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).
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.
School of Chemistry, University of Tasmania, Private Bag 75, Hobart, Tasmania 7001, Australia. allan.canty@utas.edu.au
Allan J
AJ
Canty
Michael G
MG
Gardiner
Roderick C
RC
Jones
Thomas
T
Rodemann
Manab
M
Sharma