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Published July 15, 2002 | Supplemental Material
Journal Article Open

Structural and Mechanistic Investigations of the Oxidation of Dimethylplatinum(II) Complexes by Dioxygen


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.

Additional Information

© 2002 American Chemical Society. Received December 18, 2001. Publication Date (Web): June 12, 2002. Support by the National Science Foundation (Grant No. CHE-9807496), Akzo-Nobel, and BP are gratefully acknowledged. We wish to thank Drs. William Schaefer and Richard Marsh for help with X-ray structure determinations and Professor John Eiler for help with mass spectrometry measurements. We also gratefully acknowledge Flavio Grynszpan for the cover art design.

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