Binuclear intermediates in oxidation reactions: [(Me(3)SiC[triple bond]C)Me(2)(bipy)Pt-PtMe(2)(bipy)](+) in the oxidation of Pt(II)Me(2)(bipy) (bipy = 2,2'-bipyridine) by IPh(C[triple bond]CSiMe(3))(OTf) (OTf = triflate)

Allan J Canty; Michael G Gardiner; Roderick C Jones; Thomas Rodemann; Manab Sharma

doi:10.1021/ja902799u

Binuclear intermediates in oxidation reactions: [(Me(3)SiC[triple bond]C)Me(2)(bipy)Pt-PtMe(2)(bipy)](+) in the oxidation of Pt(II)Me(2)(bipy) (bipy = 2,2'-bipyridine) by IPh(C[triple bond]CSiMe(3))(OTf) (OTf = triflate)

J Am Chem Soc. 2009 Jun 3;131(21):7236-7. doi: 10.1021/ja902799u.

Authors

Allan J Canty¹, Michael G Gardiner, Roderick C Jones, Thomas Rodemann, Manab Sharma

Affiliation

¹ School of Chemistry, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia. allan.canty@utas.edu.au

PMID: 19422235
DOI: 10.1021/ja902799u

Abstract

A study of the reaction of PtMe(2)(bipy) with IPh(C[triple bond]CSiMe(3))(OTf) at low temperature in acetone, leading to detection of the Pt-Pt-bonded cation [Pt(2)Me(4)(C[triple bond]CSiMe(3))(bipy)(2)](+), an intermediate in the oxidation of Pt(II) to Pt(IV), is reported. The cation is assessed as Pt(III)-Pt(III) <--> Pt(IV)-Pt(II), and at the other extreme may be regarded as a cationic alkynylplatinum(IV) center, "[Pt(IV)Me(2)(C[triple bond]CSiMe(3))(bipy)](+)", stabilized by "Pt(II)Me(2)(bipy)" as a donor ligand. The detection and isolation of the [Pt(2)Me(4)(C[triple bond]CSiMe(3))(bipy)(2)](+) cation provides a number of insights into the mechanisms of oxidation reactions.