Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 27, Pages 7671-7675Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201601242
Keywords
homogeneous catalysis; hydrogen-atom transfer; hydrosilylation; radicals; titanium
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Funding
- DFG [SFB 813, Ga 619/11-1]
- Jurgen Manchot Stiftung
- National Science Foundation [CHE-1123815]
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A catalytic system for titanocene-catalyzed epoxide hydrosilylation is described. It features a straightforward preparation of titanocene hydrides that leads to a reaction with low catalyst loading, high yields, and high selectivity of radical reduction. The mechanism was studied by a suite of methods, including kinetic studies, EPR spectroscopy, and computational methods. An unusual resting state leads to the observation of an inverse rate order with respect to the epoxide.
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