Published March 14, 2016
| Supplemental Material
Journal Article
Open
A Ni^0(η^2-(Si–H))(η^2-H_2) Complex That Mediates Facile H Atom Exchange between Two σ-Ligands
Chicago
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.
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.Attached Files
Supplemental Material - om5b00985_si_001.pdf
Supplemental Material - om5b00985_si_002.cif
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Additional details
- Eprint ID
- 64908
- DOI
- 10.1021/acs.organomet.5b00985
- Resolver ID
- CaltechAUTHORS:20160301-114837187
- NSF
- CHE-1305124
- Gordon and Betty Moore Foundation
- Caltech Summer Undergraduate Research Fellowship (SURF)
- Created
-
2016-03-01Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Caltech groups
- CCI Solar Fuels