DFT studies on the reaction of CO2 with allyl-bridged dinuclear palladium(I) complexes

被引：23

作者：

Wang, Meiyan ^{[1
]}

Fan, Ting ^{[1
]}

Lin, Zhenyang ^{[1
]}

机构：

[1] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China

来源：

POLYHEDRON | 2012年 / 32卷 / 01期

关键词：

Reaction mechanism; CO2; activation; Metal-metal bonds; Allyl bridging ligands; GENERALIZED GRADIENT APPROXIMATION; CARBON-DIOXIDE; CATALYZED CARBOXYLATION; HOMOGENEOUS HYDROGENATION; CHEMISTRY; ENERGIES; INSERTION; REDUCTION; MOLECULES; MECHANISM;

D O I：

10.1016/j.poly.2011.05.016

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Density functional theory (DFT) calculations have been carried out to study the reactions of dinuclear palladium(I) complexes containing two allyl bridging ligands with CO2. The mechanism of the transformations of the first and second bridging allyl ligand to the bridging carboxylate ligands has been studied. It is found that the transformation of the first bridging allyl ligand is kinetically and thermodynamically favorable, while the transformation of the second ligand is thermodynamically and kinetically unfavorable. The energy decomposition and frontier molecular orbital analyses suggest that in the dinuclear palladium(I) complexes containing two allyl bridging ligands the strong trans influencing properties of the allyl ligands weaken the metal-allyl bonding interactions, facilitating the first CO2 insertion. The dinuclear palladium(l) complexes obtained from the first CO2 insertion contain only one bridging allyl ligand and show remarkably strong metal-allyl bonding interactions, impeding the second CO2 insertion. (c) 2011 Elsevier Ltd. All rights reserved.

引用

页码：35 / 40

页数：6

共 56 条

[21] HOMOGENEOUS HYDROGENATION OF CARBON-DIOXIDE [J].

JESSOP, PG ;

IKARIYA, T ;

NOYORI, R .

CHEMICAL REVIEWS, 1995, 95 (02) :259-272

[22] Insertion of carbon dioxide into (PCP)PdII-Me bonds [J].

Johansson, R ;

Jarenmark, M ;

Wendt, OF .

ORGANOMETALLICS, 2005, 24 (19) :4500-4502

[23]

Johansson R, 2007, DALTON T, P488, DOI 10.1039/b614037h

[24] Mechanisms of the CO2 Insertion into (PCP) Palladium Allyl and Methyl σ-Bonds. A Kinetic and Computational Study [J].

Johnson, Magnus T. ;

Johansson, Roger ;

Kondrashov, Mikhail V. ;

Steyl, Gideon ;

Ahlquist, Marten S. G. ;

Roodt, Andreas ;

Wendt, Ola F. .

ORGANOMETALLICS, 2010, 29 (16) :3521-3529

[25] ENERGY-ADJUSTED PSEUDOPOTENTIALS FOR THE ACTINIDES - PARAMETER SETS AND TEST CALCULATIONS FOR THORIUM AND THORIUM MONOXIDE [J].

KUCHLE, W ;

DOLG, M ;

STOLL, H ;

PREUSS, H .

JOURNAL OF CHEMICAL PHYSICS, 1994, 100 (10) :7535-7542

[26] DEVELOPMENT OF THE COLLE-SALVETTI CORRELATION-ENERGY FORMULA INTO A FUNCTIONAL OF THE ELECTRON-DENSITY [J].

LEE, CT ;

YANG, WT ;

PARR, RG .

PHYSICAL REVIEW B, 1988, 37 (02) :785-789

[27] The accuracy of the pseudopotential approximation .2. A comparison of various core sizes for indium pseudopotentials in calculations for spectroscopic constants of InH, InF, and InCl [J].

Leininger, T ;

Nicklass, A ;

Stoll, H ;

Dolg, M ;

Schwerdtfeger, P .

JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (03) :1052-1059

[28] The coordination chemistry of carbon dioxide and its relevance for catalysis: A critical survey [J].

Leitner, W .

COORDINATION CHEMISTRY REVIEWS, 1996, 153 :257-284

[29] Density Functional Theory Studies on the Reduction of CO2 to CO by a (NHC)Ni0 Complex [J].

Li, Juan ;

Lin, Zhenyang .

ORGANOMETALLICS, 2009, 28 (14) :4231-4234

[30] Revealing a Second Transmetalation Step in the Negishi Coupling and Its Competition with Reductive Elimination: Improvement in the Interpretation of the Mechanism of Biaryl Syntheses [J].

Liu, Qiang ;

Lan, Yu ;

Liu, Jing ;

Li, Gang ;

Wu, Yun-Dong ;

Lei, Aiwen .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (29) :10201-10210

← 1 2 3 4 5 6 →