Mechanism investigation of ketone hydrogenation catalyzed by ruthenium bifunctional catalysts: insights from a DFT study

被引：26
作者：
Zhang, Xin [1 ]
Guo, Xiaojia [1 ]
Chen, Yue [1 ,2 ]
Tang, Yanhui [3 ]
Lei, Ming [1 ]
Fang, Weihai [2 ]
机构：
[1] Beijing Univ Chem Technol, State Key Lab Chem Resource Engn, Inst Mat Med, Coll Sci, Beijing 100029, Peoples R China
[2] Beijing Normal Univ, Dept Chem, Coll Chem, Beijing 100875, Peoples R China
[3] Beijing Inst Fash Technol, Sch Mat Sci & Engn, Beijing 100029, Peoples R China
来源：
PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2012年 / 14卷 / 17期
基金：
中国国家自然科学基金;
关键词：
ASYMMETRIC TRANSFER HYDROGENATION; DYNAMIC KINETIC RESOLUTION; HYDRIDOIRIDIUM(III) COMPLEXES; STEREOSELECTIVE HYDROGENATION; RACEMIZATION CATALYSTS; ALCOHOLS; HYDRIDE; ACTIVATION; LIGANDS; BEARING;
D O I：
10.1039/c2cp23936a
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
In this paper, the mechanism of ketone hydrogenation catalyzed by five Ru bifunctional catalysts with different structural frameworks was studied in detail using density functional theory (DFT). This mechanism contains hydrogen transfer, dehydrogenation of alcohol, and dihydrogen activation fundamental reactions. The involvement of alcohol is also discussed and found with different activities in hydrogen transfer, dehydrogenation and dihydrogen activation steps in five systems. Our calculated results indicate that the weak Ru-H bond, stronger basicity of hydride and stronger X-H acidity will decrease the barrier of the HT step, and that the polar micro-environment of dihydrogen coordinating with Ru catalysts and short hydrogen transfer distance would be able to facilitate the heterolytic splitting of dihydrogen in the dihydrogen
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收藏
页码：6003 / 6012
页数：10
相关论文
共 65 条
[1]   A succession of isomers of ruthenium dihydride complexes. Which one is the ketone hydrogenation catalyst? [J].
Abbel, R ;
Abdur-Rashid, K ;
Faatz, M ;
Hadzovic, A ;
Lough, AJ ;
Morris, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (06) :1870-1882
[2]   Mechanism of the hydrogenation of ketones catalyzed by trans-dihydrido(diamine)ruthenium(II) complexes [J].
Abdur-Rashid, K ;
Clapham, SE ;
Hadzovic, A ;
Harvey, JN ;
Lough, AJ ;
Morris, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (50) :15104-15118
[3]   Racemization catalysts for the dynamic kinetic resolution of alcohols and amines [J].
Ahn, Yangsoo ;
Ko, Soo-Byung ;
Kim, Mahn-Joo ;
Park, Jaiwook .
COORDINATION CHEMISTRY REVIEWS, 2008, 252 (5-7) :647-658
[4]   Ru(arene)(amino alcohol)-catalyzed transfer hydrogenation of ketones: Mechanism and origin of enantioselectivity [J].
Alonso, DA ;
Brandt, P ;
Nordin, SJM ;
Andersson, PG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (41) :9580-9588
[5]  
[Anonymous], 2008, ANGEW CHEM, V120, P954, DOI DOI 10.1002/ANGE.200705115
[6]   (CYCLOPENTADIENONE)RUTHENIUM CARBONYL-COMPLEXES - A NEW CLASS OF HOMOGENEOUS HYDROGENATION CATALYSTS [J].
BLUM, Y ;
CZARKIE, D ;
RAHAMIM, Y ;
SHVO, Y .
ORGANOMETALLICS, 1985, 4 (08) :1459-1461
[7]   An iron catalyst for ketone hydrogenations under mild conditions [J].
Bullock, R. Morris .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (39) :7360-7363
[8]   Cyclopentadienone Iron Alcohol Complexes: Synthesis, Reactivity, and Implications for the Mechanism of Iron-Catalyzed Hydrogenation of Aldehydes [J].
Casey, Charles P. ;
Guan, Hairong .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (07) :2499-2507
[9]   Hydrogen elimination from a hydroxycyclopentadienyl ruthenium(II) hydride: Study of hydrogen activation in a ligand-metal bifunctional hydrogenation catalyst [J].
Casey, CP ;
Johnson, JB ;
Singer, SW ;
Cui, Q .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (09) :3100-3109
[10]   Hydrogen transfer to carbonyls and imines from a hydroxycyclopentadienyl ruthenium hydride: Evidence for concerted hydride and proton transfer [J].
Casey, CP ;
Singer, SW ;
Powell, DR ;
Hayashi, RK ;
Kavana, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (06) :1090-1100
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