Di-, Tri-, and Tetranuclear Copper(I) Complexes of Phenanthroline-Linked Dicarbene Ligands
详细信息 查看全文
- 作者：Bo Liu ; Shanfei Pan ; Bin Liu ; Wanzhi Chen
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：October 6, 2014
- 年：2014
- 卷：53
- 期：19
- 页码：10485-10497
- 全文大小：909K
- ISSN：1520-510X
文摘
A family of 2,9-di(3-R-1H-imidazolium-1-yl)-1,10-phenanthroline iodides and hexafluorophosphates (R = allyl, benzyl, mesityl, picolyl) were synthesized from 2,9-diiodophenanthroline and imidazole or N-substituted imidazoles. Simple reactions of these diimidazolium salts with copper powder at room temperature have afforded a series of multinuclear copper(I)鈥揘HC complexes in good yields. The structures vary depending on the N substituents and counterions. [Cu4(L1)2(MeCN)4](PF6)4 (R = allyl) exhibits a zigzag Cu4 chain with two terminal [Cu(NHC)(MeCN)2] and two internal [Cu(phen)(NHC)] moieties. [Cu3(L2)2](PF6)3 (R = benzyl) contains a strictly linear Cu3 framework with two [Cu(NHC)2] units and a [Cu(phen)2] located at the center. Both complexes [Cu3(L4)2](PF6)3 (R = mesityl) and [Cu3(L5)2](PF6)3 (R = picolyl) consist of a triangular Cu3 core in which two copper(I) ions are surrounded by a phen and a NHC group and the third copper(I) is coordinated by two NHC groups. [Cu3(L3)2](PF6)3 derived from 2,9-di(3-benzyl-1H-benzimidazolium-1-yl)-1,10-phenanthroline hexafluorophosphate can undergo transannulation of the benzimidazolylidene ring giving [Cu2(L3鈥?2](PF6)2. The decomposition process might involve solvent-induced rearrangement of the ligand and hydrolysis of carbene moieties. Treatment of 2,9-di(3-mesityl-1H-benzimidazolium-1-yl)-1,10-phenanthroline iodide with copper powder generated dinuclear complex [Cu2(L4)2][Cu2(渭-I)2I2] (R = mesityl) possessing a macrocyclic cation and [Cu2(渭-I)2I2]2鈥?/sup> anion. Tetranuclear complex [Cu4(L5)2(渭-I)2](CuI3) (R = picolyl) has been obtained from its diimidazolium iodide and copper powder. All Cu(I) complexes have been characterized by X-ray single diffraction analysis, elemental analysis, and NMR spectra. Their redox behavior and fluorescent properties have also been studied.