Oxidative dimerisation of arylamido complexes of platinum: X-ray structure of [Pt2(PEt3)4Cl2(N2C12H10)] PF6
Abstract
The phenyl groups of two molecules of the phenylamido complex [Pt(PEt3)2Cl(NHPh)] are oxidatively coupled, in the para position, by AgPF6 to give the dicationic complex [Pt2(PEt3)4Cl2(N2C12H11)][PF6]2 which can be deprotonated to the paramagnetic monocationic complex [Pt2(PEt3)4Cl2(N2C12H10)] PF6. This has been examined by X-ray crystallography (orthorhombic, space group Pnnm, R= 0.024 for 2 854 diffractometer measured observed reflections). The structure shows a bridging benzidine group which is strictly planar with marked quinonoid character within the arene rings [C–C 1.355(5) and 1.427(6)Å]. The mononuclear p-tolyl complex undergoes a similar coupling in the ortho position, but the 1-naphthyl complex gives a neutral coupled complex because of the much reduced conjugation in the twisted 1,1′-binaphthyl system.