Department of Chemistry, The University of Western Ontario, London, Ontario, N6A 5B7 Canada.
Dalton Trans. 2014 Feb 7;43(5):2104-11. doi: 10.1039/c3dt52558a.
The ligation of N-heterocyclic carbenes (NHCs) to [CuS(t)Bu] and [AgS(t)Bu] was developed as an alternative to PR3 ligands as solubilizing reagents for these coordination polymers in order to form polynuclear copper and silver t-butylthiolate clusters. 1,3-Di-isopropylbenzimidazol-2-ylidene ((i)Pr2-bimy) and 1,3-di-isopropyl-4,5-dimethylimidazol-2-ylidene ((i)Pr2-mimy) were ligated to [CuS(t)Bu] and [AgS(t)Bu] forming [Cu4(S(t)Bu)4((i)Pr2-bimy)2] 1, [Cu4(S(t)Bu)4((i)Pr2-mimy)2] 2, [Ag4(S(t)Bu)4((i)Pr2-bimy)2] 5 and [Ag5(S(t)Bu)6][Ag((i)Pr2-mimy)2] 6. For comparison, the trialkyl phosphines P(n)Pr3 and P(i)Pr3 were also used to solubilize [AgS(t)Bu] and [CuS(t)Bu] to form copper and silver t-butylthiolate clusters. [Cu4(S(t)Bu)4(P(n)Pr3)2] 3, [Cu4(S(t)Bu)4(P(i)Pr3)2] 4, [Ag4(S(t)Bu)4(P(n)Pr3)2] 7 and [Ag6(S(t)Bu)6(P(i)Pr3)2] 8 were thus formed upon reaction with [CuS(t)Bu] and [AgS(t)Bu]. The synthesized complexes have been characterized via spectroscopic and crystallographic methods. The molecular structures of the clusters, which can vary according to the ligand type, are described.
将 N-杂环卡宾 (NHCs) 与 [CuS(t)Bu] 和 [AgS(t)Bu] 键合作为 PR3 配体的替代物，以将这些配位聚合物溶解在其中，从而形成多核铜和银的叔丁硫醇盐簇。1,3-二异丙基苯并咪唑-2-亚基((i)Pr2-bimy)和 1,3-二异丙基-4,5-二甲基咪唑-2-亚基((i)Pr2-mimy)与 [CuS(t)Bu] 和 [AgS(t)Bu] 键合，形成 [Cu4(S(t)Bu)4((i)Pr2-bimy)2] 1、[Cu4(S(t)Bu)4((i)Pr2-mimy)2] 2、[Ag4(S(t)Bu)4((i)Pr2-bimy)2] 5 和 [Ag5(S(t)Bu)6][Ag((i)Pr2-mimy)2] 6。为了进行比较，还使用三烷基膦 P(n)Pr3 和 P(i)Pr3 来溶解 [AgS(t)Bu] 和 [CuS(t)Bu]，以形成铜和银的叔丁硫醇盐簇。因此，与 [CuS(t)Bu] 和 [AgS(t)Bu] 反应后形成了 [Cu4(S(t)Bu)4(P(n)Pr3)2] 3、[Cu4(S(t)Bu)4(P(i)Pr3)2] 4、[Ag4(S(t)Bu)4(P(n)Pr3)2] 7 和 [Ag6(S(t)Bu)6(P(i)Pr3)2] 8。通过光谱和晶体学方法对合成的配合物进行了表征。描述了根据配体类型而变化的簇的分子结构。
