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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:
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.
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页码:1348 / 1353
页数:6
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