CH 键合效应对双（氨基膦）-钌配合物酯选择性加氢成醇反应性的影响。
CH Linkage Effects on the Reactivity of Bis(aminophosphine)-Ruthenium Complexes for Selective Hydrogenation of Esters into Alcohols.
机构信息
State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
出版信息
Sci Rep. 2017 Jun 21;7(1):3961. doi: 10.1038/s41598-017-04362-9.
A novel ruthenium complex binding to two subtly different aminophosphine ligands, (o-PPhCHCHNH)(o-PPhCHNH)RuCl, was successfully isolated. This bis(aminophosphine)-ruthenium complex shows efficient activity in both dimethyl oxalate (DMO) and methyl benzoate (MB) hydrogenation. On the contrast, similar complexes (o-PPhCHNH)RuCl and (o-PPhCHCHNH)RuCl, can only effectively catalyze the hydrogenation of DMO and MB, respectively. Our experimental studies in combination of theoretical calculations reveal that the remarkable substrate selectivity in the hydrogenation of esters arises from the nonbonding interactions operated by the CH linkage of the ligand.
成功分离出一种新型钌配合物，它与两个略有不同的氨基膦配体（o-PPhCHCHNH）（o-PPhCHNH）RuCl 结合。这种双（氨基膦）-钌配合物在草酸二甲酯（DMO）和苯甲酸甲酯（MB）氢化中均表现出高效活性。相比之下，类似的配合物（o-PPhCHNH）RuCl 和（o-PPhCHCHNH）RuCl 只能分别有效地催化 DMO 和 MB 的氢化。我们的实验研究结合理论计算表明，酯类氢化中的显著的底物选择性来自于配体的 CH 键的非键相互作用。
Zotero 插件