Methane Is the Best Substrate for C(sp3)-H Activation with Cp*(PMe3)Co(Me)(OTf): A Density Functional Theory Study

被引：10

作者：

Bellows, Sarina M. ^{[1
,4
]}

Cundari, Thomas R. ^{[2
,3
,4
]}

Jones, William D. ^{[1
,4
]}

机构：

[1] Univ Rochester, Dept Chem, New York, NY 14627 USA

[2] Univ N Texas, Dept Chem, Denton, TX 76203 USA

[3] Univ N Texas, CASCaM, Denton, TX 76203 USA

[4] Univ Washington, Dept Chem, Ctr Enabling New Technol Catalysis CENTC, Seattle, WA 98195 USA

来源：

ORGANOMETALLICS | 2015年 / 34卷 / 16期

基金：

美国国家科学基金会;

关键词：

C-H-BONDS; MOLECULAR-HYDROGEN COMPLEXES; HYDRIDE COMPLEXES; INTERMOLECULAR ACTIVATION; ETHYLENE POLYMERIZATION; SATURATED-HYDROCARBONS; OXIDATIVE ADDITION; MECHANISM; CHEMISTRY; ALKANE;

D O I：

10.1021/acs.organomet.5b00452

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The chemical inertness of C(sp(3))-H bonds has made their functionalization difficult, especially with earth-abundant 3d metals. The mechanism of C-H activation with the Co(III) complex Cp*(PMe3)Co-(CH3)(OTf) was studied by DFT at the M06/6-31+G(d) level of theory and was determined to be in very good agreement with experimental data. The Co(III) complex can activate the C-H bond of methane through an oxidative hydrogen migration mechanism with an activation free energy of 32.4 kcal/mol in CH2Cl2. Although C2H6 and c-C6H12 have weaker C-H bonds than CH4, their C-H activation barriers were greater at 34.9 and 45.9 kcal/mol, respectively. The C(sp(3))-H and C(sp(2))-H activation of this Co(III) complex is primarily driven by the sterics (-E'(s)) of the substrates and supporting ligands and not the strength of the C-H bond.

引用

页码：4032 / 4038

页数：7

共 63 条

[1] SELECTIVE INTERMOLECULAR CARBON-HYDROGEN BOND ACTIVATION BY SYNTHETIC METAL-COMPLEXES IN HOMOGENEOUS SOLUTION [J].