Synthesis, first structures, and catalytic activity of the monomeric rhodium(I)-siloxide phosphine complexes
- 1 November 2003
- journal article
- Published by Canadian Science Publishing in Canadian Journal of Chemistry
- Vol. 81 (11), 1292-1298
- https://doi.org/10.1139/v03-145
Abstract
Four new square-plane rhodium siloxide complexes of the general formula [Rh(cod)(PR3′)(OSiR3)] (where R = Me, i-Pr, O-t-Bu, R′ = Cy, Ph) were synthesized and the structures of three of them were resolved by the X-ray method. [Rh(cod)(PCy3)(OSiMe3)] (1) appeared to be a very efficient catalyst for hydrosilylation of allyl glycidyl ether to yield, selectively, 3-glycidoxypropyltriethoxysilane, a commercially important silane coupling agent. Catalytic measurements and stoichiometric experiments of 1 with triethoxysilane suggest a mechanism where an unsaturated Rh-H species is responsible for the catalysis.Key words: rhodium (phosphine) siloxides, hydrosilylation, catalysis.Keywords
This publication has 18 references indexed in Scilit:
- Silyloxy-rhodium(I) complex catalyzed disproportionation of vinylsilanes and vinylsiloxanesJournal of Molecular Catalysis A: Chemical, 2000
- Catalytic activity of silyloxy-rhodium(I) complexes in hydrosilylation of alkenesJournal of Molecular Catalysis A: Chemical, 1999
- Synthesis of a Molybdenum-Containing Silsesquioxane Which Rapidly Catalyzes the Metathesis of OlefinsJournal of the American Chemical Society, 1994
- Spectroscopic assessment of the degree of .pi.-stabilization of unsaturation in ruthenium complex, RuH(X)CO(P-tert-Bu2Me)2Inorganic Chemistry, 1992
- Trialkoxysiloxy complexes of nickel. Molecular structures of Na3(.mu.3-I){Ni[.mu.3-OSi(O-tert-Bu)3]3I}.cntdot.0.5THF.cntdot.0.5C5H12 and {(.eta.3-C3H5)Ni[.mu.2-OSi(O-tert-Bu)3]}2Inorganic Chemistry, 1990
- Synthesis and spectroscopic and x-ray structural characterization and dynamic solution behavior of the neutral cobalt(II) alkoxides [Co{OC(C6H11)3}2]2.CH3OH.1/2C6H12.THF, [Co(OCPh3)2]2.n-C6H14, [Co(OSiPh3)2(THF)]2, and Co(OCPh3)2(THF)2Inorganic Chemistry, 1987
- Di‐μ‐Chloro‐Bis(η 4 ‐1,5‐Cyclooctadlene) Dirhodium(I)Inorganic Syntheses, 1979
- Molecular mechanics calculations on alkanes and non-conjugated alkenesJournal of the Chemical Society, Perkin Transactions 2, 1977
- Determination of conformational barriers in 1,5-cyclooctadiene by proton and carbon-13 nuclear magnetic resonanceJournal of the American Chemical Society, 1973
- Homogeneous Catalysis. II. The Mechanism of the Hydrosilation of Olefins Catalyzed by Group VIII Metal Complexes1Journal of the American Chemical Society, 1965