CaltechAUTHORS
  A Caltech Library Service

Facile Si–H bond activation and hydrosilylation catalysis mediated by a nickel–borane complex

MacMillan, Samantha N. and Harman, W. Hill and Peters, Jonas C. (2013) Facile Si–H bond activation and hydrosilylation catalysis mediated by a nickel–borane complex. Chemical Science, 5 (2). pp. 590-597. ISSN 2041-6520 . https://resolver.caltech.edu/CaltechAUTHORS:20140129-104856793

[img]
Preview
PDF - Published Version
See Usage Policy.

636Kb
[img]
Preview
PDF (Supplementary Information) - Supplemental Material
See Usage Policy.

1358Kb
[img] Plain Text (Crystal Structure Data) - Supplemental Material
See Usage Policy.

107Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20140129-104856793

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/c3sc52626gDOIArticle
http://pubs.rsc.org/en/Content/ArticleLanding/2014/SC/c3sc52626g#!divAbstractPublisherArticle
ORCID:
AuthorORCID
Peters, Jonas C.0000-0002-6610-4414
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.
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
NSF Center for Chemical Innovation on Solar FuelsCHE-1305124
Gordon and Betty Moore FoundationUNSPECIFIED
Issue or Number:2
Record Number:CaltechAUTHORS:20140129-104856793
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140129-104856793
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:43544
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:29 Jan 2014 22:24
Last Modified:26 Nov 2019 11:15

Repository Staff Only: item control page