Iridium-Phosphine

Journal Title, Volume, Page:

Journal Of Organometallic Chemistry Volume 228, Issue 2, 23 March 1982, Pages 191-201

Year of Publication:

1982

Link:

http://www.sciencedirect.com/science/article/pii/S0022328X00870977

Authors:

H. S. Hilal

Department of Chemistry, The University of Manchester Institute of Science and Technology

Current Affiliation:

Department of Chemistry, An-Najah N. University, Nablus, PO Box 7, West Bank, Palestine

[email protected]

J. Dwyer

Department of Chemistry, The University of Manchester Institute of Science and Technology

R. V. Parish

Department of Chemistry, The University of Manchester Institute of Science and Technology, Manchester, M60 1QD Great Britain

Preferred Abstract (Original):

Silica-supported iridium catalysts have been evaluated in the reactions of HSiR₃ (R  Et, OEt) and Me₃SiO[Si(H)(Me)O]_nSiMe₃ (PS1, n  1; PS50, n ∼ 50) with awide variety of primary alcohols. Catalysts obtained by reaction of IrCl(CO)[Ph₂P(CH₂)₂Si(OEt)₃]₂ with silica are rapidly deactivated in a manner similar to the related homogeneous systems. More active catalysts are obtinaed by treating the silica first with Ph₂P(CH₂)₂Si(OEt)₃ and then with [IrCl(C₈H₁₄)₂]₂. The order reactivity of the silanes is PS50 ⪢ HSi(OEt)₃ > HSiEt3 ⪢ PS1, and that of the alcohols reflects principally the bulk of the organic group. Kinetic analysis indicates two pathways involving iridium bound to the phosphine and directly to the silica. The ²⁹ Si{¹H} NMR spectra of PS50 and the product of its reaction with Ph(CH₂)₂OH are reported.

An-Najah Staff

Silica-Supported Iridium-Phosphine Catalysts for the Reaction of the Silanes with Alcohols