Cu(I) and Ag(I) complexes of chalcogenide derivatives of the organometallic ligand dppf and the dppa analogue

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Authors	LIU H.Z. BANDEIRA N.A.G. CALHORDA M.J. DREW M.G.B. FELIX V. NOVOSAD J. DE BIANNI F.F. ZANELLO P.
Year of publication	2004
Type	Monograph
MU Faculty or unit	Faculty of Science
Citation
Description	New Cu(I) and Ag(I) complexes were prepared by reaction of [M(NCCH3)(4)][X] (M = Cu or Ag; X = BF4 or PF6) with the bidentate chalcogenide ligands Ph2P(E)NHP(E)Ph-2 (E = S, S(2)dppa; E = Se, Se(2)dppa), and dpspf (1, 1'-bis(diphenylselenophosphoryl)ferrocene). Copper and silver behaved differently. While three molecules of either S(2)dppa and Se(2)dppa bind to a distorted tetrahedral Cu-4 cluster, with deprotonation of the ligand, 1:2 complexes of the neutral ligands are formed with Ag(l), with a tetrahedral coordination of the metal. The [Cu-4{Ph2P(Se)NP(Se)Ph-2}(3)](+) clusters assemble as dimers, held together by weak Se...Se distances interactions. Another dimer was observed for the [Ag(dpspf)](+) cation, with two short Ag...Se distances. DFT and MP2 calculations indicated the presence of attracting interactions, reflected in positive Mayer indices (MI). The electrochemistry study of this species showed that both oxidation and reduction took place at silver.
Related projects:	Structure and character of bonding, properties and analysis of synthetic and natural molecular ensembles