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Published January 19, 2012 | Published + Supplemental Material
Journal Article Open

Thermally stable N_2 and H_2 adducts of cationic nickel(II)

Abstract

The first examples of thermally stable molecular dihydrogen adducts of nickel were synthesized from their dinitrogen adduct precursors, which are themselves among the first examples of Ni(II)-N_2 complexes. The minimal activation of the bound N_2 moieties suggests that these adducts are stabilized predominantly through σ-donation from the adduct to the electrophilic metal center. We further show that the bound H_2 ligand can undergo heterolytic cleavage to deliver hydride to the nickel center. The H_2 adducts are of particular interest in the context of hypotheses suggesting that Ni can serve as the site for H_2 binding and heterolytic activation in [NiFe] hydrogenases.

Additional Information

© 2012 The Royal Society of Chemistry. Received 8th December 2011, Accepted 18th January 2012. First published on the web 19 Jan 2012. This work was supported by the NSF (CHE-0750234) and the Gordon and Betty Moore Foundation. We are grateful to Dr Peter Müller and Dr Marc-Etienne Moret for assistance with XRD and DFT studies, respectively.

Attached Files

Published - Tsay2012p17603Chem_Sci.pdf

Supplemental Material - c2sc01033j.pdf

Supplemental Material - c2sc01033j.txt

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August 19, 2023
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