A Theoretical Study of Hydrogen Transfer Catalyzed by an IrIII PC(sp3)P Pincer Complex

被引：5

作者：

Kozuch, Sebastian ^{[1
,2
]}

Azerraf, Clarite ^{[1
]}

机构：

[1] Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel

[2] Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel

来源：

CHEMCATCHEM | 2011年 / 3卷 / 08期

关键词：

density functional calculations; energetic span model; hydrogen transfer; iridium; pincer; TRANSITION-METAL-COMPLEXES; DENSITY-FUNCTIONAL THEORY; BOND ACTIVATION; MODEL; GEOMETRIES; IRIDIUM; CHEMISTRY; MECHANISM; KETONES; CYCLES;

D O I：

10.1002/cctc.201100056

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：

A hydrogen transfer mechanism catalyzed by an Ir-III PC(sp(3))P pincer complex was studied by using DFT, and its efficiency was estimated by using the energetic span model. With the pristine complex, a hydrogen abstraction pathway could not be found, since a ligand dissociation to generate a vacant site is energetically costly. However, a nucleophilic attack of an alkoxide base (present in the reaction mixture) on the carbonyl ligand to form a carboalkoxy ligand generated an anionic catalyst that could easily provide the free site. From there, a hydride abstraction from an isopropyl ion (iPrO(-)) followed by a hydride transfer to acetophenone resulted in an efficient catalytic cycle.

引用

页码：1348 / 1353

页数：6

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