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  • 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+).
    Author: Usón R, Forniés J, Fernández Sanz J, Usón MA, Usón I, Herrero S.
    Journal: Inorg Chem; 1997 Apr 23; 36(9):1912-1922. PubMed ID: 11669797.
    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.
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