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(μ-SRF)2Pt(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(μ-SRF)2Pd(dppe)]2+/[(dppe)Pt(μ-SRF)2Pt(dppe)]2+ or by assembling the monometallic building blocks [(dppe)M(μ-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 °C to +50 °C. A single crystal of the heterobimetallic compound [(dppe)Pd(μ-SC6F5)2Pt(dppe)](SO3CF3)2(acetone)2 (2) was isolated and analyzed by X-ray diffraction. Comparison with the corresponding structures exhibited by the homobimetallic analogous, [Pd2(μ-SC6F5)2(dppe)2](SO3CF3)2(acetone)2 (5) and [Pt2(μ-SC6F5)2(dppe)2](SO3CF3)2(acetone)2 (6) shows that all three structures are isostructural in space group P1¯. All three compounds exhibit a centrosymmetric planar [M2(μ-S)2] ring in which the sulfur substituents are arranged in an anti configuration.

Heterobimetallic platinum(II)–palladium(II) complexes with polyfluorinated benzenethiolates as bridge ligand were prepared, [(dppe)Pd(μ-SRF)2Pt(dppe)](SO3CF3)2 with SRF = p-SC6F4(CF3), SC6F5, p-SC6HF4 and o-SC6H4(CF3); and studied by their independent temperature equilibrium with their homobimetallic analogous. Comparison of the single crystal X-ray structures of [(dppe)Pd(μ-SC6F5)2Pt(dppe)](SO3CF3)2 and their homobimetallic complexes is discussed.Figure optionsDownload as PowerPoint slide