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

Rostovtsev, Vsevolod V. and Henling, Lawrence M. and Labinger, Jay A. and Bercaw, John E. (2002) Structural and Mechanistic Investigations of the Oxidation of Dimethylplatinum(II) Complexes by Dioxygen. Inorganic Chemistry, 41 (14). pp. 3608-3619. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20170321-100112771

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ic0112903DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic0112903PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic0112903PublisherSupporting Information
ORCID:
AuthorORCID
Labinger, Jay A.0000-0002-1942-9232
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.
Funders:
Funding AgencyGrant Number
NSFCHE-9807496
Akzo-NobelUNSPECIFIED
BPUNSPECIFIED
Issue or Number:14
Record Number:CaltechAUTHORS:20170321-100112771
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170321-100112771
Official Citation:Structural and Mechanistic Investigations of the Oxidation of Dimethylplatinum(II) Complexes by Dioxygen Vsevolod V. Rostovtsev, Lawrence M. Henling, Jay A. Labinger, and John E. Bercaw Inorganic Chemistry 2002 41 (14), 3608-3619 DOI: 10.1021/ic0112903
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75268
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:21 Mar 2017 17:20
Last Modified:03 Oct 2019 16:48

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