Diastereospecific and Diastereoselective Syntheses of Ruthenium(II) Complexes Using N,N' Bidentate Ligands Aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N and Their Oxi
详细信息 查看全文
- 作者：Javier Gó ; mez ; Gabriel Garcí ; a-Herbosa ; José ; V. Cuevas ; Ana Arná ; iz ; Arancha Carbayo ; Asunció ; n Muñ ; oz ; Larry Falvello ; and Phillip E. Fanwick
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：March 20, 2006
- 年：2006
- 卷：45
- 期：6
- 页码：2483 - 2493
- 全文大小：366K
- 年卷期：v.45,no.6(March 20, 2006)
- ISSN：1520-510X
文摘
Coordination of N,N' bidentate ligands aryl-pyridin-2-ylmethyl-amine ArNH-CH2-2-C5H4N 1 (Ar = 4-CH3-C6H4, 1a;4-CH3O-C6H4, 1b; 2,6-(CH3)2-C6H3, 1c; 4-CF3-C6H4, 1d) to the moieties [Ru(bipy)2]2+, [Ru(
5-C5H5)L]+ (L = CH3CN,CO), or [Ru(6-arene)Cl]2+ (arene = benzene, p-cymene) occurs under diastereoselective or diastereospecificconditions. Detailed stereochemical analysis of the new complexes is included. The coordination of these secondaryamine ligands activates their oxidation to imines by molecular oxygen in a base-catalyzed reaction and hydrogenperoxide was detected as byproduct. The amine-to-imine oxidation was also observed under the experimentalconditions of cyclic voltammetry measurements. Deprotonation of the coordinated amine ligands afforded isolatableamido complexes only for the ligand (1-methyl-1-pyridin-2-yl-ethyl)-p-tolyl-amine, 1e, which doesn't contain hydrogenatoms in a 
position relative to the N-H bond. The structures of [Ru(2,2'-bipyridine)2(1b)](PF6)2, 2b; [Ru(2,2'-bipyridine)2(1c)](PF6)2, 2c; trans-[RuCl2(COD)(1a)], 3; and [RuCl2(6-C6H6)(1a)]PF6, 4a, have been confirmed byX-ray diffraction studies.
5-C5H5)L]+ (L = CH3CN,CO), or [Ru(6-arene)Cl]2+ (arene = benzene, p-cymene) occurs under diastereoselective or diastereospecificconditions. Detailed stereochemical analysis of the new complexes is included. The coordination of these secondaryamine ligands activates their oxidation to imines by molecular oxygen in a base-catalyzed reaction and hydrogenperoxide was detected as byproduct. The amine-to-imine oxidation was also observed under the experimentalconditions of cyclic voltammetry measurements. Deprotonation of the coordinated amine ligands afforded isolatableamido complexes only for the ligand (1-methyl-1-pyridin-2-yl-ethyl)-p-tolyl-amine, 1e, which doesn't contain hydrogenatoms in a position relative to the N-H bond. The structures of [Ru(2,2'-bipyridine)2(1b)](PF6)2, 2b; [Ru(2,2'-bipyridine)2(1c)](PF6)2, 2c; trans-[RuCl2(COD)(1a)], 3; and [RuCl2(6-C6H6)(1a)]PF6, 4a, have been confirmed byX-ray diffraction studies.