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A Ni^0(η^2-(Si–H))(η^2-H_2) Complex That Mediates Facile H Atom Exchange between Two σ-Ligands

Connor, Bridget A. and Rittle, Jonathan and VanderVelde, David and Peters, Jonas C. (2016) A Ni^0(η^2-(Si–H))(η^2-H_2) Complex That Mediates Facile H Atom Exchange between Two σ-Ligands. Organometallics, 35 (5). pp. 686-690. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20160301-114837187

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Abstract

σ-adduct complexes of low-valent, late first-row metal complexes are highly unusual, and this is particularly true of d^(10) systems. We have discovered a nickel/phosphine/silyl system that undergoes reaction with H_2 in solution to generate a species best described as Ni^0(η^2-(Si–H))(η^2-H_2) on the basis of multinuclear NMR studies. Theoretical calculations suggest that the Ni center facilitates H atom exchange between the η^2-(Si–H) and η^2-H_2 ligands via interconversion with a higher valent Ni^(II) isomer. This exchange is exploited in the selective, catalytic deuteration of exogenous silanes.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acs.organomet.5b00985DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.organomet.5b00985PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.organomet.5b00985PublisherSupporting Information
ORCID:
AuthorORCID
Peters, Jonas C.0000-0002-6610-4414
Additional Information:© 2016 American Chemical Society. Received: December 2, 2015; Published: February 22, 2016. This work was supported by the NSF Center for Chemical Innovation Solar Fuels Grant CHE-1305124. We also acknowledge the Gordon and Betty Moore Foundation for financial support. B.A.C. acknowledges an Arthur R. Adams SURF fellowship. The authors declare no competing financial interest.
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
NSFCHE-1305124
Gordon and Betty Moore FoundationUNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Issue or Number:5
Record Number:CaltechAUTHORS:20160301-114837187
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160301-114837187
Official Citation:A Ni0(η2-(Si–H))(η2-H2) Complex That Mediates Facile H Atom Exchange between Two σ-Ligands Bridget A. Connor, Jonathan Rittle, David VanderVelde, and Jonas C. Peters Organometallics 2016 35 (5), 686-690 DOI: 10.1021/acs.organomet.5b00985
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:64908
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:01 Mar 2016 21:26
Last Modified:26 Nov 2019 11:15

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