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Binuclear intermediates in oxidation reactions: [(Me3SiCC)Me2(bipy)Pt-PtMe2(bipy)]+ in the oxidation of PtMe2(bipy) (bipy = 2,2'-bipyridine) by IPh(CCSiMe3)(OTf) (OTf = triflate)


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Canty, AJ and Gardiner, MG and Jones, Roderick C and Rodemann, T and Sharma, M (2009) Binuclear intermediates in oxidation reactions: [(Me3SiCC)Me2(bipy)Pt-PtMe2(bipy)]+ in the oxidation of PtMe2(bipy) (bipy = 2,2'-bipyridine) by IPh(CCSiMe3)(OTf) (OTf = triflate). Journal of the American Chemical Society, 131 (21). pp. 7236-7237. ISSN 0002-7863

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A study of the reaction of dimethyl(2,2'-bipyridine)platinum(II)) with phenyl(trimethylsilylalkynyl)iodonium triflate at low temperature in acetone, leading to detection of the Pt-Pt bonded cation [Pt2Me4(CCSiMe3)(bipy)2]+, an intermediate in the oxidation of platinum(II) to platinum(IV). The cation is assessed as Pt(III)-Pt(III) = Pt(IV)-Pt(II), and at the second extreme may be regarded as a cationic alkynylplatinum(IV) centre [PtMe2(CCSiMe3)(bipy)]+ stabilised by PtMe2(bipy as a donor ligand. The Pt-Pt interaction in is not supported by bridging groups, unlike all previously reported organoplatinum dimers with (average) formal oxidation state +III for platinum. NMR data are consistent with a significant Pt(IV)-Pt(II) influence for octahedral and square pyramidal Pt, respectively. The detection and isolation of the cation provides a number of insights into the mechanism of oxidation reactions. Two pi-stacked PtMe2(bipy) units may be involved in the initial oxidation step to enhance the nucleophilic character of Pt(II). Dimeric species similar to the cation may be formed as, to date undetected, intermediates in other reactions, including for other ligands, d8 metal systems and oxidants.

Item Type: Article
Keywords: oxidative addition, metal-metal bonds, binuclear complexes, organoplatinum, iodonium, alkynylplatinum, platinum acetylides, platinum(IV)
Journal or Publication Title: Journal of the American Chemical Society
Page Range: pp. 7236-7237
ISSN: 0002-7863
Identification Number - DOI: 10.1021/ja902799u
Additional Information: Copyright © 2009 American Chemical Society
Date Deposited: 02 Jun 2009 05:11
Last Modified: 18 Nov 2014 04:00
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