Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisbon, Portugal.
Inorg Chem. 2011 May 16;50(10):4401-11. doi: 10.1021/ic102543m. Epub 2011 Apr 20.
The three novel heterometallic complexes CuCo(III)Co(II)(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.55)(H(2)O)(0.45)(0.45) (1), CuCo(III)Zn(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.74)(H(2)O)(0.26)(0.26) (2), and [CuCo(III)Zn(2)(MeDea)(3)Cl(3)(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 M(4)(μ(3)-X)(μ-X)(5) of 1-3 represent an extremely rare case of M(4)X(6) arrays. The magnetic investigations of 1 disclose antiferromagnetic coupling in a Co(II)-Cu(II)-Co(II) exchange fragment with J(Co-Cu)/hc = -4.76 cm(-1), J(Co-Co)/hc = -2.76 cm(-1), and D(Co)/hc = +34.3 cm(-1). Compounds 1-3 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.
三种新型杂金属配合物 CuCo(III)Co(II)(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.55)(H(2)O)(0.45)(0.45) (1)、CuCo(III)Zn(2)(MeDea)(3)Cl(3)(CH(3)OH)(0.74)(H(2)O)(0.26)(0.26) (2) 和 [CuCo(III)Zn(2)(MeDea)(3)Cl(3)(DMF)] (3) 是通过铜粉与氯化钴 (1) 和硝酸锌 (2,3) 在甲醇 (1,2) 或二甲基甲酰胺 (3) 溶液中的一锅反应制备的。对剑桥结构数据库的搜索表明，配合物 1-3 的四核不对称核心 M(4)(μ(3)-X)(μ-X)(5)代表了 M(4)X(6) 阵列的极其罕见的情况。对 1 的磁性研究表明，在 Co(II)-Cu(II)-Co(II) 交换片段中存在反铁磁耦合，J(Co-Cu)/hc = -4.76 cm(-1)、J(Co-Co)/hc = -2.76 cm(-1) 和 D(Co)/hc = +34.3 cm(-1)。化合物 1-3 可用作温和过氧化物氧化环己烷为环己醇和环己酮的前体，总收率高达 23%。讨论了合成和结构特征以及热重行为和电喷雾电离质谱数据。
