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Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase
Published on: December 4, 2017
Redox-switched oxidation of dihydrogen using a non-innocent ligand
Mark R Ringenberg1, Swarna Latha Kokatam, Zachariah M Heiden
1Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
Abstract:
Organometallic complexes containing non-innocent ligands of the type Cp*Ir(tBAFPh)(1), where H2tBAFPh is 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol, were found to activate H2 in a redox-switchable manner. The 16e- complex 1 was inert with respect to H2, CO, as well as conventional basic substrates until oxidation. Oxidation of 16-electron 1 with 1 equiv of Ag+ resulted in ligand-centered oxidation affording salts of [1]+, which were characterized by crystallographically, EPR, and elemental analyses. [1]+ was reduced to 1 in the presence of H2 and the sterically hindered base, 2,6-(tBu)2C5H3N, via a pathway that is first-order in both metal and dihydrogen. Compound [1]+ forms adducts with MeCN, which inhibits catalysis. The catalytic oxidation of H2 was established by electrochemical methods to be associated with the monocation.
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