Department of Chemistry, Indian Institute of Technology Guwahati, Assam 781039, India.
Chem Commun (Camb). 2012 Jan 30;48(9):1251-3. doi: 10.1039/c1cc16316g. Epub 2011 Dec 12.
Copper(II) complex, 1, of the bidentate ligand, L [L = bis(2-ethyl-4-methyl-imidazol-5yl)methane] has been synthesized and structurally characterized. Addition of nitric oxide gas to a degassed acetonitrile solution of 1 yielded the corresponding copper(ii)-nitrosyl complex, 2. In acetonitrile, complex 2 on reaction with water afforded the corresponding copper(I)-nitrite complex, 3. Single crystal structure of complex 3 reveals the bidentate nitrite (η(2)-O,O) bonding. This is the first example of a structurally characterized Cu(I)-(η(2)-O,O)nitrite complex with N-donor ligand. The sequence of the formation of these complexes is just the reverse of the key steps of the postulated nitrite reduction cycle by CuNiRs.
铜(II)配合物 1,双齿配体 L [L = 双(2-乙基-4-甲基-咪唑-5-基)甲烷]已被合成并进行了结构表征。将一氧化氮气体加入 1 的脱气乙腈溶液中,得到相应的铜(II)-亚硝酰配合物 2。在乙腈中,配合物 2 与水反应生成相应的铜(I)-亚硝酸盐配合物 3。配合物 3 的单晶结构揭示了双齿亚硝酸盐(η(2)-O,O)键合。这是首例具有 N-供体配体的结构表征的 Cu(I)-(η(2)-O,O)亚硝酸盐配合物。这些配合物的形成顺序与假定的 CuNiRs 亚硝酸还原循环的关键步骤正好相反。