RESUMO
Ferrocene-based phosphines constitute an important auxiliary ligand in inorganic chemistry. Utilizing the (ferrocenylethyl)phosphines (FcCH2CH2)3-nHnP (Fc = ferrocenyl; n = 2, 1; n = 1, 2; n = 0, 3) the synthesis of a series of coordination complexes [(FcCH2CH2)3-nHnPCuCl]4 (n = 2, 1-CuCl; n = 0, 3-CuCl), [(FcCH2CH2)2HPCuCl] (2-CuCl), {[(FcCH2CH2)H2P]2AgCl}2 (1-AgCl), [(FcCH2CH2)2HPAgCl] (2-AgCl), [(FcCH2CH2)3PAgCl]4 (3-AgCl), [(FcCH2CH2)3PM(OAc)]4 (M = Cu, 3-CuOAc M = Ag, 3-AgOAc), [(FcCH2CH2)3-nHnPAuCl] (n = 1, 2-AuCl; n = 0, 3-AuCl), via the reaction between the free phosphine and MX (M = Cu, Ag and Au; X = Cl, OAc), is described. The reaction between the respective phosphine with a suspension of metal-chloride or -acetate in a 1 : 1 ratio in THF at ambient temperature affords coordinated phosphine-coinage metal complexes. Varying structural motifs are observed in the solid state, as determined via single crystal X-ray analysis of 1-CuCl, 3-CuCl, 1-AgCl, 3-AgCl, 3-CuOAc, 3-AgOAc, 2-AuCl and 3-AuCl. Complexes 1-CuCl and 3-CuCl are tetrameric Cu(i) cubane-like structures with a Cu4Cl4 core, whereas silver complexes with primary and tertiary phosphine reveal two different structural types. The structure of 1-AgCl, unlike the rest, displays the coordination of two phosphines to each silver atom and shows a quadrangle defined by two Ag and two Cl atoms. In contrast, 3-AgCl is distorted from a cubane structure via elongation of one of the ClAg distances. 3-CuOAc and 3-AgOAc are isostructural with step-like cores, while complexes 2-AuCl and 3-AuCl reveal a linear geometry of a phosphine gold(i) chloride devoid of any aurophilic interactions. All of the complexes were characterized in solution by multinuclear (1)H, (13)C{(1)H} and (31)P NMR spectroscopic techniques; the redox chemistry of the series of complexes was examined using cyclic voltammetry. This class of complexes has been found to exhibit one reversible Fe(ii)/Fe(iii) oxidation couple, suggesting the absence of electronic communication between the ferrocenyl units on individual phosphine ligands as well as between different phosphines on the polymetallic cores.
RESUMO
Reactions of CuCl with Te(Ph)SiMe3 and solublizing trialkylphosphine ligands afford a series of polynuclear copper-phenyltellurolate complexes that has been structurally characterized. The formation of the complexes is found to be highly dependent on the ancillary phosphine ligand used. The synthesis and structures of [Cu2(mu-TePh)2(PMe3)4] 1, [Cu4(mu3-TePh)4(PPr(i)3)3] 2, [Cu5(mu-TePh)3(mu3-TePh)3(PEt3)3][PEt3Ph] 3, and [Cu12Te3(mu3-TePh)6(PEt3)6] 4 are described. The telluride (Te(2-)) ligands in 4 arise from the generation of TePh2 in the reaction mixtures. The subsequent co-condensation of clusters 3 and 4 leads to the generation of the nanometer sized complex [Cu29Te9(mu3-TePh)10(mu4-TePh)2(PEt3)8][PEt3Ph] 5 in good yield, in addition to small amounts of [Cu39(mu3-TePh)10(mu4-TePh)Te16(PEt3)13] 6. These complexes are formed via the photo elimination of TePh2. The cyclic voltammogram of 5 in THF solution exhibits two oxidation waves, assigned to the oxidation of the Cu(I) centers.