eCite Digital Repository

Binuclear Intermediates in Oxidation Reactions: [(Me3SiCC)Me2(bipy)Pt-PtMe2(bipy)]+ in the Oxidation of PtIIMe2(bipy) (bipy = 2,2'-Bipyridine) by IPh(CCSiMe3)(OTf) (OTf = Triflate)

Citation

Canty, AJ and Gardiner, MG and Jones, RC and Rodemann, T and Sharma, M, Binuclear Intermediates in Oxidation Reactions: [(Me3SiCC)Me2(bipy)Pt-PtMe2(bipy)]+ in the Oxidation of PtIIMe2(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 (2009) [Refereed Article]


Preview
PDF
Restricted - Request a copy
130Kb
  

DOI: doi:10.1021/ja902799u

Abstract

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 Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
Author:Gardiner, MG (Associate Professor Michael Gardiner)
Author:Jones, RC (Dr Roderick Jones)
Author:Rodemann, T (Dr Thomas Rodemann)
Author:Sharma, M (Dr Manab Sharma)
ID Code:57300
Year Published:2009
Web of Science® Times Cited:30
Deposited By:Chemistry
Deposited On:2009-07-05
Last Modified:2012-10-05
Downloads:0

Repository Staff Only: item control page