Platinum-catalyzed hydrosilylation of alkynes

Lewis, Lionel S.; Sy, K. G.; Bryant, G. L.; Donahue, P. E.

doi:10.1021/om00056a055

Cited by 156 publications

(82 citation statements)

References 8 publications

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“…In addition to Pt group metals and Ni, even bimetallic compositions with significant synergic effect between the components have been recommended as effective catalysts. [410][411][412][413][414][415][416] …”

Section: Hydrosilylationmentioning

confidence: 99%

Asymmetric Catalysis at Chiral Metal Surfaces

2007

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He continued his academic carrier at the Organic Chemical Technology Research Group of the Hungarian Academy of Sciences. In 1990, he moved to ETH Zurich, where he is currently a scientist. He was awarded a D.Sc. degree in 1994 by the Hungarian Academy of Sciences. His main scientific interests are the application of heterogeneous catalysts in the synthesis of fine chemicals, including asymmetric catalysis, oxidation, and hydrogenation reactions, and the application of electrochemical methods in catalysis.

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Section: Hydrosilylationmentioning

confidence: 99%

Asymmetric Catalysis at Chiral Metal Surfaces

2007

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“…The use of PhMe 2 SiH in the hydrosilylation of phenylacetylene with both catalysts resulted in a different ratio of isomers, containing: trans (63-67%), gem (27%), and cis (6-10%) isomers. Results obtained in the two catalytic systems are listed in Tables 1 and 2. To compare results, Table 3 illustrates the product distribution for the same model reactions using the well known catalytic systems of Karsted, Speier, and Wilkinson (25)(26)(27)(28).…”

Section: Resultsmentioning

confidence: 99%

Metal supported catalysts obtained by sol-gel in the hydrosilylation of phenylacetylene with R₃SiH organosilanes (R₃ = Ph₃, Ph₂Me, and PhMe₂)

González-Jiménez

López

Cervantes³

2000

Can. J. Chem.

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The hydrosilylation reaction of phenylacetylene, generated on the surface of solid catalysts (such as Pt and Ru) supported on inorganic matrices such as MgO obtained by the sol-gel process, yields vinylsilanes as the main products. The products' distribution, specific activity, and turnover reactions were determined for the case of the hydrosilylation reaction of PhCϵCH with R 3 SiH (R = Ph 3 , Ph 2 Me, and PhMe 2 ). For Ph 3 SiH and Ph 2 MeSiH, the presence of β-trans and α isomers is observed. Addition of PhMe 2 SiH to phenylacetylene leads to the formation of β (cis and trans) and α isomers. These catalytic systems provide a new synthetic route to Si-C bond formation.Résumé : La réaction d'hydrosilylation du phénylacétylène, effectuée à la surface d'un catalyseur solide tel le Pt ou le Ru fixé sur des matrices inorganiques tel le MgO obtenu selon le procédé de sol-gel, donne des vinylsilanes comme produits majoritaires. On a déterminé, la distribution des produits, l'activité spécifique et les réactions d'échange dans le cas de la réaction d'hydrosilylation du PhCϵCH avec R 3 SiH (R = Ph 3 , PH 2 Me, et PhMe 2 ). On a observé la présence d'isomères β-trans et α dans le cas du Ph 3 SiH, PH 2 MeSiH. L'addition du PH 2 MeSiH sur le phénylacétylène conduit à la formation d'isomères β(cis et trans) et α. Ces systèmes catalytiques fournissent une nouvelle voie de synthèse pour la formation de la liaison Si-C.

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“…[21] Thee nhancing effect of 1 on the homolytic cleavage of the MÀSi bonds in [(tBuMe 2 Si) 2 M] is mediated by formation of octahedral hexacoordinate PtÀMb imetallic complexes 2 (for Zn) and 3 (for Hg) which dissociate under mild warming or under photolysis to yield R 3 SiC radicals and novel square-pyramidal paramagnetic Pt III species,characterized by EPR spectroscopy and DFT calculations.T he reported activation of the SiÀMb onds in [(tBuMe 2 Si) 2 M] (M = Zn, Hg) occurs in the presence of stoichiometric amounts of [(dmpe)Pt(PEt 3 ) 2 ](1).…”

Section: Methodsmentioning

confidence: 99%

Activation of Homolytic SiZn and SiHg Bond Cleavage, Mediated by a Pt⁰ Complex, via Novel PtZn and PtHg Compounds

et al. 2015

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The thermally stable [(tBuMe 2 Si) 2 M] (M = Zn, Hg) generate R 3 SiC radicals in the presence of [(dmpe)Pt(PEt 3 ) 2 ]at 60-80 8 8C. The reaction proceeds via hexacoordinate Pt complexes,( M= Zn (2a and 2b), M = Hg (3a and 3b)) which were isolated and characterized. Mild warming or photolysis of 2 or 3 lead to homolytic dissociation of the PtÀMSiR 3 bond generating silyl radicals and novel unstable pentacoordinate platinum paramagnetic complexes (M = Zn (5), Hg (6)) whose structures were determined by EPR spectroscopya nd DFT calculations.The vigorously developing chemistry of heterometallic complexes containing two or more different metals is of considerable contemporary interest with avariety of applications in synthesis,c atalysis,a nd materials chemistry. [1] More specifically,r ecently heterometallic complexes containing Pt and Zn atoms attracted attention and several were isolated. [2][3][4] Several methodologies are available for their synthesis.O ne involves the formation of PtÀZn heteronuclear dative linkages from Lewis basic and Lewis acidic metals (termed metal-only Lewis pairs (MOLPs)). [1a] Fore xample, recently aM OLP Pt À Zn complex was isolated from the reaction of [Pt(PCy 3 ) 2 ]( Cy = cyclohexyl) and ZnBr 2 . [2] Fischer et al. reported an umber of novel {PtÀZnCp*} (Cp* = pentamethylcyclopentadienyl) complexes in which ad ivalent zinc is bonded directly to platinum. [3] Complexes in which Pt and Zn are bridged by ligands were also isolated and characterized. [4] Herein we report that thermally stable SiÀZn and SiÀHg bonds are activated towards homolytic cleavage by aP t 0 complex, [(dmpe)Pt(PEt 3 ) 2 ]( 1)d mpe = 1,2-bis(dimethylphosphanyl)ethane,y ielding hexacoordinate Pt isomers 2a and 2b (M = Zn) or 3a, 3b (M = Hg), respectively,h aving aP t ÀMSiR 3 moiety [Eq. (1)].T hese novel hexacoordinate PtÀMSiR 3 compounds were isolated and characterized by Xray crystallography and their photolysis and thermolysis is reported. Photolysis of 2 (i.e., the obtained 63:37 mixture of 2a+ 2b,respectively) or of 3 (i.e., the obtained 26:74 mixture of 3a+ 3b,r espectively) yields quantitatively the tetracoordinate platinum complex 4 and the EPR spectra of the intermediate pentacoordinate platinum paramagnetic species, 5 (M = Zn) or 6 (M = Hg), respectively,a re observed [Eq. (2)].Bis(silyl)zincs and bis(silyl)mercuries are good precursors for the photochemical generation of R 3 Si radicals. [5] For example,upon day-light exposure for 30 min [(tBuMe 2 Si) 2 Zn] (7)o r[ ( tBuMe 2 Si) 2 Hg] (8)u ndergo quantitative demetallation forming short-lived [tBuMe 2 Si]C radicals which dimerize to disilane 9 (95 %) or abstract an hydrogen (5 %) to form silane 10 [Eq. (3)].In contrast to their facile photolysis,b is(silyl)zincs and bis(silyl)mercuries are generally thermally stable;f or example no decomposition of [(tBuMe 2 Si) 2 Zn] (7), [(tBu-Me 2 Si) 2 Hg] (8), [(tBu 2 MeSi) 2 Zn] (11), or [(tBu 2 MeSi) 2 Hg] (12)isobserved after their heating at 120 8 8Cfor several days. However,i nt he presence of as toichiometri...

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Platinum-catalyzed hydrosilylation of alkynes

Cited by 156 publications

References 8 publications

Asymmetric Catalysis at Chiral Metal Surfaces

Asymmetric Catalysis at Chiral Metal Surfaces

Metal supported catalysts obtained by sol-gel in the hydrosilylation of phenylacetylene with R₃SiH organosilanes (R₃ = Ph₃, Ph₂Me, and PhMe₂)

Activation of Homolytic SiZn and SiHg Bond Cleavage, Mediated by a Pt⁰ Complex, via Novel PtZn and PtHg Compounds

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Platinum-catalyzed hydrosilylation of alkynes

Cited by 156 publications

References 8 publications

Asymmetric Catalysis at Chiral Metal Surfaces

Asymmetric Catalysis at Chiral Metal Surfaces

Metal supported catalysts obtained by sol-gel in the hydrosilylation of phenylacetylene with R3SiH organosilanes (R3 = Ph3, Ph2Me, and PhMe2)

Activation of Homolytic SiZn and SiHg Bond Cleavage, Mediated by a Pt0 Complex, via Novel PtZn and PtHg Compounds

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Metal supported catalysts obtained by sol-gel in the hydrosilylation of phenylacetylene with R₃SiH organosilanes (R₃ = Ph₃, Ph₂Me, and PhMe₂)

Activation of Homolytic SiZn and SiHg Bond Cleavage, Mediated by a Pt⁰ Complex, via Novel PtZn and PtHg Compounds