Mono- and bimetallic platinum(II) and palladium(II) complexes containing fluorinated benzothiolates

Abstract

The new mononuclear palladium(II) and platinum(II) [M(p-SC6F4(CF3))(2)(dppe)] complexes M = Pd la, Pt 2a

[M(o-SC6H4(CF3))(2)(dppe)] M = Pd Id, Pt 2d as well as the previously known [M(SC6F5)(2)(dppe)] M = Pd 1b, Pt 2b and [M(P-SC6HF4)(2)(dppe)] M = Pd 1c, Pt 2c, have been used as metalloligands for the preparation of the heteroleptic bimetallic complexes [M-2(mu-SRf)(2)(dppe)(2)](SO3CF3)(2) M = Pd, Rf = p-C6F4(CF3) 3a, C6F5 3b, p-C6HF4 3c, o-C6H4(CF3) 3d

M = Pt, Rf = p-C6F4(CF3) 4a, C6F5 4b, p-C6HF4 4c and o-C6H4(CF3) 4d. Variable temperature F-19 NMR experiments show that the fluorothiolate bridged bimetallic compounds are fluxional in solution whereas mononuclear complexes are not. The solid state X-ray diffraction structures of [Pd(p-SC6HF4)(2)(dppe)] (1c), [Pt(SC6F5)(2)(dppe)] (2b) and [Pt(o-SC6H4(CF3))(2)(dppe)] (2d) show square-planar coordination around the metal centers. The solid state molecular structure of the compound [Pt-2(mu-o-SC6H4(CF3))(2)(dppe)(2)](SO3CF3)(2) (4d), exhibit a planar [Pt-2(mu-S)(2)] ring with the sulfur substituents in an anti configuration. (c) 2007 Elsevier Ltd. All rights reserved.