title: Synthesis and Crystal and Electronic Structures of the Dinuclear Platinum Compounds [PEtPh(3)](2)[Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]: A Computational Study by Density Functional Theory.
abstract: The electrolytic behavior of the dinuclear complexes [NBu(4)](2)[MM'(&mgr;-PPh(2))(2)(C(6)F(5))(4)] (M = M' = Pt (1), Pd (1a); M = Pt, M' = Pd (1b)) has been studied, showing electrochemically irreversible oxidation and related reduction processes. The chemical oxidation of the binuclear compound for M = M' = Pt, results in the formation of the binuclear Pt(III) compound [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]. The crystal structure analysis of both complexes has been carried out, showing very similar structures with similar Pt-C and Pt-P distances and analogous skeletons. However the Pt-Pt distances are very different, 3.621(1) Å for the Pt(II) compound and 2.7245(7) Å for the Pt(III) derivative (as are the parameters geometrically related to this Pt-Pt distance), suggesting that, in the Pt(III) compound, there is a strong Pt-Pt bond. Results of DFT calculations on [Pt(2)(&mgr;-PH(2))(2)(C(6)F(5))(4)](n)()(-) (n = 2, 0) agree very well with the crystallographic data and indicate that, in the Pt(III) compound, there is approximately a single sigma bond between the metal atoms.
authors.affiliation: Departamento de Química Inorgánica and Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain, and Department of Chemistry and Laboratory for Molecular Structure and Bonding, Texas A&M University, College Station, Texas 77843.
authors.forename: Ester
authors.initials: E
authors.lastname: Alonso
authors.forename: José M.
authors.initials: JM
authors.lastname: Casas
authors.forename: F. Albert
authors.initials: FA
authors.lastname: Cotton
authors.forename: Xuejung
authors.initials: X
authors.lastname: Feng
authors.forename: Juan
authors.initials: J
authors.lastname: Forniés
authors.forename: Consuelo
authors.initials: C
authors.lastname: Fortuño
authors.forename: Milagros
authors.initials: M
authors.lastname: Tomas