Oxidation of Dimethylplatinum(II)
Complexes with a
Dioxirane: The Viability of Oxoplatinum(IV) Intermediates
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Abstract
The complexes [PtMe<sub>2</sub>(NN)] (NN = 2,2′-bipyridine
= bipy, <b>1a</b>; NN = di-2-pyridylamine = dpa, <b>1b</b>; NN = di-2-pyridyl ketone = dpk, <b>1c</b>) react with dimethyldioxirane
in moist acetone to give the hydroxoplatinum(IV) complexes [Pt(OH)<sub>2</sub>Me<sub>2</sub>(NN)] (NN = bipy, <b>2a</b>; NN = dpa, <b>2b</b>, or [Pt(OH)Me<sub>2</sub>(dpkOH)], <b>3</b>). Complex <b>2a</b> crystallizes as the hydrate <b>2a</b>·7H<sub>2</sub>O, which has a complex supramolecular network structure formed
through hydrogen bonding between PtOH groups and water molecules.
Attempts to trap a potential oxoplatinum(IV) intermediate in these
reactions were unsuccessful, and computational studies suggest that
oxoplatinum(IV) intermediates are improbable. It is suggested that
oxygen atom transfer from the dioxirane to platinum is coupled to
proton addition to give the hydroxoplatinum group directly
