Theoretical investigation on the mechanisms of transfer hydrogenation of ketones catalyzed by iridium complexes

被引：33

作者：

Bi, Siwei ^{[1
,2
]}

Xie, Qingming ^{[1
]}

Zhao, Xiaoran ^{[1
]}

Zhao, Yanyun ^{[1
]}

Kong, Xiaojian ^{[2
]}

机构：

[1] Qufu Normal Univ, Coll Chem Sci, Qufu 273165, Shandong, Peoples R China

[2] Shandong Univ, Key Lab Educ, Minist Colloid & Interface Chem, Jinan 250100, Peoples R China

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2008年 / 693卷 / 04期

基金：

中国国家自然科学基金;

关键词：

transfer hydrogenation; ketone; iridium catalyst; catalytic cycle; DFT;

D O I：

10.1016/j.jorganchem.2007.11.043

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The detailed catalytic mechanisms on transfer hydrogenation of ketones are explored by employing the representative reaction of 3-pentanone and 2-propanol catalyzed by the model complex IrH3[(Me2PC2H4)(2)NH], derived from the catalyst IrH3[((Pr2PC2H4)-Pr-i)(2)NH], with the aid of the density functional theory calculations. The geometrical transformation from an octahedron to a Y-type involved in the catalytic cycle is also elucidated in terms of molecular theory of transition metal complexes. The trend for the variation of Ir-N bond distance is also analyzed. (C) 2007 Elsevier B. V. All rights reserved.

引用

页码：633 / 638

页数：6

共 51 条

[41] Asymmetric hydrogenation of alkenyl, cyclopropyl, and aryl ketones.: RuCl2(xylbinap)(1,2-diamine) as a precatalyst exhibiting a wide scope [J].

Ohkuma, T ;

Koizumi, M ;

Doucet, H ;

Pham, T ;

Kozawa, M ;

Murata, K ;

Katayama, E ;

Yokozawa, T ;

Ikariya, T ;

Noyori, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (51) :13529-13530

[42] PREFERENTIAL HYDROGENATION OF ALDEHYDES AND KETONES [J].

OHKUMA, T ;

OOKA, H ;

IKARIYA, T ;

NOYORI, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (41) :10417-10418

[43] Stereoselective hydrogenation of simple ketones catalyzed by Ruthenium(II) complexes [J].

Ohkuma, T ;

Ooka, H ;

Yamakawa, M ;

Ikariya, T ;

Noyori, R .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (15) :4872-4873

[44] Asymmetric activation of racemic ruthenium(II) complexes for enantioselective hydrogenation [J].

Ohkuma, T ;

Doucet, H ;

Pham, T ;

Mikami, K ;

Korenaga, T ;

Terada, M ;

Noyori, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (05) :1086-1087

[45] Iridium(III) complex containing a unique bifurcated hydrogen bond interaction involving Ir-H center dot center dot center dot H(N)center dot center dot center dot F-B atoms. Crystal and molecular structure of [IrH(eta(1)-SC5H4NH)(eta(2)-SC5H4N)(PPh(3))(2)](BF4)center dot 0.5C(6)H(6) [J].

Park, SH ;

Lough, AJ ;

Morris, RH .

INORGANIC CHEMISTRY, 1996, 35 (10) :3001-3006

[46]

RACHIDI IE, 1990, NEW J CHEM, V14, P671

[47] Hydrogenation versus transfer hydrogenation of ketones: Two established ruthenium systems catalyze both [J].

Rautenstrauch, V ;

Hoang-Cong, X ;

Churlaud, R ;

Abdur-Rashid, K ;

Morris, RH .

CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (20) :4954-4967

[48] Mechanism of asymmetric hydrogenation of ketones catalyzed by BINAP/1,2-diamine-ruthenium(II) complexes [J].

Sandoval, CA ;

Ohkuma, T ;

Muñiz, K ;

Noyori, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (44) :13490-13503

[49] Breaking an electronically preferred symmetry by steric effects in a series of [Ir(biph)X(QR3)2] compounds (X = Cl or I, Q = P or As) [J].

Ujaque, G ;

Maseras, F ;

Eisenstein, O ;

Liable-Sands, L ;

Rheingold, AL ;

Yao, WB ;

Crabtree, RH .

NEW JOURNAL OF CHEMISTRY, 1998, 22 (12) :1493-1498

[50]

Yamakawa M, 2001, ANGEW CHEM INT EDIT, V40, P2818, DOI 10.1002/1521-3773(20010803)40:15<2818::AID-ANIE2818>3.0.CO

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