Heterometallic Cu/Co and Cu/Co/Zn Complexes Bearing Rare Asymmetric Tetranuclear Cores: Synthesis, Structures, and Magnetic and Catalytic Properties Toward the Peroxidative Oxidation of Cycloalkanes

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• 作者：Dmytro S. Nesterov ; Volodymyr N. Kokozay ; Julia Jezierska ; Oleksiy V. Pavlyuk ; Roman Boc虒a ; Armando J. L. Pombeiro
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：May 16, 2011
• 年：2011
• 卷：50
• 期：10
• 页码：4401-4411
• 全文大小：1044K
• 年卷期：v.50,no.10(May 16, 2011)
• ISSN：1520-510X

文摘

The three novel heterometallic complexes [CuCo^IIICo^II₂(MeDea)₃Cl₃(CH₃OH)_0.55(H₂O)_0.45](H₂O)_0.45 (1), [CuCo^IIIZn₂(MeDea)₃Cl₃(CH₃OH)_0.74(H₂O)_0.26](H₂O)_0.26 (2), and [CuCo^IIIZn₂(MeDea)₃Cl₃(DMF)] (3) have been prepared using a one-pot reaction of copper powder with cobalt chloride (1) and zinc nitrate (2, 3) in a methanol (1, 2) or dimethylformamide (3) solution of N-methyldiethanolamine. A search of the Cambridge Structural Database shows that the tetranuclear asymmetric cores M₄(渭₃-X)(渭-X)₅ of 1鈥?b>3 represent an extremely rare case of M₄X₆ arrays. The magnetic investigations of 1 disclose antiferromagnetic coupling in a Co^II鈥揅u^II鈥揅o^II exchange fragment with J_Co鈥揅u/hc = 鈥?.76 cm^鈥?, J_Co鈥揅o/hc = 鈥?.76 cm^鈥?, and D_Co/hc = +34.3 cm^鈥?. Compounds 1鈥?b>3 act as precursors for the mild peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone with overall yields up to 23%. The synthetic and structural features as well as the thermogravimetric behavior and electrospray ionization mass spectrometry data are discussed.