Jia Wei-Guo, Huang Yuan-Biao, Lin Yue-Jian, Jin Guo-Xin
Shanghai Key Laboratory of Molecular Catalysis and Innovative Material, Department of Chemistry, Fudan University, 200433, Shanghai, PR China.
Dalton Trans. 2008 Nov 7(41):5612-20. doi: 10.1039/b801862f. Epub 2008 Aug 27.
The organochalcogen ligands derived from 3-methyl-imidazole-2-thione/selone groups, Mbit, Mbis, Ebit and Ebis [Mbit = 1,1'-methylenebis(3-methyl-imidazole-2-thione); Mbis = 1,1'-methylenebis(3-methyl-imidazole-2-selone), Ebit = 1,1'-(1,2-ethanediyl)bis(3-methyl-imidazole-2-thione), Ebis = 1,1'-(1,2-ethanediyl)bis(3-methyl-imidazole-2-selone)] have been synthesized and characterized. Reactions of [CpIr(micro-Cl)Cl]2 and [CpRh(micro-Cl)Cl]2 (Cp* = eta5-pentamethylcyclopentadienyl) with Mbit, Mbis, Ebit and Ebis result in the formation of the complexes [CpIr(Mbit)Cl]Cl 1a x Cl), [CpIr(Mbis)Cl]Cl (3a x Cl), [CpIr(Ebit)Cl]Cl (1b x Cl), [CpIr(Ebis)Cl]Cl (2a x Cl), [CpRh(Mbit)Cl]Cl (2b x Cl), CpRh(Mbis)Cl][CpRhCl(3)] (3b x[CpRhCl(3)]), [CpRh(Ebit)Cl]Cl (4a x Cl) and [CpRh(Ebis)Cl]Cl (4b x Cl), respectively. All compounds have been characterized by elemental analysis, NMR and IR spectra. The molecular structures of 1b, 2b, 3a, 3b and 4a have been determined by X-ray crystallography. After activation with methylaluminoxane (MAO), the iridium complexes exhibit moderate activities for the vinyl polymerization of norbornene.
源自3-甲基咪唑-2-硫酮/硒酮基团的有机硫属元素配体，即Mbit、Mbis、Ebit和Ebis [Mbit = 1,1'-亚甲基双(3-甲基咪唑-2-硫酮)；Mbis = 1,1'-亚甲基双(3-甲基咪唑-2-硒酮)，Ebit = 1,1'-(1,2-乙二基)双(3-甲基咪唑-2-硫酮)，Ebis = 1,1'-(1,2-乙二基)双(3-甲基咪唑-2-硒酮)] 已被合成并表征。[CpIr(μ-Cl)Cl]₂和[CpRh(μ-Cl)Cl]₂（Cp* = η⁵-五甲基环戊二烯基）与Mbit、Mbis、Ebit和Ebis反应生成配合物[CpIr(Mbit)Cl]Cl (1a·xCl)、[CpIr(Mbis)Cl]Cl (3a·xCl)、[CpIr(Ebit)Cl]Cl (1b·xCl)、[CpIr(Ebis)Cl]Cl (2a·xCl)、[CpRh(Mbit)Cl]Cl (2b·xCl)、[CpRh(Mbis)Cl][CpRhCl₃] (3b·x[CpRhCl₃])、[CpRh(Ebit)Cl]Cl (4a·xCl) 和 [CpRh(Ebis)Cl]Cl (4b·xCl)。所有化合物均通过元素分析、核磁共振和红外光谱进行了表征。1b、2b、3a、'3b和4a的分子结构已通过X射线晶体学确定。用甲基铝氧烷(MAO)活化后，铱配合物对降冰片烯的乙烯基聚合表现出中等活性。
