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

Synthesis of the heterobimetallic platinum(II)-palladium(II) complexes with poly fluorinated benzenethiolates as intermetallic bridges, [(dppe) Pd(mu-SR(F))(2)Pt(dppe)](SO(3)CF(3))(2) with SR(F) = p-SC(6)F(4)(CF(3)) (1), SC(6)F(5) (2), p-SC(6)HF(4) (3) and o-SC(6)H(4)(CF(3)) (4), have been accomplished either by a redistribution reaction in mixtures of the homonuclear bimetallic species, [(dppe) Pd(mu-SR(F))(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-SC(6)F(5))(2)Pt(dppe)](SO(3)CF(3))(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-SC(6)F(5))(2)(dppe)(2)](SO(3)CF(3))(2)(acetone)(2) (5) and [Pt(2)(mu-SC(6)F(5))(2)(dppe)(2)](SO(3)CF(3))(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.