Structural and mechanistic investigations of the oxidation of dimethylplatinum(II) complexes by dioxygen

Vsevolod V Rostovtsev; Lawrence M Henling; Jay A Labinger; John E Bercaw

doi:10.1021/ic0112903

Structural and mechanistic investigations of the oxidation of dimethylplatinum(II) complexes by dioxygen

Inorg Chem. 2002 Jul 15;41(14):3608-19. doi: 10.1021/ic0112903.

Authors

Vsevolod V Rostovtsev¹, Lawrence M Henling, Jay A Labinger, John E Bercaw

Affiliation

¹ Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, USA.

PMID: 12099863
DOI: 10.1021/ic0112903

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.