一种（水杨醛缩邻苯二胺）钌（VI）氮化物配合物与异腈的反应。

Reaction of a (salen)ruthenium(VI) nitrido complex with isocyanide.

作者信息

Kwong Hoi-Ki, Man Wai-Lun, Xiang Jing, Wong Wing-Tak, Lau Tai-Chu

机构信息

Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong, China.

出版信息

Inorg Chem. 2009 Apr 6;48(7):3080-6. doi: 10.1021/ic802338f.

DOI:10.1021/ic802338f

PMID:19243154

Abstract

The treatment of [Ru(VI)(N)(L)(MeOH)]PF(6) (1) (L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion) with 2 equiv of RNC (R = (a) (t)Bu, (b) Cy) in CH(2)Cl(2) affords a mixture of blue cis-beta-[Ru(III)(NCNR)(L)(CNR)] (2) and green trans-[Ru(III)(L)(CNR)(2)]PF(6) (3) products. The reduction of 3 with a stoichiometric amount of Cp(2)Co in CH(3)CN gives red trans-[Ru(II)(L)(CNR)(2)] (4). Refluxing 4 with 3 equiv of RNC in methanol in the presence of 5 equiv of NH(4)PF(6) affords a yellow complex, mer-Ru(II)(eta(3)-HL)(CNR)(3) (5), in which the ligand is in an eta(3)-coordination mode. These complexes are characterized by IR, UV-vis, ESI-MS, CV, magnetic measurements, and CHN elemental analysis. The structures of 2a, 3a, 4a, 4b, and 5a have been determined by X-ray crystallography.

摘要

在二氯甲烷中，用2当量的RNC（R = (a)叔丁基，(b)环己基）处理[Ru(VI)(N)(L)(MeOH)]PF₆ (1)（L = N,N'-双（水杨醛）-邻环己二胺二价阴离子），得到蓝色顺式-β-[Ru(III)(NCNR)(L)(CNR)] (2)和绿色反式-[Ru(III)(L)(CNR)₂]PF₆ (3)产物的混合物。在乙腈中，用化学计量的二茂钴还原3得到红色反式-[Ru(II)(L)(CNR)₂] (4)。在5当量的六氟磷酸铵存在下，将4与3当量的RNC在甲醇中回流，得到黄色配合物，面式-Ru(II)(η³-HL)(CNR)₃ (5)，其中配体处于η³-配位模式。这些配合物通过红外光谱、紫外可见光谱、电喷雾电离质谱、循环伏安法、磁性测量和CHN元素分析进行表征。2a、3a、4a、4b和5a的结构已通过X射线晶体学确定。