Coordinatively Saturated Tris(oxazolinyl)borato Zinc Hydride-Catalyzed Cross Dehydrocoupling of Silanes and Alcohols

TitleCoordinatively Saturated Tris(oxazolinyl)borato Zinc Hydride-Catalyzed Cross Dehydrocoupling of Silanes and Alcohols
Publication TypeJournal Article
Year of Publication2011
AuthorsMukherjee D, Thompson RR, Ellern A, Sadow AD
Journal TitleACS Catalysis
Volume1
Pages698-702
Date Published07
ISBN Number2155-5435
Accession NumberWOS:000292479400004
Abstract

The four-coordinate zinc compound To(M)ZnH (1, To(M) = tris(4,4-dimethyl-2-oxazolinyl)phenylborate) catalyzes selective alcoholysis of substituted hydrosilanes. The catalytic reaction of PhMeSiH(2) and aliphatic alcohols favors the monodehydrocoupled product PhMeHSi-OR With the aryl alcohol 3,5-C(6)H(3)Me(2)OH; the selectivity for mono(aryloxy)-hydrosilane PhMeHSi-OC(6)H(3)Me(2) and bis(aryloxy)silane PhMeSi-(OC(6)H(3)Me(2))(2) is controlled by relative reagent concentrations. Reactions of secondary organosilanes and diols provide cyclic bis(oxo)silacycloalkanes in high yield. The empirical rate law for the To(M)ZnH-catalYzed.reaction of 3,5-dimethylphenol and PhMeSiH(2) is d[PhMeSiH(2)]/dt = k'(obs)[To(M)ZnH](1)[3,5-C(6)H(3)Me(2)OH](0)-, [PhMeSiH(2)](1) (determined at 96 degrees C)which indicates that Si-O bond formation is turnover limiting in the presence of excess phenol.

DOI10.1021/cs2001016