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

The new mononuclear palladium(II) and platinum(II) [M(p-SC6F4(CF3))2(dppe)] complexes M = Pd 1a, Pt 2a; [M(o-SC6H4(CF3))2(dppe)] M = Pd 1d, 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 [M2(μ-SRf)2(dppe)2](SO3CF3)2 M = Pd, Rf = p-C6F4(CF3) 3a, C6F53b, p-C6HF43c, o-C6H4(CF3) 3d; M = Pt, Rf = p-C6F4(CF3) 4a, C6F54b, p-C6HF44c and o-C6H4(CF3) 4d. Variable temperature 19F 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 [Pt2(μ-o-SC6H4(CF3))2(dppe)2](SO3CF3)2 (4d), exhibit a planar [Pt2(μ-S)2] ring with the sulfur substituents in an anti configuration.

Fluxional bimetallic complexes, [M2(μ-SRf)2(dppe)2](SO3CF3)2 M = Pd, Rf = p-C6F4(CF3) 3a, C6F53b, p-C6HF43c, o-C6H4(CF3) 3d; M = Pt, Rf = p-C6F4(CF3) 4a, C6F54b, p-C6HF44c and o-C6H4(CF3) 4d, obtained from metalloligands –[M(SRf)2(dppe)]– and “[M(dppe)]” moieties, have been studied by variable temperature 19F NMR. Crystal and molecular structures of [Pd(p-SC6HF4)2(dppe)], [Pt(SC6F5)2(dppe)], [Pt(o-SC6H4(CF3))2(dppe)], and [Pt2(μ-o-SC6H4(CF3))2(dppe)2](SO3CF3)2 have been solved.Figure optionsDownload as PowerPoint slide