Sivagamasundari M, Ramesh R
School of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, India.
Spectrochim Acta A Mol Biomol Spectrosc. 2007 Feb;66(2):427-33. doi: 10.1016/j.saa.2006.03.017. Epub 2006 Jul 24.
The reaction of the chelating ligands (obtained by the condensation of 2-hydroxy-1-naphthaldehyde with various primary amines) with [RuHCl(CO)(EPh3)2(B)] (where E=P; B=PPh3, py or pip: E=As; B=AsPh3) in benzene afforded new stable ruthenium(II) carbonyl complexes of the general formula [Ru(Cl)(CO)(EPh3)(B)(L)] (L=anion of bidentate Schiff bases). The structure of the new complexes was investigated using elemental analyses, spectral (FT-IR, UV-vis and 1H NMR) and electrochemical studies and is found to be octahedral. All the metal complexes exhibit characteristic MLCT absorption and luminescence bands in the visible region. The luminescence efficiency of the ruthenium(II) complexes was explained based on the ligand environment around the metal ion. These complexes catalyze oxidation of primary and secondary alcohols into their corresponding carbonyl compounds in the presence of N-methylmorpholine-N-oxide (NMO) as the source of oxygen. The formation of high valent Ru(IV)=O species as a catalytic intermediate is proposed for the catalytic process.
螯合配体（由2-羟基-1-萘甲醛与各种伯胺缩合得到）与[RuHCl(CO)(EPh3)2(B)]（其中E = P；B = PPh3、py或pip；E = As；B = AsPh3）在苯中反应，得到通式为[Ru(Cl)(CO)(EPh3)(B)(L)]的新型稳定钌（II）羰基配合物（L = 双齿席夫碱阴离子）。使用元素分析、光谱（傅里叶变换红外光谱、紫外可见光谱和1H核磁共振）和电化学研究对新型配合物的结构进行了研究，发现其为八面体结构。所有金属配合物在可见光区域均表现出特征性的金属-配体电荷转移吸收和发光带。基于金属离子周围的配体环境解释了钌（II）配合物的发光效率。在作为氧源的N-甲基吗啉-N-氧化物（NMO）存在下，这些配合物催化伯醇和仲醇氧化为相应的羰基化合物。催化过程中提出高价Ru(IV)=O物种作为催化中间体的形成。
