Gilroy Joe B, Patrick Brian O, McDonald Robert, Hicks Robin G
Department of Chemistry, University of Victoria, Victoria, British Columbia, Canada.
Inorg Chem. 2008 Feb 18;47(4):1287-94. doi: 10.1021/ic7019846. Epub 2008 Jan 23.
The synthesis and characterization of six transition metal complexes of 3-cyano- and 3-nitroformazans are described. Three different formazans were reacted with nickel(II) to produce complexes with bidentate formazan ligands. Mononuclear NiL2 (L = deprotonated formazan) or binuclear hydroxo-bridged (LNi)2(mu-OH) 2 species were produced depending on the steric bulk on the formazan N-aromatic substituents. 1,5-Bis(2-methoxyphenyl)-3-cyanoformazan acts as a tetradentate monoanionic ligand in a copper(II) complex, whereas the analogous 1,5-bis(2-hydroxyphenyl)-3-cyanoformazan binds as a trianion in a tetradentate manner to Fe(III) and Co(III). Crystal structures-the first examples of metal complexes of cyano- or nitroformazans-as well as the electronic spectra of the complexes are discussed in relation to each other as well as that of the uncoordinated formazans.
本文描述了六种3-氰基和3-硝基甲臜的过渡金属配合物的合成与表征。三种不同的甲臜与镍（II）反应生成具有双齿甲臜配体的配合物。根据甲臜N-芳基取代基上的空间位阻，生成单核NiL2（L = 去质子化甲臜）或双核羟基桥联的（LNi）2（μ-OH）2物种。1,5-双（2-甲氧基苯基）-3-氰基甲臜在铜（II）配合物中作为四齿单阴离子配体，而类似的1,5-双（2-羟基苯基）-3-氰基甲臜以四齿方式作为三阴离子与铁（III）和钴（III）结合。讨论了氰基或硝基甲臜金属配合物的晶体结构（这是首例）以及配合物的电子光谱，同时也讨论了未配位甲臜的电子光谱，并将它们相互关联起来。
