New Cyclosiloxanolate Cluster Complexes of Transition Metals

New cyclosiloxanolate transition metal cluster complex derivatives were prepared. PhSiO2K reacted with NiX2 (X2 = Cl2 or acac) to give K2{[g6)(PhSiO2)6]2[l3)(OH)]2Ni4K4}, a mixed group 1–group 10 metal complex. PhSiO2Na reacted with Ni(NH3)6I2 to give Na{[g6)(PhSiO2)6]2Ni6(l6)I)} as the first example of ‘‘encapsulated’’ I) ion in siloxanolate complexes. The macrocyclic Na4{[g12)(PhSiO2)12]Cu4} complex reacted with g6)(1,3,5)C7H8)Cr(CO)3 to give the heterobimetallic adduct Na4{[g12)(PhSiO2)12]Cu4}. [Cr(CO)3]3 as one of the rare examples of heterobimetallic complexes with different oxidation numbers of the metals. The copper derivative {[h)(PhSiO2)6]2Cu6(n)BuOH)5} reacted in MeOH/CHCl3 (1:6) with Et4NCN to give the hexanuclear complex {[g6)(PhSiO2)6]2Cu6(g2)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.