Redox Chemistry of Dimethylplatinum(II) Diimine Complexes. Oxidatively Induced Pt−Me Transfer between Transient Platinum(III) Cation Radicals

摘要: The redox chemistry of the series Pt(II) diimine complexes L2PtMe2 (1; L2 = Ar−NCRCRN−Ar, where Ar/R 4-MeC6H4/H (a), 4-MeOC6H4/H (b), 4-MeC6H4/Me (c), 4-MeOC6H4/Me (d)), with particular emphasis on oxidation processes, has been studied in detail. As seen by cyclic voltammetry, 1a−d undergo two successive, reversible one-electron reductions at ligands and an irreversible, metal-centered oxidation. 1b investigated some Chemical Cp2Fe+PF6- acetonitrile yields a near 1:1 ratio corresponding Pt(IV) cations L2Pt(NCMe)Me+ (2b) fac-L2Pt(NCMe)Me3+ (3b). Controlled-potential electrolysis mixtures 2b 3b ratio, as well cis,cis (4b) one cis,trans (5b) isomer dicationic L2Pt(NCMe)2Me22+. percentage dications 4b 5b depended electrode potential. A mechanism involving methyl group transfer between transient Pt(III) int...