Homogeneous Catalysis of Hydrosilation by Transition Metals

Speier, John L.

doi:10.1016/s0065-3055(08)60328-7

Cited by 596 publications

(217 citation statements)

References 53 publications

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“…In the presence of catalysts such as [118] Chlorosilanes react more readily than alkoxysilanes, but the chlorine atoms have to be replaced by alkoxy groups prior to the subsequent reaction step. The resulting w-silylalkenes are then transformed to the desired donor ligands by the photochemical addition of a secondary phosphane (HDo) to the remaining terminal double bond (Scheme 3 A).…”

Section: Synthesis Of Polysiloxane-bound Transition Metal Complexesmentioning

confidence: 99%

Chemistry in Interphases—A New Approach to Organometallic Syntheses and Catalysis

Lindner

Schneller

Auer

et al. 1999

Angew. Chem. Int. Ed.

229

114

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Combining the advantages of homogeneous and heterogeneous catalysis is still a problem that has not been satisfactorily solved. Chemistry in interphases offers a new approach for overcoming the difficulties, as is described in this article. Owing to the swellable or porous matrix, an interphase represents a state which in the most favorable case is similar to that of a solution. Moreover the proper choice of a mobile hybrid copolymer enables the control of the density and accessibility of the reactive centers, which results in a distinct improvement of the activity of the catalysts (two examples are shown schematically).

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Section: Synthesis Of Polysiloxane-bound Transition Metal Complexesmentioning

confidence: 99%

Chemistry in Interphases—A New Approach to Organometallic Syntheses and Catalysis

Lindner

Schneller

Auer

et al. 1999

Angew. Chem. Int. Ed.

229

114

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“…Reaction [5] most likely takes place through a four-center intermediate (eq. [7]), similar to that proposed for the "heterolytic" activation of Hz by copper(1) complexes (14).…”

Section: Resultsmentioning

confidence: 99%

Copper(I) chloride catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds. A new method for the copolymerization of silanes and alkynes

Liu¹,

Harrod²

1990

Can. J. Chem.

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In the presence of an amine, copper(1) chloride is an effective catalyst for the cross-dehycrocoupling of silanes with alkynes. The reactions proceed at useful rates above 100°C, but rates drop dramatically on going from lo to 2' to 3' organosilanes. Primary silanes, RSiH3 (R = Ph,n-hexyl), react in astepwisefashion with phenylacetylene to give the products RSiH3., (CCPh), (x = 1-3), each of which has been isolated and characterized. The secondary silanes RRiSiH2 (R = R' = Ph; R = Ph, R' = Me; R = n-Bu, R' = Me) also give mono-and diphenylethynyl products. The dehydrocoupling reaction has been applied to the synthesis of new polymers containing bothacetylene units and silicon atoms in the backbone. 1,3-Diethynylbenzene gives polymers of relatively high molecular weight (M, = lo4-lo5) with phenylsilane and phenylmethylsilane, but reactions of phenylmethyldiethynylsilane are too slow to give anything beyond low molecular weight oligomers.Key words: organosilanes, alkynes, dehydrocoupling, copper(1) chloride, polymers, catalysis.HUA QIN LIU et JOHN F. HARROD. Can. J. Chem. 68, 1 100 (1990).En prCsence d'une amine, le chlorure de cuivre(1) est un catalyseur efficace pour le dChydro-couplage croisC des silanes avec les alcynes. Les rCactions se produisent a des vitesses raisonnables lorsqu'on opere au-dessus de 100°C; toutefois, les vitesses diminuent d'une f a~o n dramatique lorsqu'on passe des organosilanes l o aux 2" et aux 3' . La rCaction des silanes primaires, RSiH3 (R = Ph, n-hexyle), avec le phCnylacCtylene se produit par Ctape pour donner les produits RSiH3, (CCPh), (x = 1-3); chacun de ces produits a CtC is016 et caractCrisC. Les silanes secondaires RR1SiH2 (R = R' = Ph; R = Ph, R' = Me; R = nBu, R' = Me) donnent aussi des produits mono-et di-phCnylCthynyles. On a appliquC la reaction de dthydro-couplage la synthbse de nouveaux polymeres dont la chaine fondamentale contient a la fois des unitCs acbtylbnes et des atomes de silicium. Avec le pEnylsilane et le phCnylmCthylsilane, le 1,3-diethynylbenzene fournit des polymkres de poids molCculaires relativement ClevCs (M, = lo4-lo5); toutefois, les rCactions du phCnylmCthyldiCthynylsilane sont tellement lentes que les seuls produits isolCs sont des oligombres de bas poids molCculaires.

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“…27,28 POLY(PHOSPHONOSILOXANE) AND CYCLIC MONOMER SYNTHESIS the presence of Me 2 SO. Speier 21 suggested that the electron-donating ligands form a complex with the platinum moiety, thus displacing the -bonded olefin from the Pt complex. Additional experiments are presently being conducted in this laboratory to assess the sensitivity of Pt-complex catalysts to phosphoryl ester ligands.…”

Section: Synthesismentioning

confidence: 99%

Synthesis of poly(phosphonosiloxane) and its cyclic monomer via hydrosilylation and phosphonylation of vinylbenzyl chloride

Song¹,

Cabasso²

1999

J. Polym. Sci. A Polym. Chem.

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Homogeneous Catalysis of Hydrosilation by Transition Metals

Cited by 596 publications

References 53 publications

Chemistry in Interphases—A New Approach to Organometallic Syntheses and Catalysis

Chemistry in Interphases—A New Approach to Organometallic Syntheses and Catalysis

Copper(I) chloride catalyzed cross-dehydrocoupling reactions between silanes and ethynyl compounds. A new method for the copolymerization of silanes and alkynes

Synthesis of poly(phosphonosiloxane) and its cyclic monomer via hydrosilylation and phosphonylation of vinylbenzyl chloride

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