Synthesis and transition metal complexes of 1,1′-bis(diphenylethynylphosphino)ferrocene

Abstract

The new ferrocene based bisphosphine [Fe{C5H4P(CCPh)2}2] (1) was synthesized in 82% yield by the treatment of bis(dichlorophosphino)ferrocene [Fe(C5H4PCl2)2] with four equivalents of lithium phenylacetylide. The reactions of 1 with aq. H2O2, elemental sulfur or selenium afforded bis(chalcogenide) derivatives, [Fe{C5H4P(E)(CCPh)2}2] (2 E = O, 3 E = S, 4 E = Se). The reaction of 1 with [M(NC5H11)2(CO)4] (M = Mo, W), [RuCp(PPh3)2Cl] and [M(COD)Cl2] (M = Pd, Pt) resulted in the formation of the respective chelate complexes, [Fe{C5H4P(CCPh)2}2{M(CO)4}] (5 M = Mo, 6 M = W), [Fe{C5H4P(CCPh)2}2{RuCp(Cl)}] (8) and [Fe{C5H4P(CCPh)2}2{MCl2}] (9 M = Pd, 10 M = Pt), whereas the reaction of 1 with [Ru(η6-p-cymene)Cl2]2 and [AuCl(SMe2)] yielded the corresponding bimetallic complexes [Fe{C5H4P(CCPh)2}2{RuCl2(η6-p-cymene)}2] (7) and [Fe{C5H4P(CCPh)2}2{AuCl}2] (15). The reactions between 1 and CuX in equimolar ratios also yielded binuclear complexes, [Fe{C5H4P(CCPh)2}2{CuX}2] (11 X = Cl, 12 X = Br, 13 X = I), whereas [Cu(CH3CN)4]BF4 yielded the cationic complex [(Fe{C5H4P(CCPh)2}2)2Cu]BF4 (14). All the compounds were characterized by spectroscopic methods and the structures of complexes 1, 5, 6, 8, 10, 13 and 14 were confirmed by single crystal X-ray diffraction studies.