Syntheses and properties of NCN-bridged tri- and tetranuclear complexes of cobalt and rhodium |
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| Institution: | 1. Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan;2. Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan |
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| Abstract: | The reaction of Cp1CoI2]2 (1b) with 2 equiv of NaNCNH affords the 16-membered macrocyclic NCNH-bridged tetracobalt(III) complex Cp1CoI(μ2-NCNH-N,N′)]4 (2b), while that with 2 equiv of Na2NCN yields the C3-elongated cubane-like NCN-bridged tetracobalt(III) complex Cp1Co(μ3-NCN-N,N,N′)3(CoCp1)3(μ3-NCN-N,N,N)] (4b). Treatment of Cp1RhCl2]2 (1c) with 2 equiv of NaNCNH gives the C3-elongated cubane-like tetrarhodium(III) complex Cp1Rh(μ3-NCN-N,N,N′)3(RhCp1)3(μ3-NCN-N,N,N)] (4c) via the macrocyclic complex Cp1RhCl(μ2-NCNH-N,N′)]4 (2c). On the other hand, the reaction of Cp1CoCl]2 (7) with Na2NCN affords the anionic bis(NCN)-capped tricobalt(II) complex Na(Cp1Co)3(μ3-NCN-N,N,N)2] (6). The molecular structures of complexes 2b · CH2Cl2 and 4c · 2C6H6 have been confirmed by X-ray analyses. The electrochemical properties of these types of NCN-bridged group 9 metal complexes have also been examined. |
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