Lozano A Abel, Sáez Magalí, Pérez José, García Luís, Lezama Luís, Rojo Teófilo, López Gregorio, García Gabriel, Santana Ma Dolores
Departamento de Química Inorgánica, Universidad de Murcia, 30071 Murcia, Spain.
Dalton Trans. 2006 Aug 28(32):3906-11. doi: 10.1039/b604541c. Epub 2006 Jun 13.
CO2 and HCO3- react with the dinuclear hydroxo-complex [Ni(mcN3)(mu-OH)]2(PF6)2 (mcN3 = 2,4,4,9-tetramethyl-1,5,9-triazacyclododec-1-ene) to form micro-CO3 bridged nickel(II) complexes, {Ni(mcN3)}2(mu-CO3)2 (1a) with a symmetric core in which both nickel atoms are five-coordinate and Ni(mcN3)(mu-CO3)Ni(mcN3)(MeCN)2 (1b) with an asymmetric dinuclear core containing five- and six-coordinate nickel atoms. The magnetic behaviour indicates the existence of antiferromagnetic coupling between the metallic centres. A substantial increase in the value of J occurs when the symmetric five-coordinate nickel species transforms to an asymmetric five- and six-coordinate species by axial coordination of acetonitrile.
二氧化碳和碳酸氢根与双核羟基配合物[Ni(mcN3)(μ-OH)]2(PF6)2（mcN3 = 2,4,4,9-四甲基-1,5,9-三氮杂环十二碳-1-烯）反应，形成微碳酸根桥联的镍(II)配合物，{Ni(mcN3)}2(μ-CO3)2（1a），其具有对称核心，其中两个镍原子均为五配位；以及Ni(mcN3)(μ-CO3)Ni(mcN3)(MeCN)2（1b），其具有包含五配位和六配位镍原子的不对称双核核心。磁行为表明金属中心之间存在反铁磁耦合。当对称的五配位镍物种通过乙腈的轴向配位转变为不对称的五配位和六配位物种时，J值会大幅增加。
