DFT Study on the Mechanism of the Activation and Cleavage of CO2 by (NHC)CuEPh3 (E = Si, Ge, Sn)

被引：69

作者：

Ariafard, Alireza ^{[1
,2
]}

Brookes, Nigel J. ^{[1
]}

Stranger, Robert ^{[3
]}

Yates, Brian F. ^{[1
]}

机构：

[1] Univ Tasmania, Sch Chem, Hobart, Tas 7001, Australia

[2] Islamic Azad Univ, Cent Tehran Branch, Fac Sci, Dept Chem, Tehran, Iran

[3] Australian Natl Univ, Res Sch Chem, Canberra, ACT 0200, Australia

来源：

ORGANOMETALLICS | 2011年 / 30卷 / 06期

基金：

澳大利亚研究理事会;

关键词：

DENSITY-FUNCTIONAL THEORY; EFFECTIVE CORE POTENTIALS; CARBON BOND FORMATION; AB-INITIO MO; MOLECULAR CALCULATIONS; POLARIZATION FUNCTIONS; BASIS-SETS; CATALYZED HYDROGENATION; MP2; ENERGY; DIOXIDE;

D O I：

10.1021/om100730h

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Density functional theory has been used to investigate the mechanism of the activation and cleavage of CO2 by the complexes (NHC)CuEPh3 (E = Si, Ge, Sn). Our results show that both the Cu-E and E-C(Ph) bonds are capable of activating and cleaving CO2. The reactivity of the Cu-E bond toward CO2 activation decreases as E becomes heavier, while the reactivity of the E-C(Ph) bond toward CO2 activation increases as E becomes heavier. The higher electron-releasing capability of (NHC)Cu compared to the, EPh3 group causes the EPh3 group to serve as a nucleophile (not an electrophile).

引用

收藏

页码：1340 / 1349

页数：10

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