The oxidation of a dinuclear Pt(II) complex with hydrogen peroxide is described. The dinuclear complex ion [cis-PtII-(15NH2CH2CH3)2(μ-OH)]22+undergoes oxidation in aqueous H2O2to produce dinuclear Pt(IV) ions of the type [cis-PtIV-(15NH2CH2CH3)2(OH)2(μ-OH)]22+. Following the reaction by using195Pt NMR spectroscopy and isolation of the major product pOi revealed that oxidation primarily yields a D2h-symmetry dinuclear compound having a four-membered [formula omitted] ring. However, the fact that the reaction also yields lower symmetry dinuclear Pt(IV) compounds possessing this ring indicates that the oxidation, at least in part, proceeds through an “open-ring” intermediate that allows isomerization to occur. Thel95Pt NMR chemical shifts and 1J(195Pt-15N) values, the latter measured by using both195Pt and15N NMR spectroscopies, were used to examine the effects of the four-membered ring and the various ligands on the electronic properties of the platinum ion.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry