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

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• 作者：Liu ; Huizhang ; Bandeira ; Nuno A.G. ; Calhorda ; Maria Jos?? ; Drew ; Michael G.B. ; F??lix ; Vitor ; et. al.
• 关键词：Cu(I) complexes ; Ag(I) complexes ; Crystal structures ; Clusters ; DFT calculations ; Electrochemistry
• 刊名：Journal of Organometallic Chemistry
• 出版年：2004
• 出版时间：September 1, 2004
• 年：2004
• 卷：689
• 期：17
• 页码：2808-2819
• 全文大小：564 K

文摘

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)Ph₂ (E=S, S₂dppa; E=Se, Se₂dppa), and dpspf (1,1aaa-bis(diphenylselenophosphoryl)ferrocene). Copper and silver behaved differently. While three molecules of either S₂dppa and Se₂dppa bind to a distorted tetrahedral Cu₄ cluster, with deprotonation of the ligand, 1:2 complexes of the neutral ligands are formed with Ag(I), with a tetrahedral coordination of the metal. The [Cu₄{Ph₂P(Se)NP(Se)Ph₂}₃]⁺ clusters assemble as dimers, held together by weak SeaaaSe distances interactions. Another dimer was observed for the [Ag(dpspf)]⁺ cation, with two short AgaaaSe 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.