title: Redox-switched oxidation of dihydrogen using a non-innocent ligand.
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.
authors.affiliation: Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
authors.forename: Mark R
authors.initials: MR
authors.lastname: Ringenberg
authors.forename: Swarna Latha
authors.initials: SL
authors.lastname: Kokatam
authors.forename: Zachariah M
authors.initials: ZM
authors.lastname: Heiden
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Rauchfuss