New cyclosiloxanolate cluster complexes of transition metals

New cyclosiloxanolate transition metal cluster complex derivatives were prepared. PhSiO2K reacted with NiX2 (X-2 = Cl-2 or acac) to give K-2{[eta(6)-(PhSiO2)(6)](2)[mu(3)-(OH)](2)Ni4K4}, a mixed group 1-group 10 metal complex. PhSiO2Na reacted with Ni(NH3)(6)I-2 to give Na{[eta(6)-(PhSiO2)(6)](2)Ni-6(mu(6)-I)} as the first example of "encapsulated" I- ion in siloxanolate complexes. The macrocyclic Na-4{[eta(12)-(PhSiO2)(12)]Cu-4} complex reacted with eta(6)-(1,3,5-C7H8)Cr(CO)(3) to give the heterobimetallic adduct Na-4{[eta(12)-(PhSiO2)(12)]Cu-4}center dot [Cr(CO)(3)](3) as one of the rare examples of heterobimetallic complexes with different oxidation numbers of the metals. The copper derivative {[eta(6)-(PhSiO2)(6)](2)Cu-6(n-BuOH)(5)} reacted in MeOH/CHCl3 (1:6) with Et4NCN to give the hexanuclear complex {[eta(6)-(PhSiO2)(6)](2)Cu-6(eta(2)-C3H5N2O2)(2)}, containing 2-amino-2-oxoetanimidic acid methyl ester monoanion ligands, product of an unexpected C-C coupling reaction. This latter complex was characterized also by X-ray diffraction crystal and molecular structure determination.