Gómez Javier, García-Herbosa Gabriel, Cuevas José V, Arnaiz Ana, Carbayo Arancha, Muñoz Asunción, Falvello Larry, Fanwick Phillip E
Departamento de Química, Facultad de Ciencias, Universidad de Burgos, 09001 Burgos, Spain.
Inorg Chem. 2006 Mar 20;45(6):2483-93. doi: 10.1021/ic051590a.
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(eta5-C5H5)L]+ (L = CH3CN, CO), or [Ru(eta6-arene)Cl]2+ (arene = benzene, p-cymene) occurs under diastereoselective or diastereospecific conditions. Detailed stereochemical analysis of the new complexes is included. The coordination of these secondary amine ligands activates their oxidation to imines by molecular oxygen in a base-catalyzed reaction and hydrogen peroxide was detected as byproduct. The amine-to-imine oxidation was also observed under the experimental conditions of cyclic voltammetry measurements. Deprotonation of the coordinated amine ligands afforded isolatable amido complexes only for the ligand (1-methyl-1-pyridin-2-yl-ethyl)-p-tolyl-amine, 1e, which doesn't contain hydrogen atoms in a beta position relative to the N-H bond. The structures of Ru(2,2'-bipyridine)2(1b)2, 2b; Ru(2,2'-bipyridine)(2)(1c)2, 2c; trans-[RuCl2(COD)(1a)], 3; and [RuCl2(eta6-C6H6)(1a)]PF6, 4a, have been confirmed by X-ray diffraction studies.
N,N' 双齿配体芳基 - 吡啶 -2- 基甲基 - 胺 ArNH-CH₂-2-C₅H₄N 1（Ar = 4-CH₃-C₆H₄，1a；4-CH₃O-C₆H₄，1b；2,6-(CH₃)₂-C₆H₃，1c；4-CF₃-C₆H₄，1d）与部分 [Ru(bipy)₂]²⁺、[Ru(η⁵-C₅H₅)L]⁺（L = CH₃CN，CO）或 [Ru(η⁶-芳烃)Cl]²⁺（芳烃 = 苯，对异丙基苯）的配位反应在非对映选择性或非对映特异性条件下发生。文中包含了对新配合物的详细立体化学分析。这些仲胺配体的配位作用通过碱催化反应促使它们被分子氧氧化为亚胺，并且检测到过氧化氢作为副产物。在循环伏安法测量的实验条件下也观察到了胺到亚胺的氧化反应。仅对于配体（1-甲基 -1- 吡啶 -2- 基 - 乙基）- 对甲苯胺 1e，配位胺配体的去质子化反应得到了可分离的酰胺配合物，该配体在相对于 N-H 键的 β 位不含有氢原子。Ru(2,2'- 联吡啶)₂(1b)₂，2b；Ru(2,2'- 联吡啶)₂(1c)₂，2c；反式 -[RuCl₂(COD)(1a)]，3；以及 [RuCl₂(η⁶-C₆H₆)(1a)]PF₆，4a 的结构已通过 X 射线衍射研究得到证实。
