Cycloruthenation of N-(Naphthyl)salicylaldimine and Related Ligands: Utilization of the Ru-C Bond in Catalytic Transfer Hydrogenation
Cycloruthenation of N-(Naphthyl)salicylaldimine and Related Ligands: Utilization of the Ru-C Bond in Catalytic Transfer Hydrogenation
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DOI：
10.1002/ejic.201402236
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发表时间：
2014-09-01
影响因子：
2.3
通讯作者：
Bhattacharya, Samaresh
中科院分区：
文献类型：
--
作者：
Dutta, Jayita;Richmond, Michael G.;Bhattacharya, Samaresh
N-（萘基）-4-R-水杨醛亚胺（R = OCH_3，H，Cl; H_2L_1-H_2L_3）和2-羟基- N-（萘基）萘二甲亚胺（H_2L_4）与[Ru（PPh_3）（2）（CO）（2）Cl ~-~ 2]反应后，容易通过α位的C-H键活化而发生环钌化反应，得到[Ru（PPh_3）（2）（L）（CO）]（L = L ~（1-L ~ 4）型配合物。测定了配合物[Ru（PPh 3）（2）（L）（CO）]（L = L-1，L-2，L-4）的晶体结构，并通过密度泛函理论（DFT）计算优化了配合物[Ru（PPh 3）（2）（L-3）（CO）]的结构.测定了[Ru（PPh 3）（2）（CO）（2）Cl-2]与H2 L2反应生成[Ru（PPh 3）（2）（L-2）（CO）]的热力学。所有配合物在可见光和紫外区均表现出强烈的吸收，并通过TDDFT计算进行了分析。四种环钌络合物的循环伏安法显示在0.50-1.35 V范围内相对于SCE的两次氧化和在约-1.75 V相对于SCE的还原。[Ru（PPh_3）（2）（L）（CO）]（L = L ~（-1）-L ~（-4））配合物能有效地催化羰基化合物的转移氢化反应。
Upon reaction with [Ru(PPh3)(2)(CO)(2)Cl-2], N-(naphthyl)-4-R-salicylaldimines (R = OCH3, H, Cl; H2L1-H2L3) and 2-hydroxy- N-(naphthyl) naphthaldimine (H2L4) readily undergo cycloruthenation by C-H bond activation at the peri position to afford complexes of the type [Ru(PPh3)(2)(L)(CO)] (L = L-1-L-4). The crystal structures of the [Ru(PPh3)(2)(L)(CO)] (L = L-1, L-2, L-4) complexes were determined and the structure of [Ru(PPh3)(2)(L-3)(CO)] optimized by DFT calculations. The thermodynamics for the reaction of [Ru(PPh3)(2)(CO)(2)Cl-2] with H2L2 to give [Ru(PPh3)(2)(L-2)(CO)] were determined. All the complexes show intense absorptions in the visible and UV regions, which have been analyzed by TDDFT calculations. Cyclic voltammetry of the four cycloruthenated complexes showed two oxidations within the range 0.50-1.35 V versus SCE and a reduction at around -1.75 V versus SCE. The [Ru(PPh3)(2)(L)(CO)] (L = L-1-L-4) complexes were found to efficiently catalyze the transfer hydrogenation of carbonyl compounds.