Hydrosilylation of olefins catalysed by trans-di-µ-hydrido-bis(tricyclohexylphosphine)bis(silyl)diplatinum complexes
- 1 January 1977
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 16,p. 1519-1525
- https://doi.org/10.1039/dt9770001519
Abstract
The diplatinum complexes [{Pt(SiR3)(µ-H)[(C6H11)3P]}2] catalyse the addition of silanes R3SiH (R = Me, Et, PhCH2, Ph, OEt, or Cl) to pent-1-ene, hex-1-ene, styrene, allyl chloride, and 2-methylpropene. Reactivity of the silanes is qualitatively in the order: Me2EtSiH Me2PhSiH Me2(PhCH2) SiH ClMe2SiH > Me3SiH > Cl3SiH Et3SiH (EtO)3SiH, except for allyl chloride for which it is Cl3SiH > Cl2MeSiH > Me2PhSiH ClMe2SiH. The hydrosilylations are frequently strongly exothermic, proceeding in high yield with a catalyst: reactant ratio of 10–4–10–6 : 1. Hexa-1,5-diene, octa-1,7-diene, and 4-vinylcyclohexene also react readily with silanes using the same catalyst system. Hexa-1,5-diene and octa-1,7-diene afford the bis(silicon) adducts, but with 4-vinylcyclohexene only the exocyclic double bond is hydrosilylated. Catalytic addition of silanes to bicyclo[2.2.1]heptene is also described, exo-addition products being formed in 60–85% yield. The addition of Me3GeH to hex-1-ene and to styrene is catalysed by [{Pt(GeMe3)(µ-H)[(C6H11)3P]}2].Keywords
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