Heterobimetallic platinum(II)-palladium(II) complexes bridged by fluorobenzenethiolates. Structure and equilibria

Abstract

Synthesis of the heterobimetallic platinum(II)-palladium(II) complexes with poly fluorinated benzenethiolates as intermetallic bridges, [(dppe) Pd(mu-SRF)(2)Pt(dppe)](SO3CF3)(2) with SRF = p-SC6F4(CF3) (1), SC6F5 (2), p-SC6HF4 (3) and o-SC6H4(CF3) (4), have been accomplished either by a redistribution reaction in mixtures of the homonuclear bimetallic species, [(dppe) Pd(mu-SRF)(2)Pd(dppe)](2+)/[(dppe) Pt(mu-SRF)(2)Pt(dppe)](2+) or by assembling the monometallic building blocks [(dppe) M(mu-SRF)(2)]/[(dppe)M' (solvent)(2)](2+), M, M' = Pd or Pt. Both experimental systems reach an equilibrium state which is independent of the temperature within the probed range, -90 degrees C to + 50 degrees C. A single crystal of the heterobimetallic compound [(dppe)Pd(mu-SC6F5)(2)Pt(dppe)](SO3CF3)(2)(acetone)(2) (2) was isolated and analyzed by X-ray diffraction. Comparison with the corresponding structures exhibited by the homobimetallic analogous, [Pd-2(mu-SC6F5)(2)(dppe)(2)](SO3CF3)(2)(acetone)(2) (5) and [Pt-2(mu-SC6F5)(2)(dppe)(2)](SO3CF3)(2)(acetone)(2) (6) shows that all three structures are isostructural in space group P (1) over bar. All three compounds exhibit a centrosymmetric planar [M-2(mu-S)(2)] ring in which the sulfur substituents are arranged in an anti configuration. (C) 2009 Elsevier B. V. All rights reserved.