Substituted mononuclear ruthenium complexes for catalysis of synthetic organic reactions

Abstract

Provided is a mononuclear ruthenium complex that comprises a ruthenium-silicon bond that is represented by formula (1) and that exhibits excellent catalyst activity in each of a hydrosilylation reaction, a hydrogenation reaction, and reduction of a carbonyl compound. ##STR00001## In formula (1), R.sup.1-R.sup.6 either independently represent an alkyl group, an aryl group, an aralkyl group or the like that may be substituted with a hydrogen atom or X, or represent a crosslinking substituent in which at least one pair comprising one of R.sup.1-R.sup.3 and one of R.sup.4-R.sup.6 is combined. X represents a halogen atom, an organoxy group, or the like. L represents a two-electron ligand other than CO and phosphine. When a plurality of L are present, the plurality of L may be the same as or different from each other. When two L are present, the two L may be bonded to each other. n and m independently represent an integer of 1 to 3 with the stipulation that n+m equals 3 or 4.

Claims

1. A mononuclear ruthenium complex having formula (1): ##STR00031## wherein: m is 2; n is 2; and formula (1) is selected from the group consisting of: ##STR00032## wherein: each L is independently molecular hydrogen, N(R).sub.3, RC(═NR)R, pyrrolyl, imidazolyl, pyridinyl, pyrimidinyl, oxazolinyl, isoxazolinyl, As(R).sub.3, ROH, RSH, ROR, RSR, RC≡N, RN≡C, RC(O)H, RC(O)R, C.sub.2-C.sub.30 alkenyl, C.sub.2-C.sub.30 alkynyl or R.sup.1R.sup.2R.sup.3SiH; each R is independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each independently hydrogen or alkyl, aryl, aralkyl, organooxy, monoorganoamino, diorganoamino, monoorganophosphino, diorganophosphino, monoorganosilyl, diorganosilyl, triorganosilyl or organothio, each of which is independently and optionally substituted with X; R.sup.17, R.sup.18, R.sup.19 and R.sup.20 are each independently hydrogen, halogen, C.sub.1-C.sub.10 alkyl or C.sub.1-C.sub.10 alkoxy; R.sup.25, R.sup.26, R.sup.27, R.sup.28, R.sup.29 and R.sup.30 are each independently hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.20 aralkyl or C.sub.6-C.sub.20 aryl; and X is halogen, organooxy, monoorganoamino, diorganoamino or organothio; with the proviso that two L may bond together.

2. The mononuclear ruthenium complex of claim 1, wherein: each L is independently RSH, RSR or R.sup.1R.sup.2R.sup.3SiH.

3. The mononuclear ruthenium complex of claim 2, wherein: each L is independently R.sup.1R.sup.2R.sup.3SiH, wherein R.sup.1R.sup.2R.sup.3SiH in one L is represented by R.sup.7R.sup.8R.sup.9SiH and R.sup.1R.sup.2R.sup.3SiH in the other L is represented by R.sup.10R.sup.11R.sup.12SiH; R.sup.7, R.sup.8 and R.sup.9 are each independently alkyl, aryl or aralkyl; R.sup.10, R.sup.11 and R.sup.12 are each independently alkyl, aryl or aralkyl; and (i) one pair of R.sup.7, R.sup.8 and R.sup.9, taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH.sub.2).sub.k—NH—, —NR—(CH.sub.2).sub.k—NR—, —PH—(CH.sub.2).sub.k—PH—, —PR—(CH.sub.2).sub.k—PR—, —CH═CH—, —CR═CR—, C.sub.1-C.sub.10 alkylene, C.sub.6-C.sub.30 arylene, C.sub.7-C.sub.30 aralkylene, —(CH.sub.2O).sub.k—, (CH.sub.2O).sub.k—O—(CH.sub.2).sub.k—, —O—(CH.sub.2O).sub.k—O—, —R′—O—(CH.sub.2O).sub.k—O—R′—, —(CH.sub.2S).sub.k—, (CH.sub.2).sub.k—S—(CH.sub.2).sub.k—, —S—(CH.sub.2).sub.k—S—, —R′—S—(CH.sub.2).sub.k—O—R′—, —Si(R).sub.2— and —(CH.sub.2).sub.k—Si(R).sub.2—(CH.sub.2).sub.k—; or (ii) one pair of R.sup.10, R.sup.11 and R.sup.12, taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH.sub.2).sub.k—NH—, —NR—(CH.sub.2).sub.k—NR—, —PH—(CH.sub.2).sub.k—PH—, —PR—(CH.sub.2).sub.k—PR—, —CH═CH—, —CR═CR—, C.sub.1-C.sub.10 alkylene, C.sub.6-C.sub.30 arylene, C.sub.7-C.sub.30 aralkylene, —(CH.sub.2O).sub.k—, (CH.sub.2O).sub.k—O—(CH.sub.2).sub.k—, —O—(CH.sub.2O).sub.k—O—, —R′—O— (CH.sub.2O).sub.k—O—R′—, —(CH.sub.2S).sub.k—, (CH.sub.2).sub.k—S—(CH.sub.2).sub.k—, —S—(CH.sub.2).sub.k—S—, —R′—S(CH.sub.2).sub.k—O—R′—, —Si(R).sub.2— and —(CH.sub.2).sub.k—Si(R).sub.2—(CH.sub.2).sub.k—; each R is independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; each R′ is independently C.sub.1-C.sub.10 alkylene; and each k is independently 1, 2, 3, 4, 5, 6, 7 8, 9, or 10.

4. The mononuclear ruthenium complex of claim 3, wherein: one pair of R.sup.7, R.sup.8 and R.sup.9, taken together, form a crosslinking substituent.

5. The mononuclear ruthenium complex of claim 4, wherein: formula (1) is represented by: ##STR00033##

6. The mononuclear ruthenium complex of claim 2, wherein: (a) (i) one L is RSH, wherein RSH is represented by R.sup.13SH or R.sup.14SH, and the other L is RSR, wherein RSR is represented by R.sup.15SR.sup.16, or (ii) one L is RSR, wherein RSR is represented by R.sup.13SR.sup.14, and the other L is RSH, wherein RSH is represented by R.sup.15SH or R.sup.16SH; R.sup.13 and R.sup.14 are each independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; R.sup.15 and R.sup.16 are each independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; and at least one pair of any one of R.sup.13 and R.sup.14 and any one of R.sup.15 and R.sup.16, taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH.sub.2).sub.k—NH—, —NR—(CH.sub.2).sub.k—NR—, —PH—(CH.sub.2).sub.k—PH—, —PR—(CH.sub.2).sub.k—PR—, —CH═CH—, —CR═CR—, C.sub.1-C.sub.10 alkylene, C.sub.6-C.sub.30 arylene, C.sub.7-C.sub.30 aralkylene, —(CH.sub.2O).sub.k—, (CH.sub.2O).sub.k—O—(CH.sub.2).sub.k—, —O—(CH.sub.2O).sub.k—O—, —R′—O—(CH.sub.2O).sub.k—O—R′—, —(CH.sub.2S).sub.k—, (CH.sub.2).sub.k—S—(CH.sub.2).sub.k—, —S—(CH.sub.2).sub.k—S—, —R′—S—(CH.sub.2).sub.k—O—R′—, —Si(R).sub.2— and —(CH.sub.2).sub.k—Si(R).sub.2—(CH.sub.2).sub.k—; each R is independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; each R′ is independently C.sub.1-C.sub.10 alkylene; and each k is independently 1, 2, 3, 4, 5, 6, 7 8, 9, or 10; or (b) one L is RSH, wherein RSH is represented by R.sup.13SH or R.sup.14SH, and the other L is RSH, wherein RSH is represented by R.sup.15SH or R.sup.16SH; R.sup.13 and R.sup.14 are each independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; R.sup.15 and R.sup.16 are each independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; and at least one pair of any one of R.sup.13 and R.sup.14 and any one of R.sup.15 and R.sup.16, taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH.sub.2).sub.k—NH—, —NR—(CH.sub.2).sub.k—NR—, —PH—(CH.sub.2).sub.k—PH—, —PR—(CH.sub.2).sub.k—PR—, —CH═CH—, —CR═CR—, C.sub.1-C.sub.10 alkylene, C.sub.6-C.sub.30 arylene, C.sub.7-C.sub.30 aralkylene, —(CH.sub.2O).sub.k—, (CH.sub.2O).sub.k—O—(CH.sub.2).sub.k—, —O—(CH.sub.2O).sub.k—O—, —R′—O—(CH.sub.2O).sub.k—O—R′—, —(CH.sub.2S).sub.k—, (CH.sub.2).sub.k—S—(CH.sub.2).sub.k—, —S—(CH.sub.2).sub.k—S—, —R′—S—(CH.sub.2).sub.k—O—R′—, —Si(R).sub.2— and —(CH.sub.2).sub.k—Si(R).sub.2—(CH.sub.2).sub.k—; each R is independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; each R′ is independently C.sub.1-C.sub.10 alkylene; and each k is independently 1, 2, 3, 4, 5, 6, 7 8, 9, or 10; or (c) one L is RSR, wherein RSR is represented by R.sup.13SR.sup.14, and the other L is RSR, wherein RSR is represented by R.sup.15SR.sup.16; R.sup.13 and R.sup.14 are each independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; R.sup.15 and R.sup.16 are each independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; and at least one pair of any one of R.sup.13 and R.sup.14 and any one of R.sup.15 and R.sup.16, taken together, form a crosslinking substituent selected from the group consisting of —O—, —S—, —NH—, —NR—, —PR—, —NH—(CH.sub.2).sub.k—NH—, —NR—(CH.sub.2).sub.k—NR—, —PH—(CH.sub.2).sub.k—PH—, —PR—(CH.sub.2).sub.k—PR—, —CH═CH—, —CR═CR—, C.sub.1-C.sub.10 alkylene, C.sub.6-C.sub.30 arylene, C.sub.7-C.sub.30 aralkylene, —(CH.sub.2O).sub.k—, (CH.sub.2O).sub.k—O—(CH.sub.2).sub.k—, —O—(CH.sub.2O).sub.k—O—, —R′—O—(CH.sub.2O).sub.k—O—R′—, —(CH.sub.2S).sub.k—, (CH.sub.2).sub.k—S—(CH.sub.2).sub.k—, —S—(CH.sub.2).sub.k—S—, —R′—S—(CH.sub.2).sub.k—O—R′—, —Si(R).sub.2— and —(CH.sub.2).sub.k—Si(R).sub.2—(CH.sub.2).sub.k—; each R is independently C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl or C.sub.7-C.sub.30 aralkyl; each R′ is independently C.sub.1-C.sub.10 alkylene; and each k is independently 1, 2, 3, 4, 5, 6, 7 8, 9, or 10.

7. The mononuclear ruthenium complex of claim 6, wherein: (a) (i) one L is RSH, wherein RSH is represented by R.sup.13SH or R.sup.14SH, and the other L is RSR, wherein RSR is represented by R.sup.15SR.sup.16, or (ii) one L is RSR, wherein RSR is represented by R.sup.13SR.sup.14, and the other L is RSH, wherein RSH is represented by R.sup.15SH or R.sup.16SH; and at least one pair of any one of R.sup.13 and R.sup.14 and any one of R.sup.15 and R.sup.16, taken together, form a crosslinking substituent; or (b) one L is RSH, wherein RSH is represented by R.sup.13SH or R.sup.14SH, and the other L is RSH, wherein RSH is represented by R.sup.15SH or R.sup.16SH; and at least one pair of any one of R.sup.13 and R.sup.14 and any one of R.sup.15 and R.sup.16, taken together, form a crosslinking substituent.

8. The mononuclear ruthenium complex of claim 6, wherein: formula (1) is represented by: ##STR00034## wherein: at least one pair of any one of R.sup.13 and R.sup.14 and any one of R.sup.15 and R.sup.16, taken together, form a C.sub.1-C.sub.6 alkylene.

9. A method for preparing an alkylsilane or cycloalkylsilane, comprising the step of reacting an alkene or cycloalkene with a hydrosilane or organohydropolysiloxane having a Si—H bond in the presence of the mononuclear ruthenium complex of claim 1.

10. A method for preparing an alkane or cycloalkane comprising the step of hydrogenating an alkene or cycloalkene in the presence of the mononuclear ruthenium complex of claim 1.

11. A method for preparing a linear, branched, or cyclic amine, comprising the step of reducing (i) a linear or branched amide or (ii) a lactam with a silane or organohydropolysiloxane having a Si—H bond in the presence of the mononuclear ruthenium complex of claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 illustrates the geometry of ruthenium complex A obtained in Example 1.

(2) FIG. 2 is a diagram showing .sup.1H-NMR spectrum of ruthenium complex A in Example 1.

(3) FIG. 3 is a diagram showing .sup.13C-NMR spectrum of ruthenium complex A in Example 1.

(4) FIG. 4 illustrates the geometry of ruthenium complex B obtained in Example 2.

(5) FIG. 5 is a diagram showing .sup.1H-NMR spectrum of ruthenium complex B in Example 2.

(6) FIG. 6 is a diagram showing .sup.13C-NMR spectrum of ruthenium complex B in Example 2.

DESCRIPTION OF EMBODIMENTS

(7) Now the invention is described in detail.

(8) The invention provides a mononuclear ruthenium complex having Ru—Si bonds and having at least one carbon monoxide (CO) coordinated to Ru, as represented by formula (1).

(9) ##STR00003##

(10) It is noted that in the mononuclear ruthenium complex of formula (1), when two CO's and two L's are contained (which are distinguishably represented by L.sup.1 and L.sup.2, respectively), for example, there exist coordination geometry isomers as depicted by the following formulae. The mononuclear ruthenium complex encompasses all such coordination geometry isomers.

(11) ##STR00004##

(12) In the mononuclear ruthenium complex of the invention, carbon monoxide (CO) is an essential coordinate moiety to display catalytic activity. While n is an integer of 1 to 3, n is preferably equal to 1 or 2, most preferably 2 for further enhancement of catalytic activity.

(13) R.sup.1 to R.sup.6 are each independently hydrogen, or an alkyl, aryl, aralkyl, organoxy, monoorganoamino, diorganoamino, monoorganophosphino, diorganophosphino, monoorganosilyl, diorganosilyl, triorganosilyl or organothio group which may be substituted with X, or at least one pair of any one of R.sup.1 to R.sup.3 and any one of R.sup.4 to R.sup.6, taken together, represent a crosslinking substituent, and X is a halogen atom, an organoxy, monoorganoamino, diorganoamino or organothio group.

(14) The alkyl group may be straight, branched or cyclic. Although its carbon count is not particularly limited, alkyl groups of 1 to 30 carbons, more preferably 1 to 10 carbons are preferable. Examples include straight or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-eicosanyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclononyl.

(15) For the aryl group, aryl groups of 6 to 30 carbons, more preferably 6 to 20 carbons are preferable although the carbon count is not particularly limited. Examples include phenyl, 1-naphthyl, 2-naphthyl, anthryl, phenanthryl, o-biphenylyl, m-biphenylyl, and p-biphenylyl.

(16) For the aralkyl group, aralkyl groups of 7 to 30 carbons, more preferably 7 to 20 carbons are preferable although the carbon count is not particularly limited. Examples include benzyl, phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl, and naphthylpropyl.

(17) Suitable organooxy groups include, but are not limited to, alkoxy, aryloxy and aralkyloxy groups represented by RO wherein R is a substituted or unsubstituted C.sub.1-C.sub.30 alkyl group, C.sub.6-C.sub.30 aryl group or C.sub.7-C.sub.30 aralkyl group.

(18) Suitable alkoxy group include, but are not limited to, alkoxy groups of 1 to 30 carbons, more preferably 1 to 10 carbons are preferable. Examples include methoxy, ethoxy, n-propoxy, i-propoxy, c-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, and n-decyloxy.

(19) Suitable aryloxy groups include, but are not limited to, aryloxy groups of 6 to 30 carbons, more preferably 6 to 20 carbons are preferable. Examples include phenoxy, 1-naphthyloxy, 2-naphthyloxy, anthryloxy, and phenanthryloxy.

(20) Suitable aralkyloxy groups include, but are not limited to, aryloxy aralkyloxy groups of 7 to 30 carbons, more preferably 7 to 20 carbons are preferable. Examples include benzyloxy, phenylethyloxy, phenylpropyloxy, 1 or 2-naphthylmethyloxy, 1 or 2-naphthylethyloxy, 1 or 2-naphthylpropyloxy.

(21) Suitable organothio groups include the foregoing organoxy groups whose oxygen atom is replaced by sulfur atom.

(22) The monoorganoamino group is preferably a group of RNH.sub.2 wherein R is as defined above, though not limited thereto. The preferred carbon count of R is the same as defined above for the alkoxy, aryloxy and aralkyloxy groups. Examples include straight or branched monoalkylamino groups such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, s-butylamino, t-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, n-undecylamino, n-dodecylamino, n-tridecylamino, n-tetradeylamino, n-pentadecylamino, n-hexadecylamino, n-heptadecylamino, n-octadecylamino, n-nonadecylamino, and n-eicosanylamino; monocycloalkylamino groups such as cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, cyclooctylamino, and cyclononylamino; monoarylamino groups such as anilino, 1 or 2-naphthylamino; and monoaralkylamino groups such as benzylamino, phenylethylamino, phenylpropylamino, 1 or 2-naphthylmethylamino.

(23) The diorganoamino group is preferably a group of R.sub.2NH wherein R is independently as defined above, though not limited thereto. The preferred carbon count of R is the same as defined above for the alkoxy, aryloxy and aralkyloxy groups. Examples include straight or branched dialkylamino groups such as dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, di-s-butylamino, di-t-butylamino, di-n-pentylamino, di-n-hexylamino, di-n-heptylamino, di-n-octylamino, di-n-nonylamino, di-n-decylamino, di-n-undecylamino, di-n-dodecylamino, di-n-tridecylamino, di-n-tetradeylamino, di-n-pentadecylamino, di-n-hexadecylamino, di-n-heptadecylamino, di-n-octadecylamino, di-n-nonadecylamino, di-n-eicosanylamino, N-ethylmethylamino, N-isopropylmethylamino, and N-butylmethylamino; dicycloalkylamino groups such as dicyclopropylamino, dicyclobutylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, dicyclooctylamino, dicyclononylamino, and cyclopentylcyclohexylamino; alkylarylamino groups such as N-methylanilino, N-ethylanilino, and N-n-propylanilino; diarylamino groups such as diphenylamino, 4,4′-bisnaphthylamino, N-phenyl-1 or 2-naphthylamino; and diaralkylamino groups such as dibenzylamino, bis(phenylethyl)amino, bis(phenylpropyl)amino, bis(1 or 2-naphthylmethyl)amino.

(24) The monoorganophosphino group is preferably a group of RPH wherein R is independently as defined above, though not limited thereto. The preferred carbon count of R is the same as defined above for the alkoxy, aryloxy and aralkyloxy groups. Examples include straight or branched monoalkylphosphino groups such as methylphosphino, ethylphosphino, n-propylphosphino, isopropylphosphino, n-butylphosphino, isobutylphosphino, s-butylphosphino, t-butylphosphino, n-pentylphosphino, n-hexylphosphino, n-heptylphosphino, n-octylphosphino, n-nonylphosphino, n-decylphosphino, n-undecylphosphino, n-dodecylphosphino, n-tridecylphosphino, n-tetradeylphosphino, n-pentadecylphosphino, n-hexadecylphosphino, n-heptadecylphosphino, n-octadecylphosphino, n-nonadecylphosphino, and n-eicosanylphosphino; monocycloalkylphosphino groups such as cyclopropylphosphino, cyclobutylphosphino, cyclopentylphosphino, cyclohexylphosphino, cycloheptylphosphino, cyclooctylphosphino, and cyclononylphosphino; monoarylphosphino groups such as phenylphosphino, 1 or 2-naphthylphosphino; and monoaralkylphosphino groups such as benzylphosphino.

(25) The diorganophosphino group is preferably a group of R.sub.2P wherein R is independently as defined above, though not limited thereto. The preferred carbon count of R is the same as defined above for the alkoxy, aryloxy and aralkyloxy groups. Examples include straight or branched dialkylphosphino groups such as dimethylphosphino, diethylphosphino, di-n-propylphosphino, diisopropylphosphino, di-n-butylphosphino, diisobutylphosphino, di-s-butylphosphino, di-t-butylphosphino, di-n-pentylphosphino, di-n-hexylphosphino, di-n-heptylphosphino, di-n-octylphosphino, di-n-nonylphosphino, di-n-decylphosphino, di-n-undecylphosphino, di-n-dodecylphosphino, di-n-tridecylphosphino, di-n-tetradeylphosphino, di-n-pentadecylphosphino, di-n-hexadecylphosphino, di-n-heptadecylphosphino, di-n-octadecylphosphino, di-n-nonadecylphosphino, and di-n-eicosanylphosphino; dicycloalkylphosphino groups such as dicyclopropylphosphino, dicyclobutylphosphino, dicyclopentylphosphino, dicyclohexylphosphino, dicycloheptylphosphino, dicyclooctylphosphino, and dicyclononylphosphino; alkylarylphosphino groups such as cyclohexylphenylphosphino; diarylphosphino groups such as diphenylphosphino, bis(1 or 2-naphthyl)phosphino; and diaralkylphosphino groups such as dibenzylphosphino, bis(phenylethyl)phosphino, bis(1 or 2-naphthylmethyl)phosphino.

(26) The monoorganosilyl group is preferably a group of RSiH.sub.2 wherein R is as defined above, though not limited thereto. The preferred carbon count of R is the same as defined above for the alkoxy, aryloxy and aralkyloxy groups. Examples include straight or branched monoalkylsilyl groups such as methylsilyl, ethylsilyl, n-propylsilyl, isopropylsilyl, n-butylsilyl, isobutylsilyl, s-butylsilyl, t-butylsilyl, n-pentylsilyl, n-hexylsilyl, n-heptylsilyl, n-octylsilyl, n-nonylsilyl, n-decylsilyl, n-undecylsilyl, n-dodecylsilyl, n-tridecylsilyl, n-tetradeylsilyl, n-pentadecylsilyl, n-hexadecylsilyl, n-heptadecylsilyl, n-octadecylsilyl, n-nonadecylsilyl, and n-eicosanylsilyl; monocycloalkylsilyl groups such as cyclopropylsilyl, cyclobutylsilyl, cyclopentylsilyl, cyclohexylsilyl, cycloheptylsilyl, cyclooctylsilyl, and cyclononylsilyl; monoarylsilyl groups such as phenylsilyl, 1 or 2-naphthylsilyl; and monoaralkylsilyl groups such as benzylsilyl, phenylethylsilyl, phenylpropylsilyl, 1 or 2-naphthylmethylsilyl.

(27) The diorganosilyl group is preferably a group of R.sub.2SiH wherein R is independently as defined above, though not limited thereto. The preferred carbon count of R is the same as defined above for the alkoxy, aryloxy and aralkyloxy groups. Examples include straight or branched dialkylsilyl groups such as dimethylsilyl, diethylsilyl, di-n-propylsilyl, diisopropylsilyl, di-n-butylsilyl, diisobutylsilyl, di-s-butylsilyl, di-t-butylsilyl, di-n-pentylsilyl, di-n-hexylsilyl, di-n-heptylsilyl, di-n-octylsilyl, di-n-nonylsilyl, di-n-decylsilyl, di-n-undecylsilyl, di-n-dodecylsilyl, di-n-tridecylsilyl, di-n-tetradeylsilyl, di-n-pentadecylsilyl, di-n-hexadecylsilyl, di-n-heptadecylsilyl, di-n-octadecylsilyl, di-n-nonadecylsilyl, di-n-eicosanylsilyl, ethylmethylsilyl, isopropylmethylsilyl, and butylmethylsilyl; dicycloalkylsilyl groups such as dicyclopropylsilyl, dicyclobutylsilyl, dicyclopentylsilyl, dicyclohexylsilyl, dicycloheptylsilyl, dicyclooctylsilyl, dicyclononylsilyl, and cyclopentylcyclohexylsilyl; alkylarylsilyl groups such as methylphenylsilyl, ethylphenylsilyl, and n-propylphenylsilyl; diarylsilyl groups such as diphenylsilyl, bis(1 or 2-naphthyl)silyl, phenyl-1 or 2-naphthylsilyl; and diaralkylsilyl groups such as dibenzylsilyl, bis(phenylethyl)silyl, bis(phenylpropyl)silyl, bis(1 or 2-naphthylmethyl)silyl.

(28) The triorganosilyl group is preferably a group of R.sub.3Si wherein R is independently as defined above, though not limited thereto. The preferred carbon count of R is the same as defined above for the alkoxy, aryloxy and aralkyloxy groups. Examples include straight or branched trialkylsilyl groups such as trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, triisobutylsilyl, tri-s-butylsilyl, tri-t-butylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tri-n-heptylsilyl, tri-n-octylsilyl, tri-n-nonylsilyl, tri-n-decylsilyl, tri-n-undecylsilyl, tri-n-dodecylsilyl, tri-n-tridecylsilyl, tri-n-tetradeylsilyl, tri-n-pentadecylsilyl, tri-n-hexadecylsilyl, tri-n-heptadecylsilyl, tri-n-octadecylsilyl, tri-n-nonadecylsilyl, tri-n-eicosanylsilyl, tri-n-eicosanylsilyl, ethyldimethylsilyl, diisopropylmethylsilyl, and dibutylmethylsilyl; tricycloalkylsilyl groups such as tricyclopropylsilyl, tricyclobutylsilyl, tricyclopentylsilyl, tricyclohexylsilyl, tricycloheptylsilyl, tricyclooctylsilyl, and tricyclononylsilyl; alkylarylsilyl groups such as methyldiphenylsilyl, ethyldiphenylsilyl, and n-propyldiphenylsilyl; triarylsilyl groups such as triphenylsilyl, tri(1 or 2-naphthyl)silyl, diphenyl-1 or 2-naphthylsilyl; and triaralkylsilyl groups such as tribenzylsilyl, tri(phenylethyl)silyl, tri(phenylpropyl)silyl, tri(1 or 2-naphthylmethyl)silyl.

(29) With respect to the foregoing substituent groups, at least one hydrogen atom on R may be substituted by a substituent X. Suitable substituents X include halogen, organoxy, monoorganoamino, diorganoamino, and organothio groups, and examples of the organoxy, monoorganoamino, diorganoamino, and organothio groups are as exemplified above.

(30) Exemplary of the halogen are fluorine, chlorine, bromine and iodine, with fluorine being preferred. Suitable fluorine-substituted alkyl groups include trifluoropropyl, nonafluorohexyl and heptadecylfluorodecyl.

(31) Of the foregoing substituent groups, R.sup.1 to R.sup.6 are each independently selected preferably from C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.30 aryl, and C.sub.7-C.sub.30 aralkyl groups which may be substituted with X, more preferably from C.sub.1-C.sub.10 alkyl and C.sub.6-C.sub.10 aryl groups.

(32) When a pair of any one of R.sup.1 to R.sup.3 and any one of R.sup.4 to R.sup.6, taken together, represent a crosslinking substituent, the crosslinking substituent is not particularly limited as long as it is capable of crosslinking two silicon atoms. Exemplary crosslinking substituents include —O—, —S—, —NH—, —NR— wherein R is as defined above, —PR— wherein R is as defined above, —NH—(CH.sub.2).sub.k—NH— wherein k is an integer of 1 to 10, —NR—(CH.sub.2).sub.k—NR— wherein k is as defined above and R is independently as defined above, —PH—(CH.sub.2).sub.k—PH— wherein k is as defined above, —PR—(CH.sub.2).sub.k—PR— wherein k is as defined above and R is independently as defined above, —C═C—, C.sub.1-C.sub.10 alkylene, C.sub.6-C.sub.30 arylene, C.sub.7-C.sub.30 aralkylene, —(CH.sub.2O).sub.k— wherein k is as defined above, —(CH.sub.2O).sub.k—O—(CH.sub.2).sub.k— wherein k is independently as defined above, —O—(CH.sub.2O).sub.k—O— wherein k is as defined above, —R′—O—(CH.sub.2O).sub.k—O—R′— wherein R′ is each independently a C.sub.1-C.sub.10 alkylene group, C.sub.6-C.sub.30 arylene group or C.sub.7-C.sub.30 aralkylene group and k is as defined above, —(CH.sub.2S).sub.k— wherein k is as defined above, —(CH.sub.2).sub.k—S—(CH.sub.2).sub.k— wherein k is independently as defined above, —S—(CH.sub.2).sub.k—S— wherein k is as defined above, —R′—S—(CH.sub.2).sub.k—O—R′— wherein R′ is independently as defined above and k is as defined above, —SiR.sub.2— wherein R is independently as defined above, and —(CH.sub.2).sub.k—SiR.sub.2—(CH.sub.2).sub.k— wherein R is independently as defined above and k is independently as defined above.

(33) Suitable C.sub.1-C.sub.10 alkylene groups include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene.

(34) Suitable C.sub.6-C.sub.30 arylene groups include o-phenylene(1,2-phenylene), 1,2-naphthylene, 1,8-naphthylene, and 2,3-naphthylene.

(35) Suitable C.sub.7-C.sub.30 aralkylene groups include —(CH.sub.2).sub.k—Ar— wherein Ar is a C.sub.6-C.sub.20 arylene group and k is as defined above, —Ar—(CH.sub.2).sub.k— wherein Ar and k are as defined above, and —(CH.sub.2).sub.k—Ar—(CH.sub.2).sub.k— wherein Ar is as defined above and k is independently as defined above.

(36) Notably, in the foregoing alkylene, arylene and aralkylene groups, at least one hydrogen atom may be substituted by a substituent X wherein X is as defined above.

(37) Assume that Z stands for a crosslinking substituent. Since the number of Z linking two silicon atoms is 1 to 3, the mononuclear ruthenium complex having a crosslinking substituent Z is represented by the following formulae.

(38) ##STR00005##
Herein R.sup.1, R.sup.2, R.sup.5, R.sup.6, L, n and m are as defined above, and Z is a crosslinking substituent.

(39) Illustrative examples of the disilametallacycle structure having a crosslinking substituent include those of the following formulae, but are not limited thereto.

(40) ##STR00006##
Herein Me stands for methyl.

(41) In the above formulae, R.sup.1, R.sup.2, R.sup.4 and R.sup.5 are as defined above, R.sup.17 to R.sup.20 (substituent Y) are each independently hydrogen, halogen, C.sub.1-C.sub.10 alkyl, or C.sub.1-C.sub.10 alkoxy group, R.sup.25 to R.sup.30 are each independently hydrogen or a substituted or unsubstituted, C.sub.1-C.sub.20 monovalent hydrocarbon group. Preferably R.sup.17 to R.sup.20 and R.sup.25 to R.sup.30 are hydrogen.

(42) Suitable monovalent hydrocarbon groups include alkyl, aryl and aralkyl groups, examples of which are as exemplified above.

(43) Examples of the alkyl group, alkoxy group and halogen are as exemplified above.

(44) L is a two-electron ligand other than CO and phosphine, wherein two electrons coordinate with ruthenium.

(45) The two-electron ligand is not particularly limited as long as CO and phosphine are excluded. Use may be made of any ligands which are conventionally used as the two-electron ligand in metal complexes, exclusive of CO. Typical ligands include compounds of nitrogen, oxygen, sulfur, and other elements containing an unshared electron pair (unpaired electron) such as amine, imine, nitrogen-containing heterocycle, arsine, alcohol, thiol, ether, and sulfide; compounds containing π-electron such as alkene and alkyne; compounds containing both unpaired electron and π-electron such as aldehyde, ketone, nitrile, and isonitrile; molecular hydrogen (σ-electron in H—H bond coordinates) and hydrosilane (σ-electron in Si—H bond coordinates) capable of bonding by agostic interaction.

(46) Included in the amine are tertiary amines represented by R.sub.3N wherein R is each independently as defined above.

(47) Included in the imine are those represented by RC(═NR)R wherein R is each independently as defined above.

(48) Examples of the nitrogen-containing heterocycle include pyrrole, imidazole, pyridine, pyrimidine, oxazoline, and isooxazoline.

(49) Examples of the arsine include those of R.sub.3As wherein R is each independently as defined above.

(50) Examples of the alcohol include those of ROH wherein R is as defined above.

(51) Included in the thiol are those obtained by substituting sulfur atom for oxygen atom of the above alcohols.

(52) Included in the ether are those represented by ROR wherein R is each independently as defined above.

(53) Included in the sulfide are those obtained by substituting sulfur atom for oxygen atom of the above ethers.

(54) Included in the ketone are those represented by RCOR wherein R is each independently as defined above.

(55) Included in the isonitrile are those represented by RNC wherein R is each independently as defined above.

(56) Included in the alkene are those of 2 to 30 carbon atoms such as ethene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, cyclopentene, 1-hexene, cyclohexene, 1-heptene, 1-octene, 1-nonene, and 1-decene.

(57) Included in the alkyne are those of 2 to 30 carbon atoms such as ethyne, propyne, 1-butyne, 2-butyne, 1-pentyne, 2-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, and 1-decyne.

(58) Examples of the hydrosilane include triorganohydrosilanes, specifically tri(C.sub.1-C.sub.30 organo)hydrosilanes, for example, those of R.sup.1R.sup.2R.sup.3SiH wherein R.sup.1 to R.sup.3 are as defined above.

(59) Of the foregoing, the two-electron ligand L is preferably molecular hydrogen, amine, imine, nitrogen-containing heterocycle, arsine, alcohol, thiol, ether, sulfide, nitrile, isonitrile, aldehyde, ketone, C.sub.2-C.sub.30 alkene, C.sub.2-C.sub.30 alkyne, or triorganohydrosilane.

(60) Where two L's are present, they may bond together to form a ligand containing two coordinating two-electron functional groups. Typical examples include, but are not limited to, ethylenediamine, ethylene glycol dimethyl ether, 1,3-butadiene, and those of the formulae shown below.

(61) In the mononuclear ruthenium complex, it is excluded that where three L's are present, all they bond together to form a ligand containing three coordinating two-electron functional groups.

(62) ##STR00007##
Herein Me stands for methyl, and Ph for phenyl.

(63) In the mononuclear ruthenium complex, the coordination number m of two-electron ligand L is an integer of 1 to 3, preferably 2.

(64) The sum of the coordination number n of CO and the coordination number m of L is equal to 3 or 4, preferably 4.

(65) Herein, a two-electron ligand L which forms a relatively weak bond with ruthenium is advantageous in terms of catalytic activity. Among the above examples, L is more preferably a thiol, sulfide, or triorganohydrosilane, and even more preferably two triorganohydrosilanes of SiHR.sup.7R.sup.8R.sup.9 and SiHR.sup.10R.sup.11R.sup.12 wherein R.sup.7 to R.sup.12 are each independently an alkyl, aryl or aralkyl group which may be substituted with X which is as defined above, and two sulfides or thiols of SR.sup.13R.sup.14 and SR.sup.15R.sup.16 wherein R.sup.13 to R.sup.16 are each independently hydrogen, or an alkyl, aryl or aralkyl group which may be substituted with X which is as defined above.

(66) Examples of the alkyl, aryl and aralkyl group are the same as exemplified above, while C.sub.1-C.sub.10 alkyl, C.sub.6-C.sub.20 aryl and C.sub.7-C.sub.20 aralkyl groups are preferred, and C.sub.1-C.sub.10 alkyl and C.sub.6-C.sub.20 aryl groups are more preferred.

(67) When L's are triorganohydrosilanes of SiHR.sup.7R.sup.8R.sup.9 and SiHR.sup.10R.sup.11R.sup.12 wherein R.sup.7 to R.sup.12 are as defined above, at least two of four silicon atoms in the mononuclear ruthenium complex may be linked by the crosslinking substituent Z. A combination of silicon atoms may be either a combination of silicon atoms having a silicon-ruthenium covalent bond, a combination of silicon atoms in Si—H coordination, or a combination of a silicon-ruthenium covalent bond with a silicon atom in Si—H coordination. Herein, the number of Z linking two silicon atoms is 1 to 3 whereas the total number of Z in the overall complex is 1 to 12.

(68) When a mononuclear ruthenium complex having crosslinking substituent Z is represented by a single coordination geometry, exemplary geometries are those of the following formulae, but not limited thereto. As alluded to previously, there are present coordination geometry isomers other than the illustrated ones, and in such cases, similar geometries having crosslinking substituent Z are present.

(69) ##STR00008##
Herein R.sup.1 to R.sup.12 and Z are as defined above.

(70) Exemplary geometries of the mononuclear ruthenium complex having disilametallacycle structure include those of the following formulae (depicted with CO omitted), but are not limited thereto.

(71) ##STR00009##
Herein Me stands for methyl.

(72) When L's are two sulfides or thiols of SR.sup.13R.sup.14 and SR.sup.15R.sup.16 wherein R.sup.13 to R.sup.16 are as defined above, two sulfur atoms in the mononuclear ruthenium complex may be linked by the crosslinking substituent Z.

(73) When a mononuclear ruthenium complex having crosslinking substituent Z is represented by a single coordination geometry, exemplary geometries are those of the following formulae, but not limited thereto. As alluded to previously, there are present coordination geometry isomers other than the illustrated ones, and in such cases, similar geometries having crosslinking substituent Z are present.

(74) In these cases, two silicon atoms in the mononuclear ruthenium complex may be linked by the crosslinking substituent Z.

(75) ##STR00010##
Herein R.sup.1 to R.sup.6, R.sup.13, R.sup.16 and Z are as defined above.

(76) Exemplary geometries of the dithia(dithio)metallacycle structure include those of the following formulae, but are not limited thereto.

(77) ##STR00011##
Herein R.sup.13, R.sup.16, R.sup.25 to R.sup.30 are as defined above.

(78) Exemplary geometries of the mononuclear ruthenium complex having dithiametallacycle structure include those of the following formulae, but are not limited thereto.

(79) ##STR00012##
Herein R.sup.1 to R.sup.6 are as defined above and Me stands for methyl.

(80) Especially preferred in the invention are mononuclear ruthenium complexes having two CO's coordinated and triorganohydrosilanes (as two-electron ligand) in agostic Si—H bond coordination. When such a ruthenium complex is represented for convenience sake by a single coordination geometry, exemplary geometries are those of formula (2). As alluded to previously, other coordination geometry isomers are acceptable.

(81) ##STR00013##

(82) Herein R.sup.1 to R.sup.12 are as defined above. Preferably R.sup.1 to R.sup.6 are each independently an alkyl, aryl or aralkyl group which may be substituted with X which is as defined above.

(83) Examples of the alkyl, aryl and aralkyl groups are the same as exemplified above, while C.sub.1-C.sub.10 alkyl, C.sub.6-C.sub.20 aryl and C.sub.7-C.sub.20 aralkyl groups are preferred, and C.sub.1-C.sub.10 alkyl and C.sub.6-C.sub.20 aryl groups are more preferred.

(84) In formula (2) as well, at least two of four silicon atoms in the mononuclear ruthenium complex may be linked by the crosslinking substituent. Specifically, at least one pair of any one of R.sup.1 to R.sup.3 and any one of R.sup.4 to R.sup.6 or any one of R.sup.7 to R.sup.9, or at least one pair of any one of R.sup.10 to R.sup.12 and any one of R.sup.4 to R.sup.6 or any one of R.sup.7 to R.sup.9 may bond together to form a crosslinking substituent such as alkylene, arylene or aralkylene. Alternatively, at least one pair of any one of R.sup.1 to R.sup.3 and any one of R.sup.4 to R.sup.6 or any one of R.sup.7 to R.sup.9 may bond together to form a crosslinking substituent such as alkylene, arylene or aralkylene, and at least one pair of any one of R.sup.10 to R.sup.12 and any one of R.sup.4 to R.sup.6 or any one of R.sup.7 to R.sup.9 may bond together to form a crosslinking substituent such as alkylene, arylene or aralkylene.

(85) Examples of the alkylene, arylene and aralkylene groups are the same as exemplified above, while C.sub.1-C.sub.10 alkylene, C.sub.7-C.sub.20 arylene and C.sub.7-C.sub.20 aralkylene groups are preferred, and C.sub.1-C.sub.6 alkylene and C.sub.7-C.sub.20 arylene groups are more preferred.

(86) Also useful are mononuclear ruthenium complexes having two CO's coordinated and two sulfides or thiols (as two-electron ligand) coordinated. When such a ruthenium complex is represented for convenience sake by a single coordination geometry, exemplary geometries are those of formula (3). As alluded to previously, other coordination geometry isomers are acceptable.

(87) ##STR00014##

(88) In formula (3), R.sup.1 to R.sup.6 and R.sup.13 to R.sup.16 are as defined above. Preferably R.sup.13 to R.sup.16 are each independently an alkyl, aryl or aralkyl group which may be substituted with X which is as defined above.

(89) Examples of the alkyl, aryl and aralkyl groups are the same as exemplified above, while C.sub.1-C.sub.10 alkyl, C.sub.6-C.sub.20 aryl and C.sub.7-C.sub.20 aralkyl groups are preferred, and C.sub.1-C.sub.10 alkyl and C.sub.6-C.sub.20 aryl groups are more preferred.

(90) In formula (3) as well, two sulfur atoms in the mononuclear ruthenium complex may be linked by the crosslinking substituent. Specifically, at least one pair of either one of R.sup.13 and R.sup.14 and either one of R.sup.15 and R.sup.16 may bond together to form a crosslinking substituent such as alkylene, arylene or aralkylene.

(91) In this case, two silicon atoms in the mononuclear ruthenium complex may be linked by the crosslinking substituent. Specifically, at least one pair of any one of R.sup.1 to R.sup.3 and any one of R.sup.4 to R.sup.6 may bond together to form a crosslinking substituent such as alkylene, arylene or aralkylene.

(92) Examples of the alkylene, arylene and aralkylene groups are the same as exemplified above, while C.sub.1-C.sub.10 alkylene, C.sub.7-C.sub.20 arylene and C.sub.7-C.sub.20 aralkylene groups are preferred, and C.sub.1-C.sub.6 alkylene and C.sub.7-C.sub.20 arylene groups are more preferred.

(93) When the preferred mononuclear ruthenium complex which can be used herein is represented by a single coordination geometry, exemplary geometries are those of formulae (4) and (5), more specifically formulae (6) and (7). As alluded to previously, other coordination geometry isomers are acceptable.

(94) ##STR00015##
Herein, R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.7, R.sup.8, R.sup.10, R.sup.11, R.sup.13, and R.sup.16 to R.sup.20 are as defined above, and R.sup.21 to R.sup.24 are as defined for R.sup.17.

(95) In formula (5), “a” is an integer of 1 to 6, preferably 2 or 3.

(96) ##STR00016##
Herein Me stands for methyl.

(97) The mononuclear ruthenium complex of the invention may be prepared by any combination of well-known organic synthetic reactions.

(98) For example, the ruthenium complex having formula (4) or (6) may be obtained by irradiating with light a ruthenium-carbonyl complex having a cycloalkadienyl group such as cyclohexadienyl or cyclooctadienyl as a ligand and a bissilyl compound such as 1,2-bis(dimethylsilyl)benzene in an inert gas atmosphere such as argon gas.

(99) In this case, the amount of the bissilyl compound used may be about 1 to 10 moles, preferably 2 to 5 moles per mole of the ruthenium-carbonyl complex.

(100) As the organic solvent, any solvents may be used as long as they do not adversely affect the reaction. Suitable solvents used herein include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, and 1,4-dioxane; and aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene.

(101) The reaction temperature may be set as appropriate in the range from the melting point to the boiling point of the organic solvent, preferably in the range of 10 to 50° C., and more preferably 15 to 30° C.

(102) The reaction time is typically about 1 to about 48 hours.

(103) After the completion of reaction, the solvent is distilled off, whereupon the target compound may be isolated by well-known purifying means such as recrystallization. Without isolation, the ruthenium complex as prepared may be used as a catalyst for the intended reaction.

(104) Also, the ruthenium complex having a sulfide ligand as represented by formula (5) or (7) may be prepared by starting with the ruthenium complex of formula (4) or (6) obtained by the above method, for example, and reacting it with a dithia hydrocarbon compound (e.g., 2,6-dithiaheptane) or a thiol compound (e.g., 1,3-propanedithiol) in an organic solvent as exemplified above in an inert gas atmosphere such as argon gas.

(105) In this case, the amount of the dithia hydrocarbon compound used may be about 1 to 3 moles, preferably 1 to 1.5 moles, and more preferably 1 to 1.2 moles per mole of the ruthenium complex.

(106) The reaction temperature may be set as appropriate in the range from 0° C. to the boiling point of the organic solvent, preferably in the range of 10 to 50° C., and more preferably 15 to 30° C.

(107) The reaction time is typically about 1 to about 48 hours.

(108) After the completion of reaction, the solvent is distilled off, whereupon the target compound may be isolated by well-known purifying means such as recrystallization. Without isolation, the ruthenium complex as prepared may be used as a catalyst for the intended reaction.

(109) As alluded to previously, the mononuclear ruthenium complex of the invention displays catalytic activity to three reactions: hydrosilylation reaction, hydrogenation reaction, and reductive reaction of carbonyl compounds.

(110) For hydrosilylation reaction between a compound having an aliphatic unsaturated bond such as an olefin, silane or organopolysiloxane compound and a compound having a Si—H bond such as a silane or organopolysiloxane compound in the presence of the inventive mononuclear ruthenium complex as catalyst, the amount of the catalyst used, though not particularly limited, is preferably at least 0.5 mol % when it is taken into account that the target compound is obtained in high yields by driving reaction under mild conditions at room temperature to about 100° C.

(111) When an olefin compound having an aliphatic unsaturated bond is reduced with hydrogen gas in the presence of the inventive mononuclear ruthenium complex as catalyst, to produce a saturated compound, the amount of the catalyst used, though not particularly limited, is preferably at least 1 mol % when it is taken into account that the target compound is obtained in high yields by driving reaction under mild conditions at room temperature and a hydrogen pressure of about 1 atm.

(112) In either of the reactions, the upper limit of the amount of the catalyst used is about 10 mol % from the economic aspect, though not critical.

(113) Also, when a carbonyl compound is reduced with a silane or siloxane compound having a Si—H group in the presence of the inventive mononuclear ruthenium complex as catalyst, the amount of the catalyst used, though not particularly limited, is preferably at least 0.01 mol % when it is taken into account that the target compound is obtained in high yields by driving reaction under mild conditions. The upper limit of the amount of the catalyst used is about 5 mol % from the economic aspect, though not critical.

(114) Examples of the carbonyl compound which can be subjected to reductive reaction include compounds having an amide, aldehyde, ketone, ester, carboxylic acid, and carboxylic acid salt (e.g., sodium or potassium salt) group. The carbonyl compound can be converted to a corresponding amine or alcohol compound by reacting it with a silane or siloxane having a Si—H group in the presence of the inventive ruthenium complex catalyst.

EXAMPLES

(115) Examples of the invention are given below by way of illustration and not by way of limitation.

(116) For synthesis of ruthenium complexes, a Schlenk system or glovebox was used, and all steps were performed in nitrogen or argon atmosphere. All the solvents used in the preparation of transition metal compounds were deoxygenated and dried by well-known techniques prior to use.

(117) Hydrosilylation reaction of alkene, reductive reaction of amide, and solvent purification were all performed in an inert gas atmosphere. All the solvents and ingredients used in these reactions were purified, dried and deoxygenated by well-known techniques prior to use.

(118) Analysis of .sup.1H, .sup.13C and .sup.29Si-NMR was performed by JNM-ECA600 and JNM-LA400 (JEOL Ltd.); IR spectroscopy by FT/IR-550 (JASCO Corp.); elemental analysis by 2400II/CHN (Perkin Elmer); X-ray crystallography by VariMax (Rigaku Corp.) with MoK α-ray of 0.71069 angstrom.

(119) It is noted that in the chemical structural formulae shown below, hydrogen atoms are omitted according to the standard nomenclature. Me stands for methyl.

(1) Synthesis of Ruthenium Complex

Example 1

Synthesis of Ruthenium Complex A

(120) A 100-mL Schlenk tube under argon atmosphere was charged with (η.sup.4-1,3-cyclohexadiene)ruthenium(0) tricarbonyl complex (500 mg, 1.87 mmol) and 1,2-bis(dimethylsilyl)benzene (800 mg, 4.11 mmol), to which hexane (50 mL) which had been deaerated and dried was added. Under light irradiation using a high-pressure mercury lamp (UM-453B-A, 450 W, by Ushio Inc.), the contents were stirred at room temperature for 22 hours. After the completion of reaction, the reaction mixture was dried in vacuum. The dry product was dissolved in hexane (40 mL), from which a small amount of brown insoluble matter as by-product was removed by centrifugation. Thereafter, the hexane solution was concentrated under reduced pressure to about 25 mL. Subsequent recrystallization at −35° C. yielded ruthenium complex A (274 mg, 0.50 mmol, 27%) typically represented by formula (6). For the resulting ruthenium complex A, the geometry is shown in FIG. 1, the measurement results of .sup.1H-NMR in FIG. 2, and the measurement results of .sup.13C-NMR in FIG. 3.

(121) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=−7.3 (s, Jsi-.sub.H=16.8 Hz, 2H, Si—H), 0.75 (s, 24H, SiMe.sub.2), 7.23-7.28 (m, 4H, C.sub.6H.sub.4), 7.53-7.58 (m, 4H, C.sub.6H.sub.4).

(122) .sup.13C NMR (CDCl.sub.3, 395 MHz): δ=8.4, 128.9, 131.4, 152.5, 198.4.

(123) IR (KBr pellet): ν=1975 (ν.sub.Si-H), 1978 (ν.sub.Ru-OH) cm.sup.−1

(124) Anal. calcd. for C.sub.22H.sub.34O.sub.2RuSi.sub.4:

(125) C, 48.58; H, 6.30 Found: C, 48.34; H, 6.29.

Example 2

Synthesis of Ruthenium Complex B

(126) In a 50-mL Schlenk tube under argon atmosphere, ruthenium complex A (100 mg, 0.18 mmol) was dissolved in toluene (20 mL) which had been deaerated and dried, to which 2,6-dithiaheptane (26 mg, 0.19 mmol) was added. The contents were stirred at room temperature for 12 hours. After the completion of reaction, the reaction mixture was dried in vacuum. The dry product was dissolved in diethyl ether (10 mL). Thereafter, the solution was concentrated under reduced pressure to about 5 mL. Subsequent recrystallization at −35° C. yielded ruthenium complex B (82 mg, 0.17 mmol, 94%) typically represented by formula (7). For the resulting ruthenium complex B, the geometry is shown in FIG. 4, the measurement results of .sup.1H-NMR in FIG. 5, and the measurement results of .sup.13C-NMR in FIG. 6.

(127) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=0.82 (s, 12H, SiMe.sub.2), 1.24 (quint, 2H, —CH.sub.2CH.sub.2CH.sub.2—), 1.81 (t, 4H, —CH.sub.2CH.sub.2CH.sub.2—), 1.87 (s, 6H, Sme), 7.32-7.38 (m, 2H, C.sub.6H.sub.4), 7.83-7.87 (m, 2H, C.sub.6H.sub.4).

(128) .sup.13C NMR (CDCl.sub.3, 395 MHz): δ=1.53, 6.39, 23.1, 25.6, 37.4, 127.5, 131.6, 157.5.

(129) Anal. Calcd. for C.sub.22H.sub.28O.sub.2RuSi.sub.2S.sub.2:

(130) C, 42.03; H, 5.81 Found: C, 42.21; H, 5.69.

(2) Hydrosilylation Reaction Using Ruthenium Complex a

Example 3

Hydrosilylation of 2-octene with 1,1,1,3,3-pentamethyldisiloxane

(131) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (8 mg, 0.015 mmol) was admitted as catalyst. To the tube, 1-octene (78.2 μL, 0.5 mmol) was added, after which 1,1,1,3,3-pentamethyldisiloxane (97.6 μL, 0.5 mmol) was added. The solution was stirred at 80° C. for 3 hours. The solution was cooled, to which anisole (108.6 μL, 1.0 mmol, the amount used is identical hereinafter) was added as internal standard. By .sup.1H-NMR spectroscopy, the geometry and yield of the product were determined. The results are shown as Entry 1 in Table 1.

(132) .sup.1H NMR (400 MHz, CDCl.sub.3): δ=0.03 (s, 6H, Si(CH.sub.3).sub.2), 0.06 (s, 9H, Si(CH.sub.3).sub.3), 0.45-0.55 (m, 2H, SiCH.sub.2), 0.88 (t, J.sub.HH=7.2 Hz, 3H, CH.sub.2CH.sub.3), 1.20-1.34 (m, 12H, (CH.sub.2).sub.6).

Example 4

Hydrosilylation of 2-octene with 1,1,1,3,5,5,5-heptamethyltrisiloxane

(133) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (8 mg, 0.015 mmol) was admitted as catalyst. To the tube, 2-octene (78.2 μL, 0.5 mmol) was added, after which 1,1,1,3,5,5,5-heptamethyltrisiloxane (135.7 μL, 0.5 mmol) was added. The solution was stirred at 80° C. for 3 hours. The solution was cooled, to which anisole was added as internal standard. By .sup.1H-NMR spectroscopy, the geometry and yield of the product were determined. The results are shown as Entry 2 in Table 1.

(134) .sup.1H NMR (600 MHz, CDCl.sub.3): δ=−0.01 (s, 3H, SiCH.sub.3), 0.09 (s, 18H, (Si(CH.sub.3).sub.3).sub.2), 0.42-0.47 (m, 2H, SiCH.sub.2), 0.88 (t, J.sub.HH=6.8 Hz, 3H, CH.sub.2CH.sub.3), 1.23-1.33 (m, 12H, (CH.sub.2).sub.6).

Example 5

Hydrosilylation of 2-octene with Triethoxysilane

(135) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (8 mg, 0.015 mmol) was admitted as catalyst. To the tube, 2-octene (78.2 μL, 0.5 mmol) was added, after which triethoxysilane (92.3 μL, 0.5 mmol) was added. The solution was stirred at 80° C. for 3 hours. The solution was cooled, to which anisole was added as internal standard substance. By .sup.1H-NMR spectroscopy, the geometry and yield of the product were determined. The results are shown as Entry 3 in Table 1.

(136) .sup.1H NMR (400 MHz, CDCl.sub.3): δ=0.63 (m, 2H, Si(CH.sub.2)), 0.72 (t, 3H, CH.sub.3), 1.15 (t, J.sub.HH=7.2 Hz, 9H, Si(OCH.sub.2CH.sub.3)), 1.29 (m, 12H, CH.sub.2), 3.73 (q, J.sub.HH=7.2 Hz, 9H, Si(OCH.sub.2CH.sub.3)).

Example 6

Hydrosilylation of 2-octene with Triethylsilane

(137) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (8 mg, 0.015 mmol) was admitted as catalyst. To the tube, 2-octene (78.2 μL, 0.5 mmol) was added, after which triethylsilane (79.8 μL, 0.5 mmol) was added. The solution was stirred at 80° C. for 3 hours. The solution was cooled, to which anisole was added as internal standard. By .sup.1H-NMR spectroscopy, the geometry and yield of the product were determined. The results are shown as Entry 4 in Table 1.

(138) .sup.1H NMR (400 MHz, CDCl.sub.3): δ=0.51 (m, 8H, Si(CH.sub.2).sub.4), 0.84-1.04 (m, 12H, Si(CH.sub.2CH.sub.3) and CH.sub.3), 1.18-1.38 (m, 12H, CH.sub.2).

(139) TABLE-US-00001 TABLE 1 Entry Si—H Yield .sup.a 1 TMSOSiMe.sub.2H 16 2 (TMSO).sub.2SiMeH 15 3 (EtO).sub.3SiH 20 4 Et.sub.3SiH 40 .sup.a Yield was determined by .sup.1H NMR analysis with anisole as an internal standard.

Example 7

Hydrosilylation of 1-octene with 1,1,1,3,3-pentamethyldisiloxane

(140) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (8 mg, 0.015 mmol) was admitted as catalyst. To the tube, 1-octene (78.2 μL, 0.5 mmol) was added, after which 1,1,1,3,3-pentamethyldisiloxane (97.6 μL, 1.0 mmol) was added. The solution was stirred at 80° C. for 3 hours. The solution was cooled, to which anisole was added as internal standard. By .sup.1H-NMR spectroscopy, the geometry and yield of the product were determined. The results are shown as Entry 1 in Table 2.

(141) .sup.1H NMR (400 MHz, CDCl.sub.3): δ=0.03 (s, 6H, Si(CH.sub.3).sub.2), 0.06 (s, 9H, Si(CH.sub.3).sub.3), 0.45-0.55 (m, 2H, SiCH.sub.2), 0.88 (t, J.sub.HH=7.2 Hz, 3H, CH.sub.2CH.sub.3), 1.20-1.34 (m, 12H, (CH.sub.2).sub.6).

Example 8

Hydrosilylation of 1-octene with 1,1,1,3,5,5,5-heptamethyltrisiloxane

(142) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (8 mg, 0.015 mmol) was admitted as catalyst. To the tube, 1-octene (78.2 μL, 0.5 mmol) was added, after which 1,1,1,3,5,5,5-heptamethyltrisiloxane (135.7 μL, 0.5 mmol) was added. The solution was stirred at 80° C. for 3 hours. The solution was cooled, to which anisole was added as internal standard. By .sup.1H-NMR spectroscopy, the geometry and yield of the product were determined. The results are shown as Entry 2 in Table 2.

(143) .sup.1H NMR (600 MHz, CDCl.sub.3): δ=−0.01 (s, 3H, SiCH.sub.3), 0.09 (s, 18H, (Si(CH.sub.3).sub.3).sub.2), 0.42-0.47 (m, 2H, SiCH.sub.2), 0.88 (t, J.sub.HH=6.8 Hz, 3H, CH.sub.2CH.sub.3), 1.23-1.33 (m, 12H, (CH.sub.2).sub.6).

Example 9

Hydrosilylation of cyclopentene with 1,1,1,3,3-pentamethyldisiloxane

(144) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (8 mg, 0.015 mmol) was admitted as catalyst. To the tube, cyclopentene (44.2 μL, 0.5 mmol) was added, after which 1,1,1,3,3-pentamethyldisiloxane (97.6 μL, 0.5 mmol) was added. The solution was stirred at 80° C. for 3 hours. The solution was cooled, to which anisole was added as internal standard. By .sup.1H-NMR spectroscopy, the geometry and yield of the product were determined. The results are shown as Entry 3 in Table 2.

(145) .sup.1H NMR (400 MHz, C.sub.6D.sub.6): δ=0.10 (s, 6H, SiCH.sub.3), 0.13 (s, 9H, (Si(CH.sub.3).sub.3), 0.81-0.93 (m, 1H, SiCH(CH.sub.2).sub.2), 1.28-1.40 (m, 2H, CH.sub.2), 1.46-1.63 (m, 4H, CH.sub.2), 1.65-1.79 (m, 2H, CH.sub.2).

(146) TABLE-US-00002 TABLE 2 Entry Olefin Si—H Yield .sup.a 1 1-octene TMSOSiMe.sub.2H 15 2 1-octene (TMSO).sub.2SiMeH 15 3 cyclopentene TMSOSiMe.sub.2H 17 .sup.a Yield was determined by .sup.1H NMR analysis with anisole as an internal standard.

(3) Hydrogenation Reaction Using Ruthenium Complex a

Example 10

Hydrogenation of Styrene

(147) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (14 mg, 0.02 mmol) was admitted as catalyst and dissolved in toluene (1 mL). To the solution, styrene (57 μL, 0.5 mmol) was added. The solution was freeze deaerated, after which the Schlenk tube was purged with hydrogen atmosphere. The solution was stirred at room temperature for 3 hours. With anisole added as internal standard, the geometry and yield of the product were determined by .sup.1H-NMR spectroscopy. The resulting compound was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy. The results are shown as Entry 1 in Table 3.

(148) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=1.13 (t, J.sub.HH=7.2 Hz, 3H, CH.sub.2CH.sub.3), 2.54 (q, J.sub.HH=7.2 Hz, 2H, CH.sub.2CH.sub.3), 7.02-7.11 (m, 3H, C.sub.6H.sub.5), 7.11-7.20 (m, 2H, C.sub.6H.sub.5).

(149) .sup.13C NMR (100 MHz, CDCl.sub.3): δ=15.6, 28.8, 125.6, 127.8, 128.3, 144.3.

Example 11

Hydrogenation of Trans-Stilbene

(150) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (14 mg, 0.025 mmol) was admitted as catalyst and dissolved in toluene (1 mL). To the solution, trans-stilbene (90 mg, 0.5 mmol) was added. The solution was freeze deaerated, after which the Schlenk tube was purged with hydrogen atmosphere. The solution was stirred at room temperature for 6 hours. With anisole added as internal standard, the geometry and yield of the product were determined by .sup.1H-NMR spectroscopy. The resulting compound was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy. The results are shown as Entry 2 in Table 3.

(151) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=2.93 (s, 4H, CH.sub.2), 7.12-7.23 (m, 6H, C.sub.6H.sub.5), 7.24-7.32 (m, 4H, C.sub.6H.sub.5).

(152) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=37.9, 125.9, 128.3, 128.5, 141.8.

Example 12

Hydrogenation of Cyclohexene

(153) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (14 mg, 0.025 mmol) was admitted as catalyst and dissolved in toluene (1 mL). To the solution, cyclohexene (54 μL, 0.5 mmol) was added. The solution was freeze deaerated, after which the Schlenk tube was purged with hydrogen atmosphere. The solution was stirred at room temperature for 6 hours. With anisole added as internal standard, the geometry and yield of the product were determined by .sup.1H-NMR spectroscopy. The resulting compound was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy. The results are shown as Entry 3 in Table 3.

(154) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=1.43 (s, 12H, CH.sub.2).

(155) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=27.0.

Example 13

Hydrogenation of Cyclopentene

(156) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (14 mg, 0.025 mmol) was admitted as catalyst and dissolved in toluene (2 mL). To the solution, cyclopentene (44.2 μL, 0.5 mmol) was added. The solution was freeze deaerated, after which the Schlenk tube was purged with hydrogen atmosphere. The solution was stirred at room temperature for 6 hours. With anisole added as internal standard, the geometry and yield of the product were determined by .sup.1H-NMR spectroscopy. The resulting compound was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy. The results are shown as Entry 4 in Table 3.

(157) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=1.52 (s, 10H, CH.sub.2).

(158) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=25.9.

Example 14

Hydrogenation of 1-methyl-1-cyclohexene

(159) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (14 mg, 0.025 mmol) was admitted as catalyst and dissolved in toluene (1 mL). To the solution, 1-methyl-1-cyclohexene (54 μL, 1.0 mmol) was added. The solution was freeze deaerated, after which the Schlenk tube was purged with hydrogen atmosphere. The solution was stirred at room temperature for 6 hours. With anisole added as internal standard, the geometry and yield of the product were determined by .sup.1H-NMR spectroscopy. The resulting compound was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy. The results are shown as Entry 5 in Table 3.

(160) .sup.1H NMR (CDCl.sub.3, 395 MHz) δ=0.86 (d, J.sub.HH=5.8 Hz, 3H, CH.sub.3), 1.04-1.28 (m, 4H, CH.sub.2), 1.28-1.39 (m, 1H, CH), 1.54-1.72 (m, 6H, CH.sub.2).

(161) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=22.9, 26.3, 26.4, 32.7, 35.4.

Example 15

Hydrogenation of 2,3-dimethyl-2-butene

(162) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex A (14 mg, 0.025 mmol) was admitted as catalyst and dissolved in toluene (1 mL). To the solution, 2,3-dimethyl-2-butene (54 μL, 1.0 mmol) was added. The solution was freeze deaerated, after which the Schlenk tube was purged with hydrogen atmosphere. The solution was stirred at room temperature for 6 hours. With anisole added as internal standard, the geometry and yield of the product were determined by .sup.1H-NMR spectroscopy. The resulting compound was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy. The results are shown as Entry 6 in Table 3.

(163) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=0.84 (d, J.sub.HH=6.7 Hz, 12H, CH.sub.3), 1.40 (septet, J.sub.HH=6.7 Hz, 2H, CH).

(164) .sup.13C NMR (CDCl.sub.3, 100 MHz): δ=19.4, 33.7.

(165) TABLE-US-00003 TABLE 3 0 Entry Olefin Yield .sup. 1 .sup.a styrene 99 2 trans-stilbene 70 3 cyclohexene 96 4 cyclopentene 99 5 33 6 20 .sup.a Reaction time is 2 hours.

(4) Reductive Reaction of Amide Using Ruthenium Complex A

Example 16

Reduction of N,N-dimethyl-4-methoxybenzamide

(166) A 20-mL eggplant flask equipped with a three-way cock and a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the flask, ruthenium complex A (0.27 mg, 5.0×10.sup.−4 mmol) was admitted as catalyst. To the flask, dimethylphenylsilane (681 μL) was added through a syringe, and N,N-dimethyl-4-methoxybenzamide (179 mg, 1.0 mmol) was added. The solution was stirred at 25° C. for 5 hours. The remaining dimethylphenylsilane was distilled off in vacuum. The crude product was purified by silica gel-packed column chromatography using hexane/ethyl acetate (10/1) as developing solvent, obtaining N,N-dimethyl-4-methoxybenzylamine (149 mg, 0.90 mmol, 90%). The results are shown as Entry 1 in Table 4. The resulting amine was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy and IR spectroscopy.

(167) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=2.22 (s, 6H, NMe.sub.2), 3.35 (s, 2H, CH.sub.2), 3.80 (s, 3H, OMe), 6.85 (d, J=8.7 Hz, 2H, C.sub.6H.sub.4), 7.21 (d, J=8.7 Hz, 2H, C.sub.6H.sub.4).

(168) .sup.13C NMR (CDCl.sub.3, 395 MHz): δ=45.22, 55.07, 63.74, 130.23, 113.58, 131.15, 158.71.

(169) IR (neat): ν=1038, 1241, 1510, 2766, 2813, 2941 cm.sup.−1

Example 17

Reduction of N,N-dimethyl-4-bromobenzamide

(170) A 20-mL eggplant flask equipped with a three-way cock and a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the flask, ruthenium complex A (2.4 mg, 4.5×10.sup.−3 mmol) was admitted as catalyst. To the flask, dimethylphenylsilane (681 μL) was added through a syringe, and N,N-dimethyl-4-bromobenzamide (228 mg, 1.0 mmol) was added. The solution was stirred at 25° C. for 23 hours. The remaining dimethylphenylsilane was distilled off in vacuum. The crude product was purified by silica gel-packed column chromatography using hexane/ethyl acetate (20/1) as developing solvent, obtaining N,N-dimethyl-4-bromobenzylamine (184 mg, 0.86 mmol, 86%). The results are shown as Entry 2 in Table 4. The resulting amine was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy and IR spectroscopy.

(171) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=2.22 (s, 6H, NMe.sub.2), 3.36 (s, 2H, CH.sub.2), 7.18 (d, J=8.70 Hz, 2H, C.sub.6H.sub.4), 7.44 (d, J=8.70 Hz, 5H, C.sub.6H.sub.4).

(172) .sup.13C NMR (CDCl.sub.3, 395 MHz): δ=45.97, 64.30, 121.45, 131.33, 131.97, 138.67.

(173) IR (neat): ν=1011, 1487, 2767, 2815, 2941 cm.sup.−1.

Example 18

Reduction of N,N-dimethyl-3-phenylpropanamide

(174) A 20-mL eggplant flask equipped with a three-way cock and a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the flask, ruthenium complex A (0.27 mg, 5.0×10.sup.−4 mmol) was admitted as catalyst. To the flask, dimethylphenylsilane (681 μL) was added through a syringe, and N,N-dimethyl-3-phenylpropanamide (177 mg, 1.0 mmol) was added. The solution was stirred at 25° C. for 7 hours. The remaining dimethylphenylsilane was distilled off in vacuum. The crude product was purified by silica gel-packed column chromatography using hexane/ethyl acetate (10/1) as developing solvent, obtaining N,N-dimethyl-3-phenylpropylamine (151 mg, 0.79 mmol, 79%). The results are shown as Entry 3 in Table 4. The resulting amine was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy and IR spectroscopy.

(175) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=1.80 (quint, J=7.7 Hz, 2H, CH.sub.2), 2.23 (s, 6H, NMe.sub.2), 2.30 (t, J=7.7 Hz, 2H, CH.sub.2), 2.65 (t, J=7.7 Hz, 2H, CH.sub.2), 7.24-7.16 (m, 3H, C.sub.6H.sub.4), 7.35-7.25 (m, 2H, C.sub.6H.sub.4).

(176) .sup.13C NMR (CDCl.sub.3, 395 MHz): δ=29.57, 33.79, 45.60, 59.41, 125.84, 128.42, 128.50, 142.40.

(177) IR (neat): ν=1030, 1496, 2764, 2942, 3025, 3060 cm.sup.−1.

Example 19

Reduction of N-benzyl-ε-caprolactam

(178) A 20-mL eggplant flask equipped with a three-way cock and a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the flask, ruthenium complex A (0.27 mg, 5.0×10.sup.4 mmol) was admitted as catalyst. To the flask, dimethylphenylsilane (681 μL) was added through a syringe, and N-benzyl-ε-caprolactam (203 mg, 1.0 mmol) was added. The solution was stirred at 25° C. for 7 hours. The remaining dimethylphenylsilane was distilled off in vacuum. The crude product was purified by silica gel-packed column chromatography using hexane/ethyl acetate (10/1) as developing solvent, obtaining 1-benzylazepane (165 mg, 0.87 mmol, 87%). The results are shown as Entry 4 in Table 4. The resulting amine was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy and IR spectroscopy.

(179) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=1.58 (br, 8H, CH.sub.2), 2.57 (d, J=5.8 Hz, 2H, CH.sub.2), 3.60 (s, 2H, PhCH.sub.2), 7.22-7.13 (m, 2H, C.sub.6H.sub.4), 7.33-7.22 (m, 3H, C.sub.6H.sub.4).

(180) .sup.13C NMR (CDCl.sub.3, 395 MHz): δ=27.19, 28.40, 55.76, 62.90, 126.79, 128.22, 128.90, 140.30.

(181) IR (neat): ν=1071, 1354, 1452, 2851, 2923 cm.sup.−1.

(182) TABLE-US-00004 TABLE 4 Catalyst Reaction Reaction concentration time temperature Yield Entry Reactant (mol %) (hr) (° C.) Product (%) 1 0.05  5 25 90 2 0.45 23 25 86 3 0.05  7 25 79 4 0.05  7 25 0 87

(5) Hydrosilylation Reaction Using Ruthenium Complex B

Example 20

Hydrosilylation of ethylene with 1,1,1,3,3-pentamethyldisiloxane

(183) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex B (14 mg, 0.03 mmol) was admitted as catalyst. To the tube, 1,1,1,3,3-pentamethyldisiloxane (195.2 μL, 1.0 mmol) was added. The solution was freeze deaerated, after which the Schlenk tube was purged with ethylene atmosphere. The solution was stirred at 80° C. for 16 hours. After cooling, with anisole added as internal standard, the geometry and yield of the product were determined by .sup.1H-NMR spectroscopy (yield 55%). The resulting compound was identified for geometry by .sup.1H, .sup.13C and .sup.29Si-NMR spectroscopy.

(184) .sup.1H NMR (600 MHz, CDCl.sub.3): δ=0.03 (s, 6H, Si(CH.sub.3).sub.2), 0.06 (s, 9H, Si(CH.sub.3).sub.3), 0.49 (q, J.sub.HH=8.2 Hz, 2H, SiCH.sub.2CH.sub.3), 0.92 (t, J.sub.HH=8.2 Hz, 3H, CH.sub.2CH.sub.3).

(185) .sup.13C NMR (100 MHz, CDCl.sub.3): δ=−0.28, 1.93, 6.72, 10.03.

(186) .sup.29Si NMR (119 MHz, CDCl.sub.3): δ=7.05, 8.60.

(6) Hydrogenation Reaction Using Ruthenium Complex B

Example 21

Hydrogenation of Styrene

(187) A 20-mL Schlenk tube equipped with a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the Schlenk tube, ruthenium complex B (12 mg, 0.025 mmol) was admitted as catalyst and dissolved in toluene (1 mL). To the solution, styrene (57 μL, 0.5 mmol) was added. The solution was freeze deaerated, after which the Schlenk tube was purged with hydrogen atmosphere. The solution was stirred at 100° C. for 16 hours. With anisole (108.6 μL, 1.0 mmol) added as internal standard, the geometry and yield of the product were determined by .sup.1H-NMR spectroscopy (yield 71%). The resulting compound was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy.

(188) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=1.13 (t, J.sub.HH=7.2 Hz, 3H, CH.sub.2CH.sub.3), 2.54 (q, J.sub.HH=7.2 Hz, 2H, CH.sub.2CH.sub.3), 7.02-7.11 (m, 3H, C.sub.6H.sub.5), 7.11-7.20 (m, 2H, C.sub.6H.sub.5).

(189) .sup.13C NMR (100 MHz, CDCl.sub.3): δ=15.6, 28.8, 125.6, 127.8, 128.3, 144.3.

(7) Reductive Reaction of Amide Using Ruthenium Complex B

Example 22

Reduction of N,N-dimethyl-4-methoxybenzamide

(190) A 20-mL eggplant flask equipped with a three-way cock and a magnetic stirrer was heat dried while pumping to a vacuum of 5 Pa before its interior was purged with argon atmosphere. Into the flask, ruthenium complex B (12 mg, 0.025 mmol) was admitted as catalyst and dissolved in toluene (0.25 mL). To the solution, 1,2-bis(dimethylsilyl)benzene (238 μL) was added through a syringe, and N,N-dimethyl-4-methoxybenzamide (90 mg, 0.5 mmol) was added. The solution was stirred at 100° C. for 16 hours. After cooling, with ferrocene (18.6 mg, 1.0 mmol) added as internal standard, the geometry and yield of the product were determined by .sup.1H-NMR spectroscopy (yield 99%). The resulting compound was identified for geometry by .sup.1H and .sup.13C-NMR spectroscopy and IR spectroscopy.

(191) .sup.1H NMR (CDCl.sub.3, 395 MHz): δ=2.22 (s, 6H, NMe.sub.2), 3.35 (s, 2H, CH.sub.2), 3.80 (s, 3H, OMe), 6.85 (d, J=8.7 Hz, 2H, C.sub.6H.sub.4), 7.21 (d, J=8.7 Hz, 2H, C.sub.6H.sub.4).

(192) .sup.13C NMR (CDCl.sub.3, 395 MHz): δ=45.22, 55.07, 63.74, 130.23, 113.58, 131.15, 158.71.

(193) IR (neat): ν=1038, 1241, 1510, 2766, 2813, 2941 cm.sup.−1