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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, Gardiner, MG, Jones, Roderick C, 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, vol. 131, no. 21 , pp. 7236-7237 , doi: 10.1021/ja902799u.

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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
Authors/Creators:Canty, AJ and Gardiner, MG and Jones, Roderick C and Rodemann, T and Sharma, M
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
ISSN: 0002-7863
DOI / ID Number: 10.1021/ja902799u
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Copyright © 2009 American Chemical Society

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