title: Structural and mechanistic investigations of the oxidation of dimethylplatinum(II) complexes by dioxygen.
abstract: The oxidation of (tmeda)Pt(II)(CH(3))(2) (1, tmeda = N,N,N',N'-tetramethylethylenediamine) to (tmeda)Pt(IV)(OH)(OCH(3))(CH(3))(2) (3) by dioxygen in methanol proceeds via a two-step mechanism. The initial reaction between (tmeda)Pt(CH(3))(2) and dioxygen yields a hydroperoxoplatinum(IV) intermediate, (tmeda)Pt(OOH)(OCH(3))(CH(3))(2) (2), which reacts with a second equivalent of (tmeda)Pt(CH(3))(2) to afford the final product 3. Both 2 and 3 have been fully characterized, including X-ray crystallographic structure determinations. The effect of ligand variation on the oxidation of several dimethylplatinum(II) complexes by 2 as well as by dioxygen has been examined.
authors.affiliation: Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, USA.
authors.forename: Vsevolod V
authors.initials: VV
authors.lastname: Rostovtsev
authors.forename: Lawrence M
authors.initials: LM
authors.lastname: Henling
authors.forename: Jay A
authors.initials: JA
authors.lastname: Labinger
authors.forename: John E
authors.initials: JE
authors.lastname: Bercaw