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{[η6−(PhSiO2)6]2[μ3−(OH)]2Ni4K4}, a mixed group 1–group 10 metal complex. PhSiO2Na reacted with Ni(NH3)6I2 to give Na{[η6−(PhSiO2)6]2Ni6(μ6−I)} as the first example of “encapsulated” I− ion in siloxanolate complexes. The macrocyclic Na4{[η12−(PhSiO2)12]Cu4} complex reacted with η6−(1,3,5−C7H8)Cr(CO)3 to give the heterobimetallic adduct Na4{[η12−(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 {[η6−(PhSiO2)6]2Cu6(n−BuOH)5} reacted in MeOH/CHCl3 (1:6) with Et4NCN to give the hexanuclear complex {[η6−(PhSiO2)6]2Cu6(η2−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