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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

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.

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