| Dinuclear versus mononuclear zinc compounds from reduction of LZnCl2 (L = a-Diimine ligands): effects of the ligand substituent, reducing agent, and solvent | |
| Department | 羰基合成与选择氧化国家重点实验室 ; 精细石油化工中间体国家工程研究中心 |
Yu J(俞洁); Yang XJ(杨晓娟) ; Liu YY(刘艳艳); Pu ZF(蒲志峰); Li QS(李乾树); Xie YM(谢耀明); Henry F. Schaefer; Wu B(吴彪)
| |
| 2008 | |
| Source Publication | Organometallics
 |
| ISSN | 0276-7333 |
| Volume | 27Issue:22Pages:5800-5805 |
| Abstract | A Zn-Zn-bonded compound, [K(THF)2]2[(LiPr)Zn-Zn(LiPr)] (2) and three mononuclear zinc compounds, [Zn(LMe)2Na2(Et2O)2] (3), [Zn(LEt)2Na2(THF)2] (4), and [Zn(LEt)2K2]n (5), with N-aryl substituted R-diimine ligands LiPr, LMe, and LEt (L ) [(2,6-R2C6H3)N(Me)C]2, R ) iPr, Me, Et, respectively) have been synthesized from the reduction of the LZnCl2 precursors by the alkali metal Na or K. X-ray structural analyses show that the compounds have a [Zn2L2]2- (2) or [ZnL2]2- (3-5) core incorporating Na+ or K+ ions solvated by THF or Et2O molecules, except for 5, which displays a 2D polymeric structure formed by intermolecular K-C bonds due to the lack of K-solvent interactions. In compound 2, the formal Zn2+ ion in the precursor is reduced to Zn+, while in 3-5 it remains unreduced. The neutral ligands in the precursor, however, are doubly reduced to a dianion, L2-, in all compounds, as evidenced by the bond lengths of the N–CdC–N moiety of the ligands. Effects of the ligand substituent, reducing agent, and solvent on the products have been studied, which reveal that the steric bulk of the ligand is the most important factor that determines whether the Zn-Zn bond can be formed. DFT computations show that the Zn-Zn bond in 2 is formed mainly by the 4s orbitals of zinc. The results of natural charge and orbital analyses also confirm the reduction of the ligands to their dianionic forms. |
| Subject Area | 金属有机与超分子催化 |
| Funding Organization | the National Natural Science Foundation of China (NSFC Grant No. 20771103);the “Bairen Jihua” project of Chinese Academy of Sciences;the 111 Project (No. B07012) in China;the U.S. National Science Foundation (No. CHE-0749868) |
| Indexed By | SCI |
| Language | 英语 |
| Funding Project | 金属有机与超分子催化研究组 ; 金属有机功能材料研究组 |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/1949 |
| Collection | 羰基合成与选择氧化国家重点实验室（OSSO） 精细石油化工中间体国家工程研究中心（ERC） |
| Corresponding Author | Yang XJ(杨晓娟); Wu B(吴彪) |
| Recommended Citation GB/T 7714 | Yu J,Yang XJ,Liu YY,et al. Dinuclear versus mononuclear zinc compounds from reduction of LZnCl2 (L = a-Diimine ligands): effects of the ligand substituent, reducing agent, and solvent[J]. Organometallics,2008,27(22):5800-5805. |
| APA | 俞洁.,杨晓娟.,刘艳艳.,蒲志峰.,李乾树.,...&吴彪.(2008).Dinuclear versus mononuclear zinc compounds from reduction of LZnCl2 (L = a-Diimine ligands): effects of the ligand substituent, reducing agent, and solvent.Organometallics,27(22),5800-5805. |
| MLA | 俞洁,et al."Dinuclear versus mononuclear zinc compounds from reduction of LZnCl2 (L = a-Diimine ligands): effects of the ligand substituent, reducing agent, and solvent".Organometallics 27.22(2008):5800-5805. |
| Files in This Item: | ||||||
| File Name/Size | DocType | Version | Access | License | ||
| 14_Organometallics,2（908KB） | 开放获取 | License | View Application Full Text | |||
Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.
Edit Comment