Mechanism of the MoO2Cl2-catalyzed hydrosilylation:: a DFT study

被引：40

作者：

Drees, Markus ^{[1
]}

Strassner, Thomas ^{[1
]}

机构：

[1] Tech Univ Dresden, D-01062 Dresden, Germany

来源：

INORGANIC CHEMISTRY | 2007年 / 46卷 / 25期

关键词：

D O I：

10.1021/ic7017314

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A detailed mechanistic study of the hydrosilylation of benzaldehyde catalyzed by MoO2Cl2 is reported. On the basis of DFT calculations (B3LYP/6-311++G**), a reaction pathway via initial silane activation is proposed. SiH and CH activation energies by other metal-oxo compounds like RuO4, OsO4, and MnO4- are compared to MoO2Cl2. MO4-type metal-oxo compounds follow a different mechanism, forming highly exergonic intermediates, which prevent a catalytic reaction, whereas MoO2Cl2 prefers a reaction pathway via thermoneutral intermediates.

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页码：10850 / 10859

页数：10

相关论文

共 38 条

[1] ENERGY-ADJUSTED ABINITIO PSEUDOPOTENTIALS FOR THE 2ND AND 3RD ROW TRANSITION-ELEMENTS [J].

ANDRAE, D ;

HAUSSERMANN, U ;

DOLG, M ;

STOLL, H ;

PREUSS, H .

THEORETICA CHIMICA ACTA, 1990, 77 (02) :123-141

[2]

[Anonymous], 1999, HDB REAGENTS ORGANIC

[3] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[4] Computational study on the reaction mechanism of hydrosilylation of carbonyls catalyzed by high-valent rhenium(V)-di-oxo complexes [J].

Chung, Lung Wa ;

Lee, Hung Gai ;

Lin, Zhenyang ;

Wu, Yun-Dong .

JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (16) :6000-6009

[5] EFFICIENT DIFFUSE FUNCTION-AUGMENTED BASIS SETS FOR ANION CALCULATIONS. III. THE 3-21+G BASIS SET FOR FIRST-ROW ELEMENTS, LI-F [J].

CLARK, T ;

CHANDRASEKHAR, J ;

SPITZNAGEL, GW ;

SCHLEYER, PV .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1983, 4 (03) :294-301

[6] Catalyzing aldehyde hydrosilylation with a molybdenum(VI) complex: A density functional theory study [J].

Costa, Paulo Jorge ;

Romao, Carlos C. ;

Fernandes, Ana C. ;

Royo, Beatriz ;

Reis, Patricia M. ;

Calhorda, Maria Jose .

CHEMISTRY-A EUROPEAN JOURNAL, 2007, 13 (14) :3934-3941

[7]

DENNINGTON R, 2003, GAUSSVIEW 3 09

[8] Ruthenium tetraoxide oxidations of alkanes: DFT calculations of barrier heights and kinetic isotope effects [J].

Drees, M ;

Strassner, T .

JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (05) :1755-1760

[9] Mechanistic insight into hydrosilylation reactions catalyzed by high valent Re≡X (X = O, NAr, or N) complexes:: The silane (SiH) does not add across the metal-ligand multiple bond [J].

Du, Guodong ;

Fanwick, Phillip E. ;

Abu-Omar, Mahdi M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (16) :5180-5187

[10] [MoO2Cl2] as catalyst for hydrosilylation of aldehydes and ketones [J].

Fernandes, AC ;

Fernandes, R ;

Romao, CC ;

Royo, B .

CHEMICAL COMMUNICATIONS, 2005, (02) :213-214

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