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

• Published in: Inorganica Chimica Acta 2009-11, Vol.362 (14), p.5122-5125
• Main Authors: Rivera, Guillermina, Bernès, Sylvain, Barbarín, Cecilia Rodríguez de, Torrens, Hugo
• Format: Article
• Language: English
• Subjects: Crystal structures; Fluorinated-thiolates; Heterobimetallics; Palladium; Platinum
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2009.07.036

Heterobimetallic platinum(II)–palladium(II) complexes with polyfluorinated benzenethiolates as bridge ligand were prepared, [(dppe)Pd(μ-SR F) 2Pt(dppe)](SO 3CF 3) 2 with SR F = p-SC 6F 4(CF 3), SC 6F 5, p-SC 6HF 4 and o-SC 6H 4(CF 3); and studied by their independent temperature equilibrium with their homobimetallic analogous. Comparison of the single crystal X-ray structures of [(dppe)Pd(μ-SC 6F 5) 2Pt(dppe)](SO 3CF 3) 2 and their homobimetallic complexes is discussed. Synthesis of the heterobimetallic platinum(II)–palladium(II) complexes with poly fluorinated benzenethiolates as intermetallic bridges, [(dppe)Pd(μ-SR F) 2Pt(dppe)](SO 3CF 3) 2 with SR F = p-SC 6F 4(CF 3) ( 1), SC 6F 5 ( 2), p-SC 6HF 4 ( 3) and o-SC 6H 4(CF 3) ( 4), have been accomplished either by a redistribution reaction in mixtures of the homonuclear bimetallic species, [(dppe)Pd(μ-SR F) 2Pd(dppe)] 2+/[(dppe)Pt(μ-SR F) 2Pt(dppe)] 2+ or by assembling the monometallic building blocks [(dppe)M(μ-SR F) 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-SC 6F 5) 2Pt(dppe)](SO 3CF 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(μ-SC 6F 5) 2(dppe) 2](SO 3CF 3) 2(acetone) 2 ( 5) and [Pt 2(μ-SC 6F 5) 2(dppe) 2](SO 3CF 3) 2(acetone) 2 ( 6) shows that all three structures are isostructural in space group P 1 ¯ . All three compounds exhibit a centrosymmetric planar [M 2(μ-S) 2] ring in which the sulfur substituents are arranged in an anti configuration.