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Coordination Chemistry with the Complex Chelating Ligands [{Fe2Cp2(CO)3)2{CN[CH2]n NC}] (n = 2, 3). Heteropentanuclear “Supercomplexes” with μ5-Diisocyanide Bridges The tetranuclear complexes [(Fe2Cp2(CO)2(μ-CO)}2(μ4-CN[CH2]nNC}] [n = 2 (2), 3 (3)] act as bidentate chelating ligands towards the Lewis-acidic metal halides MnCl2, MnBr2, FeCl2, CoCl2, NiCl2, NiBr2, CuCl2, CuBr2, ZnCl2, ZnI2, CdCl2, CdI2, HgCl2, the chloro complexes [MCl2-(NCPh)2] (M = Pd, Pt), Zn(OAc)2 · H2O, and [Mo(CO)4(η-NBD)] (NBD = 2,5-norbornadiene) to give a total of 22 pentanuclear “supercomplexes” ,6–21, which have been characterized by elemental analyses and IR and NMR (1H, 13C) spectra. Reaction of 2 with [Ni(COD)2] in CH2Cl2 gave only rise to the dichloronickel(II) species 9a. Very remarkably, the pentairon complex [(Fe2Cp2(CO)2(μ-CO)2(μ5-CN(CH2)2-NC)}]FeCl2 (7) also formed spontaneously (!) when 2 was refluxed in chloroform for several hours. The X-ray structure analysis of [{Fe2Cp2(CO)2(μ-CO))2{μ5-CN(CH2)2NC}]CdI2 (14b) confirms the twofold μ3-(C,C,N) bridging mode of a diisocyanide ligand in a cis/cis-anti-configurated [Fe2]2Cd pentanuclear system of crystallographic C2 symmetry. |
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