Facile Si–H bond activation and hydrosilylation catalysis mediated by a nickel–borane complex
Abstract
Metal–borane complexes are emerging as promising systems for study in the context of bifunctional catalysis. Herein we describe diphosphineborane nickel complexes that activate Si–H bonds and catalyze the hydrosilylation of aldehydes. Treatment of [^(Mes)DPB^(Ph)]Ni (1) ([^(Mes)DPB^Ph] = ^(Mes)B(o-Ph_2PC_6H_4)_2) with organosilanes affords the complexes [^(Mes)DPB^(Ph)](μ-H)NiE (E = SiH_2Ph (3), SiHPh_2 (4)). Complex 4 is in solution equilibrium with 1 and the thermodynamic and kinetic parameters of their exchange have been characterized by NMR spectroscopy. Complex 1 is a catalyst for the hydrosilylation of a range of para-substituted benzaldehydes. Mechanistic studies on this reaction via multinuclear NMR spectroscopy are consistent with the intermediacy of a borohydrido-Ni-siloxyalkyl species.
Additional Information
© 2014 Royal Society of Chemistry. Received 18th September 2013; accepted 22nd October 2013. First published online 22 Oct 2013. This work was supported by the National Science Foundation Center for Chemical Innovation on Solar Fuels (CCI Solar, Grant CHE-1305124) and the Gordon and Betty Moore Foundation. We thank David VanderVelde for assistance with NMR experiments.Attached Files
Supplemental Material - c3sc52626g.pdf
Supplemental Material - c3sc52626g.txt
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Additional details
- Eprint ID
- 43544
- Resolver ID
- CaltechAUTHORS:20140129-104856793
- CHE-1305124
- NSF Center for Chemical Innovation on Solar Fuels
- Gordon and Betty Moore Foundation
- Created
-
2014-01-29Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field
- Caltech groups
- CCI Solar Fuels