New Cyclosiloxanolate Cluster Complexes of Transition Metals |
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| Authors: | Cecilia Mortalò Andrea Caneschi Andrea Cornia Eliano Diana Silvia Faranda Valérie Marvaud Maddalena Pizzotti Olga I. Shchegolikhina Claudia Zucchi Gyula Pályi |
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| Affiliation: | (1) Department of Chemistry, University of Modena and Reggio Emilia, Via G. Campi 183, I-41100 Modena, Italy;(2) INSTM and Department of Chemistry, University of Firenze, Via della Lastruccia 3, I-50019, Sesto Fiorentino, Firenze, Italy;(3) Department of Inorganic, Physical and Materials Chemistry, University of Torino, Via P. Giuria 7, I-10125 Torino, Italy;(4) Laboratory of Inorganic Chemistry and Molecular Materials, UPMC, Case 42, 4 place Jussieu, F-75252 Paris Cedex 05, France;(5) Department of Inorganic and Organometallic Chemistry and CNR Centre, University of Milano, Via Venezian 21, I-20133 Milano, Italy;(6) A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, Moscow, 117813, Russia |
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| Abstract: | ![]()
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. This paper is dedicated to the 70th birthday of Professor Dr. Gunter Schmid (Essen), pioneer of large cluster chemistry, known to friends as GOLD-Schmid, because of his famous discovery of the Au55 cluster. The Authors are proud to be within his many friends. |
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| Keywords: | Cyclosiloxanolate complexes cluster complexes bimetallic complex C– C coupling cyanide– cyanide coupling |
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