National Changhua University of Education Institutional Repository : Item 987654321/18917
English  |  正體中文  |  简体中文  |  全文筆數/總筆數 : 6507/11669
造訪人次 : 29944281      線上人數 : 476
RC Version 3.2 © Powered By DSPACE, MIT. Enhanced by NTU Library IR team.
搜尋範圍 進階搜尋

請使用永久網址來引用或連結此文件: http://ir.ncue.edu.tw/ir/handle/987654321/18917

題名: Chemistry of the PCNHCP Ligand: Silver and Ruthenium Complexes, Facial/Meridional Coordination, and Catalytic Transfer Hydrogenation
作者: Chiu, Pei-Ling;Lee, Hon Man
貢獻者: 化學系
日期: 2005-03
上傳時間: 2014-08-14T04:29:02Z
出版者: American Chemical Society
摘要: The silver complex of PCNHCP was identified as [Ag3(μ-Cl)(PCNHCP)2]Cl2 (1). Anion exchange of 1 with AgNO3 affords a white compound, which crystallizes into two forms, [Ag3(μ-Cl)(PCNHCP)]2(NO3)2 (2a) and [Ag3(Cl)(NO3)(0.5DMF)(PCNHCP)2]NO3 (2b), from different solvent combinations. Their structural determination reveals interesting structural features, including a short Ag···Ag interaction in both of them. Unlike the common preparation of ruthenium(II) NHC complexes in the literature, a novel silver carbene transfer reaction between 1 and RuCl2(PPh)3 produces fac-[Ru2(μ-Cl)3(PCNHCP)2]Cl (3) in good yield. The nonredox nature of the carbene transfer reaction is different from that of an earlier report and shows that the preparation of divalent ruthenium NHC complexes via silver carbene transfer is a feasible synthetic route. Significantly, complex 3 can also be prepared directly from PCNHCP·HCl and RuCl2(PPh3)3 in the absence of base. Reactions of 3 with CO, phenylacetylene, and pyridine afford mer complexes mer,cis-RuCl2(CO)(PCNHCP) (4), mer,trans-RuCl2(CCHPh)(PCNHCP) (6), and mer,trans-[RuCl(py)2(PCNHCP)]Cl (7), respectively. The fac complex, fac,cis-[RuCl(bipy)(PCNHCP)]Cl (8), was produced in reaction of either 3 or 7 with 2,2‘-bipyridine. Treatment of 4 with excess NaBH4 produced the hydride complex mer-RuHCl(CO)(PCNHCP) (5). Complex 7 is slowly oxidized to mer-[RuIIICl3(PCNHCP)] (9) in the air. The structures of 2a, 2b, 3, 4, 7, 8, and 9 have been confirmed by X-ray crystallography. The reactivity study shows that PCNHCP is capable of accommodating extra steric requirement by readily switching from facial to meridional coordination mode, and the preliminary catalytic study indicates that 3 is effective in transfer hydrogenation of ketones.
關聯: Organometallics, 24(7): 1692-1702
顯示於類別:[化學系] 期刊論文

文件中的檔案:

檔案 大小格式瀏覽次數
index.html0KbHTML479檢視/開啟


在NCUEIR中所有的資料項目都受到原著作權保護.

 

DSpace Software Copyright © 2002-2004  MIT &  Hewlett-Packard  /   Enhanced by   NTU Library IR team Copyright ©   - 回饋