Department of Chemistry, The University of Western Ontario, London, Ontario N6A 5B7, Canada.
Dalton Trans. 2012 Apr 21;41(15):4413-22. doi: 10.1039/c2dt11998f. Epub 2012 Feb 22.
The ligation of a N-heterocyclic carbene (NHC) to group 11 metal salts (Cu, Ag) was explored as an alternative to PR(3) ligands for the formation of copper- and silver-chalcogenolate cluster complexes. AgOAc and CuCl salts ligate with the NHC 1,3-di-isopropylbenzimidazole-2-ylidene ((i)Pr(2)-bimy) forming [Ag(OAc)((i)Pr(2)-bimy)] 1, [Ag(OAc)((i)Pr(2)-bimy)(2)] 2, CuCl((i)Pr(2)-bimy)3 and [CuCl((i)Pr(2)-bimy)(2)] 4 depending on the ratio of ligand to metal used. These have been characterized via spectroscopic and crystallographic methods. Complexes 1 and 3 were reacted with S(Ph)SiMe(3) and Se(Ph)SiMe(3) to form the polynuclear metal-chalcogenolates [Ag(4)(μ-EPh)(4)((i)Pr(2)-bimy)(4)] (5, E = S; 6, E = Se) and [Cu(3)(μ-EPh)(3)((i)Pr(2)-bimy)(3)] (7, E = S; 8, E = Se) in good yields. The structures of 5-8, as determined by single crystal X-ray crystallography, are described.
探索将 N-杂环卡宾 (NHC) 与第 11 族金属盐 (Cu、Ag) 键合，作为 PR(3)配体的替代物，用于形成铜和银硫属元素簇配合物。AgOAc 和 CuCl 盐与 NHC 1,3-二异丙基苯并咪唑-2-亚基（(i)Pr(2)-bimy）键合，形成 [Ag(OAc)((i)Pr(2)-bimy)] 1、[Ag(OAc)((i)Pr(2)-bimy)(2)] 2、CuCl((i)Pr(2)-bimy)3 和 [CuCl((i)Pr(2)-bimy)(2)] 4，具体取决于所用配体与金属的比例。这些通过光谱和晶体学方法进行了表征。复合物 1 和 3 与 S(Ph)SiMe(3)和 Se(Ph)SiMe(3)反应，形成多核金属硫属元素配合物 [Ag(4)(μ-EPh)(4)((i)Pr(2)-bimy)(4)] (5，E = S；6，E = Se) 和 [Cu(3)(μ-EPh)(3)((i)Pr(2)-bimy)(3)] (7，E = S；8，E = Se)，产率良好。通过单晶 X 射线晶体学确定了 5-8 的结构，并进行了描述。
