14 mmol) was added to this solution, and the mixture was stirred at room temperature overnight. All volatile constituents were removed under reduced pressure, and the product was obtained as a white solid.

(72) Deprotonation of I1 to I2: I1 was suspended in 20 mL of THF. To this was added lithium hexamethyldisilazide (LiHMDS, 0.22 g, 1.34 mmol), and the mixture was stirred at room temperature for two hours. The reaction mixture was filtered and the resulting solids were suspended in DMSO and stirred for 30 min. The solids were filtered off and washed repeatedly with diethyl ether. All volatile constituents were removed under reduced pressure and the product was obtained as a pale yellow solid. .sup.1H MAS NMR (400.13 MHz): =6.59 (H.sub.arom); 3.28 (CH.sub.2, CH); 1.67, 0.87, 0.03 (CH.sub.3).

Example 35 (Immobilization of [Mo(N-2,6-Me2C6H3)(CHC(CH3)2Ph)(OTf)2(DME)] on I2 (IMo-1))

(73) Mo(N-2,6-Me.sub.2C.sub.6H.sub.3)(CHC(CH.sub.3).sub.2Ph)(OTf).sub.2(DME) (100 mg, 0.14 mmol) was dissolved in 3 mL of benzene. I2 was added to this solution and stirred at room temperature for three hours. The solvent was decanted off and the solids were washed repeatedly with benzene, diethyl ether and CH.sub.2Cl.sub.2 until the solvents were no longer colored. All volatile components were removed under reduced pressure and the product was obtained as an orange solid. .sup.1H MAS NMR (400.13 MHz): =12.60 (CHCMe.sub.2Ph); 6.88 (H.sub.arom); 2.54 (CH.sub.3, CH.sub.2, CH); 0.13 (CH.sub.3).

Example 36 (Immobilization of [Mo(N-2,6-Cl2C6H3)(CHC(CH3)3)(OTf)2(DME)] on 12 (IMo2))

(74) Mo(N-2,6-Cl.sub.2C.sub.6H.sub.3)(CHC(CH.sub.3).sub.3)(OTf).sub.2(DME) (200 mg, 0.26 mmol) was dissolved in 3 mL of benzene. I2 was added to this solution and stirred at room temperature for three hours. The solvent was decanted off and the solids were washed repeatedly with benzene, diethyl ether and CH.sub.2Cl.sub.2 until the solvents were no longer colored. All volatile components were removed under reduced pressure and the product was obtained as an orange solid. .sup.1H MAS NMR (400.13 MHz): =13.77 (CHCMe.sub.2Ph); 6.96 (H.sub.arom); 2.69 (CH.sub.3, CH.sub.2, CH); 0.11 (CH.sub.3).

Example 37 (General Procedure for Metathesis Reactions with IMo1 and IMo2)

(75) The metathesis substrate was dissolved in CH.sub.2Cl.sub.2 (or ClH.sub.2CCH.sub.2Cl) which had been filtered through Al.sub.2O.sub.3, and 50 L of dodecane were added as internal standard for GC-MS determination of conversion. The immobilized catalyst was suspended in CH.sub.2Cl.sub.2 (or ClH.sub.2CCH.sub.2Cl) which had been filtered through Al.sub.2O.sub.3 and added rapidly to the solution prepared beforehand. The reaction mixture was stirred at 40 C. (or 80 C.) for 4 h. After cooling to room temperature, the reaction mixture was filtered through a glass fiber filter paper. For the GC-MS analysis, a sample was taken directly from this solution. If the conversion was determined by means of NMR, no internal standard was added and the solvent was removed completely for the analysis.

(76) TABLE-US-00008 Ratio Yield Turnover Substrate Initiator (cat:substrate) [%] number 0 IMo1 IMo2 1:563 1:590 38 90 210 532 IMo1 IMo2 1:1000 1:1000 3 12 30 120 IMo1 IMo2 1:440 1:305 41 30 184 90 IMo1 IMo2 1:1000 1:1000 10 10 100 100 IMo1 IMo2 1:448 1:478 24 48 106 217 Ratio Yield Turnover Substrate Initiator (cat:substrate) [%] number trans:cis IMo1 IMo2 1:481 1:836 68 4.3 327 37 1:0 1:0 IMo1 IMo2 1:571 1:548 100 100 571 548 1:1.3 1:1.1 IMo1 IMo2 1:123 1:76 100 100 123 76 1:0.6 1:0.7 IMo1 IMo2 1:251 1:59 100 100 251 59 1:9.4 1:21.8 Ratio Yield Turnover Substrate Initiator (cat:substrate) [%] number IMo1 1:59 42 25

Structures of Tungsten-Oxo-Alkylidene-NHC Complexes Prepared

(77) ##STR00020## ##STR00021## ##STR00022## ##STR00023## Mes=mesityl, OTf.sup.=CF.sub.3SO.sub.3.sup., BAr.sup.F=tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, Me=methyl.

Example 38 (Preparation of W(O)Cl2(PPhMe2)(IMes)-(CHCMe2Ph)) (W2)

(78) W(O)Cl.sub.2(PPhMe.sub.2)(CHCMe.sub.2Ph) (2.42 g, 3.56 mmol) was dissolved in 50 mL of toluene. A solution of 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (1.08 g, 3.56 mmol, 1 equiv.) in 10 mL of toluene was prepared. Both solutions were cooled at 40 C. for 30 min. The cold NHC solution was added gradually to the stirred solution of W(O)Cl.sub.2(PPhMe.sub.2).sub.2(CHCMe.sub.2Ph). The reaction mixture was stirred at room temperature for 2 h. The slightly cloudy solution was filtered through Celite and the solvent was removed under reduced pressure. An orange oil was obtained. The oil was taken up in 50 mL of dimethyl ether and filtered rapidly once again. A yellow solid now begins to precipitate out. The solution was stored in the refrigerator at 40 C. overnight. Yield: 2.63 g (87%) of a pale yellow solid. .sup.1H NMR (400 MHz, C.sub.6D.sub.6): =1.28 (d, 3H, PMe.sub.2, J.sub.PH=10.1 Hz), 1.32 (s, 3H, CMe.sub.2Ph), 1.59 (s, 3H, CMe.sub.2Ph), 1.66 (d, 3H, PMe.sub.2, J.sub.PH=10.3 Hz), 2.11 (s, 6H, Mes-Me), 2.24 (s, br, 6H, Mes-Me), 2.38 (s, br, 6H, Mes-Me), 6.16 (s, br, 2H, NCHCHN), 6.80 (s, br, 2H, Mes-Ar), 6.83 (s, br, 2H, Mes-Ar), 6.87 (m, 3H, CMe.sub.2Ph), 6.99-7.09 (m, 5H, Ar), 7.25 (m, 2H, Ar), 7.46 (m, 2H, PMe.sub.2Ph), 11.9 (d, 1H, J.sub.PH=3.6 Hz); .sup.13C NMR (100 MHz, C.sub.6D.sub.6): =14.0 (d, PMe.sub.2, J.sub.CP=34.8), 15.3 (d, PMe.sub.2, J.sub.CP=31.2), 19.5 (o-Mes-Me), 19.7 (o-Mes-Me), 21.2 (p-Mes-Me), 31.1 (CMe.sub.2Ph), 32.9 (CMe.sub.2Ph), 51.7 (CMe.sub.2Ph), 124.4 (br, NCCN), 126.0 (p-CMe.sub.2Ph), 126.8 (o-CMe.sub.2Ph), 128.2 (m-CMe.sub.2Ph), 128.5 (p-PPh), 129.3 (d, m-PPh, J.sub.CP=2.0 Hz), 129.5 (d, o-PPh, J.sub.CP=2.7 Hz), 131.4 (d, ipso-PPh, J.sub.CP=8.6 Hz), 135.9 (br), 137.6 (m-Mes), 138.7 (o-Mes), 152.3 (ipso-CMe.sub.2Ph), 193.1 (d, NCN, J.sub.CP=71.1 Hz) 309.5 (WC, J.sub.CP=125.3 Hz); .sup.31P NMR (160 MHz, C.sub.6D.sub.6): =8.28 (PW), 33.2 (PMe.sub.2Ph). CHN anal. calc. for C.sub.39H.sub.47Cl.sub.2N.sub.2OPW: C, 55.40; H, 5.60; N, 3.31. Found: C, 55.58; H, 5.74; N, 3.32.

Example 39 (Preparation of W(O)(OTf)Cl(PPhMe2)(IMes)-(CHCMe2Ph)) (W3)

(79) W(O)Cl.sub.2(PPhMe.sub.2)(IMes)(CHCMe.sub.2Ph) (0.067 g, 0.08 mmol) was dissolved in 2 mL of dichloromethane and cooled at 40 C. The cold solution was added to solid silver triflate (0.020 g, 1 equiv.) and stirred vigorously. A white precipitate formed. The suspension was stirred with exclusion of light for 30 minutes and filtered through Celite. After the solvent had been removed, the yellow oil was taken up once again in 1 mL of dichloromethane and filtered once more. In order to remove residues of silver chloride, the step has to be repeated a few times. Yield: 0.061 g (81%) of a pale yellow solid. .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =0.97 (s, 3H, CMe.sub.2Ph), 1.15 (d, 3H, PMe.sub.2, J.sub.PH=10.52 Hz), 1.36 (d, 3H, PMe.sub.2, J.sub.PH=10.53 Hz), 1.81 (s, 3H, CMe.sub.2Ph), 1.97 (s, 6H, Mes-Me), 2.16 (s, 6H, Mes-Me), 2.39 (s, 6H, Mes-Me), 6.92 (s, br, 2H, Mes-Ar), 6.93-7.10 (m, 2H, Ar), 7.11 (s, br, 2H, Mes-Ar), 7.11-7.16 (m, 2H, Ar), 7.21-7.38 (m, 6H, Ar), 7.40 (s, 2H, NCHCHN), 7.4-7.5 (m, 1H, Ar), 10.08 (d, 1H, WCH, J.sub.PH=2.2 Hz); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2): =11.60 (d, PMe.sub.2, J.sub.CP=35.4), 13.9 (d, PMe.sub.2, J.sub.CP=31.2), 18.7 (p-Mes-Me), 21.5 (o-Mes-Me), 28.7 (CMe.sub.2Ph), 32.7 (CMe.sub.2Ph), 52.0 (CMe.sub.2Ph), 126.1, 126.3 (br, NCCN), 128.0, 128.7, 129.5, 129.5, 129.6, 129.6, 130.5 (d, PPh, J.sub.CP=26.3 Hz), 131.4 (d, PPh, J.sub.CP=9.3 Hz), 131.7 (d, PPh, J.sub.CP=2.8 Hz), 134.5 (p-Mes), 135.4 (m-Mes), 136.5 (o-Mes), 141.4, 147.9 (ipso-CMe.sub.2Ph), 191.1 (d, NCN, J.sub.CP=55.1 Hz), 302.4 (d, WC, J.sub.CH=116.9 Hz, J.sub.CP=9.5 Hz); 19F NMR (375 MHz, CD.sub.2Cl.sub.2) =78.82 (OSO.sub.2CF.sub.3); .sup.31P NMR (160 MHz, CD.sub.2Cl.sub.2): =17.34. CHN anal. calc. for C.sub.40H.sub.48ClF.sub.3N.sub.2O.sub.4PSW: C, 50.04; H, 5.04; N, 2.92. Found: C, 49.34; H, 4.80; N, 2.89.

Example 40 (Preparation of W(O)(OCCH3(CF3)2)Cl(IMes)-(CHCMe2Ph)) (W4))

(80) In the glovebox, W(O)Cl.sub.2(PPhMe.sub.2)(IMes)(CHCMe.sub.2Ph) (0.568 g, 0.67 mmol) was initially charged in a 25 mL Schlenk flask. The compound was dissolved in 10 mL of toluene and at 40 C. for 30 min. Subsequently, LiOCMe(CF.sub.3).sub.2 (0.170 g, 0.67 mmol, 1 equiv.) was added in solid form. The suspension turned dark orange. After it had been stirred at room temperature for 3 h, the suspension was filtered and the solvent was removed. A dark orange oil was obtained. This was washed with 5 mL of n-pentane and taken up in a minimal amount of diethyl ether. The solution was stored at 40 C. overnight. In the course of this, a pale yellow solid precipitated out. The solids were filtered off and the mother liquor was concentrated further in order to precipitate a second fraction of the product. The combined fractions can be recrystallized once more from diethyl ether. The product is obtained as a pale yellow solid or as yellow crystals (0.470 g, 82%). .sup.1H NMR (400 MHz, C.sub.6D.sub.6): =1.49 (m, 3H, CMe(CF.sub.3).sub.2), 1.54 (s, 3H, CMe.sub.2Ph), 1.60 (s, 3H, CMe.sub.2Ph), 1.91 (s, 6H, Mes-Me), 2.05 (s, 6H, Mes-Me), 2.14 (s, 6H, Mes-Me), 5.97 (s, 2H, NCHCHN), 6.39 (s, br, 2H, Mes-Ar), 6.69 (s, br, 2H, Mes-Ar), 7.00 (m, 5H, Ar), 9.76 (s, 1H, WCH); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2): =17.3 (OCMe(CF.sub.3).sub.2), 19.1 (o-Mes-Me), 19.1 (o-Mes-Me), 21.3 (p-Mes-Me), 28.8 (CMe.sub.2Ph), 33.4 (CMe.sub.2Ph), 50.3 (CMe.sub.2Ph), 78.4 (m, CMe(CF.sub.3).sub.2, 3H), 124.7 (NCCN), 126.3 (p-CMe.sub.2Ph), 126.6 (o-CMe.sub.2Ph), 128.5 (m-CMe.sub.2Ph), 129.9, 135.6 (p-Mes), 135.9 (m-Mes), 137.2 (o-Mes), 140.5 (ipso-Mes), 151.0 (CMe.sub.2Ph), 192.1 (NCN), 282.1 (WC, J.sub.CH=121.3 Hz); .sup.19F NMR (375 MHz, C.sub.6D.sub.6): =76.70-78.00 (dq). CHN anal. calc. for C.sub.35H.sub.39ClF.sub.6N.sub.2O.sub.2W: C, 49.28; H, 4.61; N, 3.28. Found: C, 49.24; H, 4.73; N, 3.28.

Example 41 (Preparation of W(O)(2,6-diphenylphenoxide)-Cl(IMes)(CHCMe2Ph)) (W5)

(81) W(O)Cl.sub.2(PPhMe.sub.2)(IMes)(CHCMe.sub.2Ph) (0.850 g, 1 mmol) was dissolved in 30 mL of toluene. Lithium 2,6-diphenylphenoxide (0.266 g, 1.06 mmol, 1.05 equiv.) was added in solid form at room temperature. The solution turned cloudy. The reaction mixture was stirred at room temperature for 12 h. The toluene was reduced to half the volume and the colorless precipitate was filtered off using Celite. The filtrate was concentrated further until precipitate formed again. The solution was stored in a refrigerator at 40 C. overnight. A yellow-orange solid was filtered off (0.830 g, 90%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =1.33 (s, 3H, CMe.sub.2Ph), 1.40 (s, 6H, Mes-Me), 1.55 (s, 3H, CMe.sub.2Ph), 1.80 (s, 6H, Mes-Me), 2.33 (s, 6H, Mes-Me), 6.66 (m, 2H, Ar), 6.81 (s, 2H, NCHCHN), 6.83 (s, br, 2H, Mes-Ar), 6.86 (m, 1H, Ar), 6.89 (br, 2H, Mes-Ar), 6.97 (m, 4H, Ar), 7.09 (m, 1H, Ar), 7.17 (m, 2H, Ar), 7.22-7.36 (m, 5H, Ar), 7.40 (m, 2H, Ar), 7.81 (m, 2H, Ar), 9.90 (s, 1H, WCH); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2): =18.6 (o-Mes-Me), 19.2 (o-Mes-Me), 21.4 (p-Mes-Me), 29.6 (CMe.sub.2Ph), 32.3 (CMe.sub.2Ph), 50.3 (CMe.sub.2Ph), 120.5, 125.5, 126.4, 126.5, 127.1, 128.4, 129.2, 129.3, 129.5, 130.5, 130.8, 131, 131.8, 133.2, 134.8, 135.4, 135.4, 136.6, 139.8, 141.1, 142, 150.8 (ipso-CMe.sub.2Ph), 159.6 (ipso-OAr), 191.6 (NCN), 288 (WC, J.sub.CH=123.1 Hz), 298.2 (J.sub.CH=123.3 Hz). CHN anal. calc. for C.sub.49H.sub.49ClN.sub.2O.sub.2W: C, 64.16; H, 5.38; N, 3.05. Found: C, 64.16; H, 5.41; N, 3.13.

Example 42 (Preparation of [W(O)(CHCMe2Ph)(IMes)(OTf)-(MeCN)2 B(3,5-(CF3)2C6H3)4]) (W6)

(82) The compound was prepared in situ, immediately prior to the catalyses conducted. W(O)(OTf)Cl(PPhMe.sub.2)(IMes)-(CHCMe.sub.2Ph) was dissolved in 5 mL of dichloromethane and cooled at 40 C. for 30 min. Subsequently, Ag(MeCN).sub.2B(Ar.sup.F).sub.4 (2.05 equiv.) was added in solid form. A colorless precipitate formed immediately. The suspension was stirred with exclusion of light at room temperature for 30 min. Thereafter, the precipitate was filtered off using Celite. The intense yellow solution was used as catalyst stock solution. .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =1.49 (s, 3H, CMe.sub.2Ph), 1.92 (s, 3H, CMe.sub.2Ph), 2.03 (s, 6H, MeCN), 2.12 (s, 6H, Mes-Me), 2.18 (s, 6H, Mes-Me), 2.37 (s, 6H, Mes-Me), 6.96 (s, br, 2H, Mes-Ar), 7.10 (s, br, 2H, Mes-Ar), 7.20-7.38 (m, 5H, Ar), 7.42 (s, 2H, NCHCHN), 7.63 (s, br, 4H, BAr.sup.F), 7.80 (s, br, 8H, BAr.sup.F), 11.47 (s, 1H, WCH); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2): =2.9 (MeCN), 18.5 (o-Mes-Me), 19.0 (o-Mes-Me), 21.4 (p-Mes-Me), 29.2 (CMe.sub.2Ph), 31.0 (CMe.sub.2Ph), 53.5 (CMe.sub.2Ph), 118.2 (sept, J.sub.CF=3.8 Hz, p-CH (BAr.sup.F)), 125.3 (q, J.sub.CF=272.4 Hz, 42CF.sub.3 (BAr.sup.F)), 126.9, 127.2, 127.4, 129.2, 129.7 (qq, J.sub.CF=31.6 Hz, J.sub.CB=2.7 Hz, 4CCF3 (BAr.sup.F)), 129.8, 130.1, 130.9, 132.4, 134.6, 135.5 (s, br, 42C, o-CH (BAr.sup.F)), 136.9, 141.7 (ipso-Mes), 148.8 (ipso-CMe.sub.2Ph), 162.4 (q, J.sub.CH=49.8 Hz, 4BC(BAr.sup.F)), 187.0 (NCN), 324.3 (WC, J.sub.CH=125.3 Hz); .sup.19F NMR (375 MHz, CD.sub.2Cl.sub.2): =62.77 (BAr.sup.f), 77.82 (OSO.sub.2CF.sub.3).

Example 43 (Preparation of [W(O)(CHCMe2Ph)(IMes)-OCCH3(CF3)2) B(3,5-(CF3)2C6H3)4]) (W7)

(83) W(O)(OCCH.sub.3(CF.sub.3).sub.2)Cl(IMes)(CHCMe.sub.2Ph) (0.032 g, 0.0375 mmol) was dissolved in 5 mL of dichloromethane and cooled at 40 C. for 30 min. The solution was added to solid NaB(Ar.sup.F).sub.4 (0.0333 g, 1 equiv.). The suspension was stirred at room temperature for 30 min. A colorless precipitate formed. The solution was stored at 40 C. for 30 min and filtered cold through a glass fiber filter. The filtrate was concentrated under reduced pressure to one third of the volume and filtered once again. After the solvent had been removed, an orange oil was obtained. The latter was stirred with n-pentane until an orange solid formed. The pentane phase was decanted and the solids were dried under reduced pressure. Yield: 0.055 g (87%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =1.29 (s, 3H, CMe.sub.2Ph), 1.32 (sept, 3H, CCH.sub.3(CF.sub.3).sub.2), 1.64 (s, 3H, CMe.sub.2Ph), 1.94 (s, 6H, Mes-Me), 2.05 (s, 6H, Mes-Me), 2.37 (s, 6H, Mes-Me), 7.02 (s, br, 2H, Mes-Ar), 7.16 (s, br, 2H, Mes-Ar), 7.18-7.31 (m, 5H, Ar), 7.57 (s, br, 4H, BAr.sup.F), 7.68 (s, 2H, NCHCHN), 7.74 (s, br, 8H, BAr.sup.F), 10.52 (s, 1H, WCH); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2): =17.8 (o-Mes-Me), 17.9 (o-Mes-Me), 19.3 (OCMe(CF.sub.3).sub.2), 21.5 (p-Mes-Me), 29.4 (CMe.sub.2Ph), 31.9 (CMe.sub.2Ph), 52.7 (CMe.sub.2Ph), 86.3 (m, OCMe(CF.sub.3).sub.2), 118.1 (sept, J.sub.CF=3.8 Hz, p-CH (BAr.sup.F)), 123.8 (q, J.sub.CF=273.4 Hz, 42CF.sub.3 (BAr.sup.F)), 126.3 (NCCN), 127.9 (o-Ar), 128.6 (p-Ar), 129.4 (m-Ar), 129.5 (qq, J.sub.CF=31.6 Hz, J.sub.CB=2.7 Hz, 4CCF3 (BAr.sup.F)), 131.1 (m-Mes), 131.2 (m-Mes), 133.0 (o-Mes), 134.3 (o-Mes), 135.3 (p-Mes), 135.4 (s, br, 42C, o-CH (BAr.sup.F)), 143.6 (ipso-Mes), 147.6 (ipso-CMe.sub.2Ph), 162.4 (q, J.sub.CB=49.8 Hz, 4BC(BAr.sup.F)), 181.8 (NCN), 297.3 (WC, J.sub.CH=123.3 Hz); .sup.19F NMR (375 MHz, CD.sub.2Cl.sub.2): =62.86 (BAr.sup.F), 78.61 (dq). CHN anal. calc. for C.sub.67H.sub.51BF.sub.30N.sub.2O.sub.2W: C, 47.88; H, 3.06; N, 1.67. Found: C, 47.96; H, 3.279; N, 1.84.

Example 44 (Preparation of [W(O)(CHCMe2Ph)(IMes)(2,6-diphenylphenoxide) B(3,5-(CF3)2C6H3)4)]) (W8)

(84) W(O)(2,6-diphenylphenoxide)Cl(IMes)(CHCMe.sub.2Ph) (0.0171 g, 0.0186 mmol) was dissolved in 5 mL of dichloromethane and cooled at 40 C. for 30 min. The solution was added to solid NaB(Ar.sup.F).sub.4 (0.0165 g, 1 equiv.). The suspension was stirred for 30 minutes. A colorless precipitate formed. The reaction mixture was cooled at 40 C. for 30 min and filtered. The filtrate was concentrated down to one third and filtered once again. After the solvent had been removed, a yellow foam was obtained. This was stirred with n-pentane until a yellow precipitate formed. The pentane phase was decanted and the solids were dried under reduced pressure. Yield 0.029 g (89%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =0.72 (s, 3H, CMe.sub.2Ph), 1.58 (s, 3H, CMe.sub.2Ph), 1.67 (s, 6H, Mes-Me), 1.71 (s, 6H, Mes-Me), 2.34 (s, 6H, Mes-Me), 6.83 (s, br, 2H, Mes-Ar), 6.99 (s, br, 2H, Mes-Ar), 7.01-7.09 (m, 4H), 7.17-7.27 (m, 12H), 7.30-7.40 (m, 4H), 7.45-7.52 (m, 1H), 7.56 (s, br, p-CH (BAr.sup.F)), 7.73 (s, 8H, o-CH (BAr.sup.F)), 11.82 (s, 1H, WCH); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2, MeCN adduct): =2.5 (MeCN), 18.6 (o-Mes-Me), 18.9 (o-Mes-Me), 21.4 (p-Mes-Me), 30.1 (CMe.sub.2Ph), 30.5 (CMe.sub.2Ph), 52.1 (CMe.sub.2Ph), 118.1 (sept, J.sub.CF=3.8 Hz, p-CH (BAr.sup.F)), 123.5 (MeCN), 123.8 (q, J.sub.CF=273.4 Hz, 42CF.sub.3 (BAr.sup.F)), 126.7 (br, NCCN), 126.8, 127.2, 128.8, 129.5 (qq, J.sub.CF=31.6 Hz, J.sub.CB=2.7 Hz, 4CCF3 (BAr.sup.F)), 129.9, 130.0, 135.4, 135.4 (s, br, 42C, o-CH (BAr.sup.F)), 135.5, 135.6, 141.4 (ipso-Mes), 147.3 (ipso-CMe.sub.2Ph), 157.5 (ipso-OAr), 162.4 (q, J.sub.CB=49.8 Hz, 4BC(BAr.sup.F)), 188.6 (NCN), 309.9 (WC, J.sub.CH=121.2 Hz); .sup.19F NMR (375 MHz, CD.sub.2Cl.sub.2): =62.87 (BAr.sup.F). CHN anal. calc. for C.sub.81H.sub.61BF.sub.24N.sub.2O.sub.2W: C, 55.75; H, 3.52; N, 1.61. Found: C, 55.69; H, 3.913; N, 1.72.

Example 45 (Preparation of [W(O)(CHCMe2Ph)(IMes)-(OCCH3(CF3)2)(MeCN)2 B(3,5-(CF3)2(C6H3)4]) (W9)

(85) The compound was prepared in situ, immediately before the catalyses conducted. W(O)(OCCH.sub.3(CF.sub.3).sub.2)Cl(IMes)-(CHCMe.sub.2Ph) was dissolved in 5 mL of dichloromethane and cooled at 40 C. for 30 minutes. Subsequently, Ag(MeCN).sub.2B(Ar.sup.F).sub.4 (1.0 equiv.) was added in solid form. A colorless precipitate formed immediately. The suspension was stirred with exclusion of light at room temperature for 30 min. Thereafter, the precipitate was filtered off using Celite. The intense yellow solution was utilized as catalyst stock solution.

Example 46 (Preparation of [W(O)(CHCMe2Ph)(IMes)(2,6-diphenylphenoxide)(MeCN)2 B(3,5-(CF3)2(C6H3)4]) (W10)

(86) The compound was prepared in situ, immediately before the catalyses conducted. W(O)(2,6-diphenylphenoxide)-Cl(IMes)(CHCMe.sub.2Ph) was dissolved in 5 mL of dichloromethane and cooled at 40 C. for 30 minutes. Subsequently, Ag(MeCN).sub.2B(Ar.sup.F).sub.4 (1.0 equiv.) was added in solid form. A colorless precipitate formed immediately. The suspension was stirred with exclusion of light at room temperature for 30 min. Thereafter, the precipitate was filtered off using Celite. The intense yellow solution was utilized as catalyst stock solution.

Example 47 (Preparation of [W(O)Cl2(IMes)(CHCMe2Ph)) (W11)

(87) W(O)(2,6-diphenylphenoxide)Cl(IMes)(CHCMe.sub.2Ph) (0.023 g, 0.249 mmol) was dissolved in 2 mL of acetonitrile and cooled at 40 C. for 30 minutes. Subsequently, a cold solution of AlCl.sub.3 (0.0033 g, 0.249 mmol, 1 equiv.) in 1 mL of acetonitrile was added. The solution turned intense yellow and was stirred at room temperature for 3 h. Thereafter, the solvent was removed and the oily residue was taken up in 1 mL of dichloromethane. The solution was filtered and concentrated to 0.3 mL. After a few days, yellow crystals of the product formed. Yield: 0.013 g (74%).

Example 48 (Preparation of W(O)(OTf)(OCCH3(CF3)2)(IMes)-(CHCMe2Ph)) (W12)

(88) W(O)(OCCH.sub.3(CF.sub.3).sub.2)Cl(IMes)(CHCMe.sub.2Ph) (0.0495 g, 0.058 mmol) was dissolved in 2 mL of dichloromethane and cooled at 40 C. for 30 min. Silver triflate (0.015 g, 0.058 mmol, 1 equiv.) was added to the cold solution. A colorless precipitate was immediately observed. The suspension was stirred with exclusion of light for 1 h and filtered through Celite. The solvent was removed. A yellow oil remained, which was taken up in 1 mL of dichloromethane and filtered once again. This step was repeated a few times in order to remove residues of silver chloride. The product is obtained as a yellow solid. Yield: 0.041 g (74%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =0.74 (s, 3H, CMe.sub.2Ph), 0.81 (s, 3H, CMe(CF.sub.3).sub.2), 1.45 (s, 3H, CMe.sub.2Ph), 2.13 (s, 6H, Mes-Me), 2.18 (s, 6H, Mes-Me), 2.31 (s, 6H, Mes-Me), 6.96 (s, br, 2H, Mes-Ar), 7.03 (s, br, 2H, Mes-Ar), 7.05-7.11 (m, 1H, Ar), 7.14-7.25 (m, 4H, Ar), 7.26 (s, 2H, N-CHCHN), 10.69 (s, 1H, WCH); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2) =17.6 (OCMe(CF.sub.3).sub.2), 18.4 (o-Mes-Me), 18.5 (o-Mes-Me), 21.3 (p-Mes-Me), 29.0 (CMe.sub.2Ph), 29.9 (CMe.sub.2Ph, 50.8 (CMe.sub.2Ph), 82.3 (m, CMe(CF.sub.3).sub.2), 125.8, 126.1, 126.5, 128.6, 130.4, 130.4, 136.4 (p-Mes), 137.1 (m-Mes), 141.7 (ipso-Mes), 150.9 (CMe.sub.2Ph), 186.0 (NCN), 278.2 (WC, J.sub.CH=127.1 Hz); .sup.19F NMR (375 MHz, C.sub.6D.sub.6): =77.71 (s, br, OSO.sub.2CF.sub.3), 77.76 (m, br, OCCH.sub.3(CF.sub.3).sub.2).

Example 49 (Preparation of W(O)(OTf)2(IMes)(CHCMe2Ph)) (W13)

(89) W(O)Cl.sub.2(PPhMe.sub.2)(IMes)(CHCMe.sub.2Ph) (0.26 g, 0.83 mmol) was dissolved in 8 mL of dichloromethane. The solution was cooled at 40 C. for 30 min. While stirring, Silver triflate (0.200 g, 0.766 mmol, 2.01 equiv.) was added in solid form. A colorless solid immediately precipitated out. The suspension was stirred with exclusion of light at room temperature for 1 h. In the course of this, the color changed to yellow. The solution was filtered through Celite. The solvent was removed. A pale yellow foam was obtained. The latter was dissolved in a small amount of dichloromethane and filtered once again. This step was repeated a few times in order to remove silver chloride residues. The crude product can be recrystallized from dichloromethane/diethyl ether. The product is obtained as a yellow crystalline solid. Yield: 0.303 g (85%).

Example 50 (Preparation of W(O)(2,6-diphenylphenoxide)2 (1,3-Me2-4,5-Cl2-imidazol-2-ylidene)(CHCMe2Ph)) (W14)

(90) W(O)(2,6-diphenylphenoxide).sub.2(PMePh.sub.2)(CHCMe.sub.2Ph) (0.12 g, 0.117 mmol) was dissolved in 8 mL of toluene. 1,3-Me.sub.2-4,5-Cl.sub.2-imidazol-2-ylidene-AgI (0.048 g, 0.12 mmol, 1.01 equiv.) was added in solid form. The suspension was kept in an ultrasound bath at 70 C. for 1 hour. Subsequently, the suspension was filtered through Celite and the solvent was removed. The pale yellow solid was taken up in 4 mL of dichloromethane and filtered once more. The solvent was removed and the oily solid was washed with n-pentane. The product was obtained as a pale orange solid. Yield: 0.1 g (86%). .sup.1H NMR (400 MHz, C.sub.6D.sub.6): =1.08 (s, 3H, CMe.sub.2Ph), 1.44 (s, 3H, CMe.sub.2Ph), 6.73-6.82 (m, 6H, Ar), 6.96-7.03 (m, 8H, Ar), 7.05-7.12 (m, 6H, Ar), 7.17-7.28 (m, 12H, Ar), 7.47 (d, 2H, p-Ar, J=7.56 Hz), 7.47 (m, 4H, p-Ar), 10.25 (s, 1H, WCH); .sup.13C NMR (100 MHz, C.sub.6D.sub.6): =29.4 (CMe.sub.2Ph), 31.5 (CMe.sub.2Ph), 36.3 (Me-NHC), 48.5 (CMe.sub.2Ph), 117.1 (NCCN), 125.6, 125.8, 126.4, 126.8, 128.9, 129.8, 130.4, 131.1, 132.1, 133.2, 133.4, 133.9, 140.6 (ipso-Ar), 142.0 (ipso-Ar), 151.5 (ipso-CMe.sub.2Ph), 157.8 (ipso-OAr), 163.4 (ipso-OAr), 191.3 (NCN), 279.5 (WC, J.sub.CH=124.0 Hz).

Example 51 (Preparation of W(NtBu)(Cl)2(1,3-Me2-4,5-Cl2-imidazol-2-ylidene)(pyridine)(CHCMe3)) (W15)

(91) W(NtBu)(Cl).sub.2 (pyridine).sub.2(CHCMe.sub.3) (0.2 g, 0.36 mmol) was dissolved in 8 mL of dichloroethane. 1,3-Me.sub.2-4,5-Cl.sub.2-imidazol-2-ylidene-AgI (0.145 g, 0.36 mmol, 1.0 equiv.) was added in solid form. The suspension was kept in an ultrasound bath at 70 C. for 1 hour. Subsequently, the suspension was filtered through Celite and the solvent was removed. The pale yellow solid was taken up in 4 mL of dichloromethane and filtered once more. The solvent was removed and the solids were washed with n-pentane. The product was obtained as a pale orange solid. Two isomers form in equal proportions. Yield: 0.19 g (82%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =1.21 (s, 9H, tBu), 1.28 (s, 9H, tBu), 1.38 (s, 9H, tBu), 1.41 (s, 9H, tBu), 3.76 (s, 6H, Me.sub.2-NHC), 4.21 (s, 6H, Me.sub.2-NHC), 7.28 (m, 2H, pyr), 7.41 (m, 2H, pyr), 7.68 (m, 1H, pyr), 7.86 (m, 1H, pyr), 8.60 (m, br, 2H, pyr), 9.40 (m, 2H, pyr), 10.58 (s, 1H, WCH), 12.0 (s, 1H, WCH); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2): =15.7, 31.0, 31.4, 31.4, 32.6, 34.3, 34.8, 39.2, 40.4, 44.8, 45.4, 66.2 (CMe.sub.3), 69.6 (CMe.sub.3), 118.9, 119.0, 124.2, 124.8, 124.9, 136.3, 139.1, 139.4, 150.5, 156.8, 157.1, 191.0 (NCN), 191.2 (NCN), 279.9 (WCH), 301.0 (WCH).

Example 52 (Preparation of W(NtBu)(Cl)(1,3-Me2-4,5-Cl2-imidazol-2-ylidene)(OHIPT)(CHCMe3)) (W16)

(92) W(NtBu)(Cl).sub.2(1,3-Me.sub.2-4,5-Cl.sub.2-imidazol-2-ylidene)-(pyridine) (CHCMe.sub.3) (0.15 g, 0.234 mmol) was dissolved in 8 mL of benzene. Lithium 2,6-di(2,4,6-triisopropylphenyl)phenoxide (0.118 g, 0.234 mmol, 1.0 equiv.) was added in solid form. The solution was stirred at room temperature overnight. A colorless precipitate formed. Subsequently, the suspension was filtered through Celite and the solvent was removed. The dark orange foam was taken up in 4 mL of toluene and filtered once more. The solvent was removed and the solids were recrystallized from n-pentane. The product was obtained as an orange solid. Yield: 0.13 g (87%). .sup.1H NMR (400 MHz, C.sub.6D.sub.6): =0.72 (d, 3H, iPr), 1.00 (m, 6H, iPr), 1.14 (d, 3H, iPr), 1.20 (s, 9H, tBu), 1.24 (s, 9H, tBu), 1.26 (m, 6H, iPr), 1.30 (m, 9H, iPr), 1.36 (m, 6H, iPr), 1.66 (m, 6H, iPr), 2.70-3.30 (m, 10H, Me.sub.2-NHC, CH-iPr), 3.93 (m, 2H, CH-iPr), 6.9 (m, 1H, Ar), 7.02 (m, 1H, Ar), 7.13 (m, 1H, Ar), 7.16 (m, 1H, Ar), 7.26 (m, 2H, Ar), 7.40 (m, 1H, Ar), 10.37 (s, 1H, WCH); .sup.13C NMR (100 MHz, C.sub.6D.sub.6): =14.3, 22.3, 22.7, 22.9, 24.2, 24.5, 24.7, 24.8, 25.2, 25.5, 27.1, 27.6, 30.4, 31.0, 31.5, 34.2, 34.5, 34.6, 34.8, 43.8, 68.1 (CMe.sub.3), 118.2, 119.7, 120.1, 121.9, 122.7, 131.5, 132.0, 132.4, 138.1, 138.4, 147.2, 147.3, 147.4, 148.1, 149.5, 149.9, 162.0, 192.0 (NCN), 281.9 (WCH).

Example 53 (Preparation of [W(NtBu)(1,3-Me2-4,5-Cl2-imidazol-2-ylidene)(OHIPT)(CHCMe3) AlpftBu]) (W17)

(93) W(NtBu)(Cl)(1,3-Me.sub.2-4,5-Cl.sub.2-imidazol-2-ylidene)(OHIPT)-(CHCMe.sub.3) (0.0331 g, 0.0323 mmol) was dissolved in 3 mL of dichloromethane. Lithium tetrakis(nonafluoro-t-butoxy)aluminate (LiAlpftBu, 0.0315 g, 0.0323 mmol, 1.0 equiv.) was added in solid form. The solution was stirred at room temperature for 1 h. A colorless precipitate formed. At the same time, the solution turned intense yellow. Subsequently, the suspension was filtered through Celite and the solvent was removed. The yellow foam was taken up in 4 mL of toluene and filtered once more. The solvent was removed and the yellow oil was stirred with n-pentane. A yellow solid formed. The product was filtered off and dried under reduced pressure. Yield: 0.055 g (87%). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): =0.81 (d, 6H, iPr), 0.95 (d, 6H, iPr), 0.99 (d, 6H, iPr), 1.01 (s, 9H, tBu), 1.02 (d, 6H, iPr), 1.09 (s, 9H, tBu), 1.23 (d, 12H, iPr), 2.49 (sept, 2H, CH-iPr), 2.58 (sept, 2H, CH-iPr), 2.89 (sept, 2H, CH-iPr), 3.29 (s, 6H, Me.sub.2-NHC), 7.0 (m, 2H, Ar), 7.03 (m, 1H, Ar), 7.05 (s, 1H, Ar), 7.08 (m, 2H, Ar), 7.15 (m, 1H, Ar), 10.74 (s, 1H, WCH); .sup.13C NMR (100 MHz, CD.sub.2Cl.sub.2): =24.2, 24.4, 24.5, 24.6, 24.8, 31.6, 32.7, 33.6, 34.7, 40.2, 47.2, 74.4, 120.4, 122.0, 122.3, 122.8, 123.3, 124.9, 131.8, 132.6, 133.2, 147.5, 147.8, 149.9, 158.6, 178.0, 289.0 (WCH); .sup.19F NMR (375 MHz, CD.sub.2Cl.sub.2): =75.72 (s, CF.sub.3).

Example 54 (General Method for In Situ Catalyst Syntheses)

(94) The tungsten oxo precursors W3-W5 (about 0.05 mmol) were dissolved in 2 mL of 1,2-dichloroethane. An equimolar amount of Ag(MeCN).sub.2B(Ar.sup.F).sub.4 (W4, W5) or 2 equiv. (W3) and/or excess AlCl.sub.3 was added. The solution was stirred for 30 min and filtered. The filtrate was used as catalyst stock solution.

Example 55 (General Method for Ring-Closing, Homo- and Self-Metatheses)

(95) About 20 mg of the substrate were weighed into a 10 mL screwtop bottle. The appropriate amount of solvent was added (0.1 M solution). Thereafter, 0.5 equiv. of dodecane (internal standard) was added. An aliquot with 1 mg of substrate was taken for the t.sub.0 sample. A 0.0005 M catalyst stock solution was prepared. The appropriate amount of stock solution was added to the substrate solution. The solution was stirred at the given temperature for the given period of time. The reactions were stopped by means of air atmosphere and a sample was taken for the GC-MS analysis. The exact monomer/catalyst compositions and the turnover numbers (TONs) determined for these can be found in table 8.

Example 56 (General Method for Cross-Metatheses (CM) with Allyltrimethylsilane)

(96) The same general method was followed as for the ring-closing metatheses (example 53). An additional 10 equivalents of allyltrimethylsilane were merely added to the substrate. The exact monomer/catalyst compositions and the turnover numbers (TONs) determined for these can likewise be found in table 8.

Example 57 (Z-Selective Metathesis)

(97) In a protective gas box, 1-octene (about 22 mg) is weighed into a 4 mL screwtop bottle and dissolved in 1 mL of benzene. While stirring, a solution of W17 (3.6 mg) in benzene (0.2 mL) is added. The mixture is stirred at room temperature for one hour. To monitor the course of the reaction and the selectivity, an aliquot is taken and diluted with undried CDCl.sub.3 in order to stop the reaction. The reaction mixture was analyzed by .sup.1H NMR (100% conversion >99.9% Z-configured product).

(98) TABLE-US-00009 TABLE 8 TONs with AlCl.sub.3-activated 3-5 and with cationic complexes W6-W8. Reaction conditions, unless stated otherwise: T = 25 C. in 1,2-dichloroethane for 4 h, ubstrate:catalyst 1:2000 Substrate W6 W7 W8 W3.sup.[a] W4.sup.[a] W5.sup.[a] Ring-closing metathesis (RCM) Diallyldiphenylsilane 4800.sup.[c] 3400.sup.[e] 7600.sup.[e] 0.sup.[c] 0.sup.[c] 0.sup.[c] N,N-Diallyl-p- 1700.sup.[c] 1350 1700.sup.[b] 0.sup.[c] 0.sup.[c] 0.sup.[c] toluenesulfonamide Octa-1,7-diene 970.sup.[c] 710 1500.sup.[b] 980.sup.[c] 4300.sup.[c] 4700.sup.[c] Diallylmalonitrile 130.sup.[c] 660 1400.sup.[e] 0.sup.[c] 0.sup.[c] 0.sup.[c] Diallyl ether 0 0 5700.sup.[e] 0.sup.[c] 0.sup.[c] 0.sup.[c] Diallyl thioether 4800.sup.[c] 0 4900.sup.[e] 4800.sup.[c] 1200 1400 4,4-Dicyanoocta-1,7- 470.sup.[c] 430 2600.sup.[e] 0.sup.[c] 0.sup.[c] 0.sup.[c] diene Diethyldiallyl 1600.sup.[c] 660 3200.sup.[e] 0.sup.[c] 0.sup.[c] 0.sup.[c] malonate Homometathesis (HM), in brackets = E content (%) Allylbenzene 200 480 635 640 430 410 (55).sup.[c] (60) (85).sup.[e] (55) (55) (80) 1-Hexene 2000 1640 5400 4900 5000 9800 (60).sup.[c] (65) (85).sup.[e] (60).sup.[c] (65).sup.[c] (80).sup.[e] 1-Octene 3300 1320 6100 4830 5000 2000 (60).sup.[c] (65) (85).sup.[e] (55).sup.[c] (60).sup.[c] (80).sup.[c] Allylphenyl sulfide 0 0 300 0 0 280 (>95).sup.[d] (>95).sup.[d] Trimethylallylsilane 4100 1710 1500 0 0 0 (55).sup.[c] (55) (60) Cross-metathesis (CM).sup.[d] with allyltrimethylsilane, in brackets = E content (%) Hex-5-en-1-yl acetate 480 450 500 0 0 0 (55) (60) (80) 4-Octene 500 490 500 0 0 0 (50) (65) (80) N-Phenyl-(1-phenyl- 200 0 0 0 0 0 but-3-en-1-yl)amine (60) Self-metathesis (SM), in brackets = E content (%) Methyl oleate 1500 0.sup.[c] 10 000 0.sup.[c] 0.sup.[c] 0.sup.[c] (60) (70).sup.[f] .sup.[a]activated with excess AlCl.sub.3, CH.sub.2Cl.sub.2, room temperature, catalyst:substrate = 1:5000. .sup.[b]catalyst:substrate = 1:2000, 70 C. .sup.[c]catalyst:substrate = 1:5000, 70 C. .sup.[d]catalyst:substrate = 1:500, 25 C. .sup.[e]catalyst:substrate = 1:10 000, 25 C. .sup.[f]catalyst: substrate = 1:20 000, 70 C.