title: Halogen oxidation and halogen photoelimination chemistry of a platinum-rhodium heterobimetallic core.
abstract: The heterobimetallic complexes, PtRh(tfepma)(2)(CN(t)Bu)X(3) (X = Cl, Br), are assembled by the treatment of Pt(cod)X(2) (cod =1,5-cyclooctadiene) with {Rh(cod)X}(2), in the presence of tert-butylisonitrile (CN(t)Bu) and tfepma (tfepma = bis(trifluoroethoxyl)phosphinomethylamine). The neutral complexes contain Pt-Rh single bonds with metal-metal separations of 2.6360(3) and 2.6503(7) Å between the square planar Pt and octahedral Rh centers for the Cl and Br complexes, respectively. Oxidation of the XPt(I)Rh(II)X(2) cores with suitable halide sources (PhICl(2) or Br(2)) furnishes PtRh(tfepma)(2)(CN(t)Bu)X(5), which preserves a Pt-Rh bond. For the chloride system, the initial oxidation product orients the platinum-bound chlorides in a meridional geometry, which slowly transforms to a facial arrangement in pentane solution as verified by X-ray crystal analysis. Irradiation of the mer- or fac-Cl(3)Pt(III)Rh(II)Cl(2) isomers with visible light in the presence of olefin promotes the photoelimination of halogen and regeneration of the reduced ClPt(I)Rh(II)Cl(2) core. In addition to exhibiting photochemistry similar to that of the chloride system, the oxidized bromide cores undergo thermal reduction chemistry in the presence of olefin with zeroth-order olefin dependence. Owing to an extremely high photoreaction quantum yield for the fac-ClPt(I)Rh(II)Cl(2) isomer, details of the X(2) photoelimination have been captured by transient absorption spectroscopy. We now report the first direct observation of the photointermediate that precedes halogen reductive elimination. The intermediate is generated promptly upon excitation (<8 ns), and halogen is eliminated from it with a rate constant of 3.6 × 10(4) s(-1). As M-X photoactivation and elimination is the critical step in HX splitting, these results establish a new guidepost for the design of HX splitting cycles for solar energy storage.
authors.affiliation: Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
authors.forename: Timothy R
authors.initials: TR
authors.lastname: Cook
authors.forename: Brian D
authors.initials: BD
authors.lastname: McCarthy
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Lutterman
authors.forename: Daniel G
authors.initials: DG
authors.lastname: Nocera
mesh_terms: D006859:Hydrogen / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D010984:Platinum / Q000737:chemistry*; D011789:Quantum Theory; D012238:Rhodium / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D010984:Platinum; D006859:Hydrogen; D012238:Rhodium