title: Reactions of {[Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd](&mgr;-SC(6)F(5))}(4).2O(C(2)H(5))(2). Crystal Structures of the Complexes [(Ph(3)P)Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd(SC(6)F(5))].1.4CH(2)Cl(2) and [(Ph(3)P)Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd(PPh(3))]SO(3)CF(3).2CH(2)Cl(2) and ab Initio MO Calculations on the Model Systems [(H(3)P)Pd(&mgr;-H(2)PCH(2)PH(2))(&mgr;-SH)Pd(PH(3))](+) and [(H(3)P)Pd(&mgr;-H(2)PCH(2)PH(2))Pd(PH(3))](2+).
abstract: {[Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd](&mgr;-SC(6)F(5))}(4) reacts 1:4 with neutral ligands L to give [LPd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd(SC(6)F(5))] or 1:8 to form [LPd(&mgr;-SC(6)F(5))(&mgr;-dppm)PdL](+) (dppm = bis(diphenylphosphino)methane). These binuclear complexes retain the palladium-palladium bond and the two dissimilar bridging ligands, as demonstrated by the X-ray structural determinations carried out on [(Ph(3)P)Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd(SC(6)F(5))].1.4CH(2)Cl(2) and [(Ph(3)P)Pd(&mgr;-SC(6)F(5))(&mgr;-dppm)Pd(PPh(3))]SO(3)CF(3).2CH(2)Cl(2). Ab initio calculations on the model systems [(H(3)P)Pd(&mgr;-H(2)PCH(2)PH(2))(&mgr;-SH)Pd(PH(3))](+) and [(H(3)P)Pd(&mgr;-H(2)PCH(2)PH(2))Pd(PH(3))](2+) show that the metal-metal bond arises mainly from interactions between palladium sp orbitals, which also play a predominant role in the binding with the sulfur bridge.
authors.affiliation: Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain, Departamento de Química Física, Facultad de Químicas, Universidad de Sevilla, E-41012 Sevilla, Spain, and Institut für Anorganische Chemie, Universität Göttingen, Tammanstrasse 4, D-3400 Göttingen, Germany.
authors.forename: Rafael
authors.initials: R
authors.lastname: Usón
authors.forename: Juan
authors.initials: J
authors.lastname: Forniés
authors.forename: Javier
authors.initials: J
authors.lastname: Fernández Sanz
authors.forename: Miguel A.
authors.initials: MA
authors.lastname: Usón
authors.forename: Isabel
authors.initials: I
authors.lastname: Usón
authors.forename: Santiago
authors.initials: S
authors.lastname: Herrero