Synthesis and catalytic performance of ruthenium complexes ligated with rigid o-(diphenylphosphino)aniline for chemoselective hydrogenation of dimethyl oxalate

被引：19

作者：

Fang, Xiaolong ^{[1
]}

Zhang, Chunyan ^{[1
]}

Chen, Jin ^{[1
]}

Zhu, Hongping ^{[1
]}

Yuan, Youzhu ^{[1
]}

机构：

[1] Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Natl Engn Lab Green Chem Prod Alcohols Ethers Est, iChEM,Coll Chem & Chem Engn, Xiamen 361005, Fujian, Peoples R China

来源：

RSC ADVANCES | 2016年 / 6卷 / 51期

基金：

国家教育部科学基金资助;

关键词：

CARBOXYLIC-ACID ESTERS; ETHYLENE-GLYCOL; EFFICIENT HYDROGENATION; ASYMMETRIC HYDROGENATION; BIFUNCTIONAL ADDITION; MOLECULAR-HYDROGEN; HYDRIDE COMPLEXES; CHIRAL CATALYSTS; BOND ACTIVATION; ALCOHOLS;

D O I：

10.1039/c6ra00320f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A series of new ruthenium complexes with rigid ligand o-(diphenylphosphino) aniline, including [(PPh3)(o-PPh2C6H4NH2)RuCl2](2) (1), (o-PPh2C6H4NH2)(2)RuCl2 (2), [(o-PPh2C6H4NH2)(2)(o-PPh2C6H4NH)Ru]Cl-+(-) (3), Ph3P(eta(2)-H-2)Ru(mu-H)(mu-o-PPh2C6H4NH)(2)RuH(PPh3) (4), (o-PPh2C6H4NH2)(o-PPh2C6H4NH)RuCl(CO) (5), (o-PPh2C6H4NH2)(o-PPh2C6H4NH)RuH(CO) (6), and [(o-PPh2C6H4NH)(2)Ru(CO)](2) (7) were synthesized and employed as catalysts for chemoselective hydrogenation of esters. Among them, complexes 1, 2, and 5 exhibited excellent performance in hydrogenation of dimethyl oxalate to methyl glycolate, in comparison with the ruthenium complexes with a flexible aminophosphine ligand, such as (Ph2P(CH2)(2)NH2)(2)RuCl2, (Ph2P(CH2)(3)NH2)(2)RuCl2, and (o-Ph2PC6H4CH2NH2)(2)RuCl2, under identical conditions. Complexes 1 and 2 also displayed good activities in the hydrogenation of other aliphatic and cyclic esters. The catalytic mechanism of hydrogenation was discussed according to the results of NMR spectroscopic studies and control experiments.

引用

页码：45512 / 45518

页数：7

共 65 条

[21] ANIONIC METAL HYDRIDE CATALYSTS .2. APPLICATION TO THE HYDROGENATION OF KETONES, ALDEHYDES, CARBOXYLIC-ACID ESTERS, AND NITRILES [J].