title: Oxygen reduction to water mediated by a dirhodium hydrido-chloride complex.
abstract: The two-electron mixed-valence dirhodium complex Rh(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2) (tfepma = CH(3)N[P(OCH(2)CF(3))(2)](2)) reacts with HCl to furnish two isomeric dirhodium hydrido-chloride complexes, Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(3)H. In the presence of HCl, the hydride complex effects the reduction of 0.5 equiv of O(2) to 1 equiv of H(2)O, generating Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(4), which can be prepared independently by chlorine oxidation of the Rh(2)(0,II) precursor. The starting Rh(2)(0,II) complex is regenerated photochemically to close an oxygen-to-water reduction photocycle.
authors.affiliation: Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
authors.forename: Thomas S
authors.initials: TS
authors.lastname: Teets
authors.forename: Timothy R
authors.initials: TR
authors.lastname: Cook
authors.forename: Brian D
authors.initials: BD
authors.lastname: McCarthy
authors.forename: Daniel G
authors.initials: DG
authors.lastname: Nocera