A Frustrated Phosphane-Borane Lewis Pair and Hydrogen: A Kinetics Study

被引：20

作者：

Oezguen, Thomas ^{[1
]}

Bergander, Klaus ^{[1
]}

Liu, Lei ^{[2
]}

Daniliuc, Constantin G. ^{[1
]}

Grimme, Stefan ^{[2
]}

Kehr, Gerald ^{[1
]}

Erker, Gerhard ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, Corrensstr 40, D-48149 Munster, Germany

[2] Univ Bonn, Mulliken Ctr Theoret Chem, Inst Phys & Theoret Chem, Beringstr 4, D-53115 Bonn, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 34期

关键词：

density dunctional calculations; deuterium isotope effect; frustrated Lewis pairs; hydrogen splitting; kinetics; phosphane-boranes; HETEROLYTIC DIHYDROGEN ACTIVATION; CATALYTIC-HYDROGENATION; BASIS-SETS; REACTIVITY; REDUCTION; MECHANISM; MODELS;

D O I：

10.1002/chem.201603050

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The energy profile of a frustrated Lewis pair (FLP) dihydrogen splitting system was determined by a combined experimental kinetic and DFT study. A trimethylene-bridged phosphane-borane FLP was converted into its endothermic H-2-cleavage product by sequential H+/H- addition. The system could be handled at low temperature, and the kinetics of the H-2 elimination were determined to give a rate constant of k(HH,exp)(299 K)=(2.87 +/- 0.1) x 10(-4) s(-1) in solution. The primary kinetic isotope effects were determined; for example, (k(HH)/k(DD)) exp=3.19. The system was accurately analyzed by DFT calculations.

引用

页码：11958 / 11961

页数：4

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