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.

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页码：4032 / 4038

页数：7

相关论文

共 63 条

[51] ALKYLCOBALOXIMES AND THEIR RELATION TO ALKYLCOBALAMINS [J].

SCHRAUZER, GN ;

WINDGASSEN, RJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (16) :3738-+

[52] Oxidative addition and C-H activation chemistry with a PNP pincer-ligated cobalt complex [J].

Semproni, Scott P. ;

Atienza, Crisita Carmen Hojilla ;

Chirik, Paul J. .

CHEMICAL SCIENCE, 2014, 5 (05) :1956-1960

[53] Activation of C-H bonds by metal complexes [J].

Shilov, AE ;

Shul'pin, GB .

CHEMICAL REVIEWS, 1997, 97 (08) :2879-2932

[54] Heats of Formation of C6H5•, C6H5+, and C6H5NO by Threshold Photoelectron Photoion Coincidence and Active Thermochemical Tables Analysis [J].

Stevens, William R. ;

Ruscic, Branko ;

Baer, Tomas .

JOURNAL OF PHYSICAL CHEMISTRY A, 2010, 114 (50) :13134-13145

[55] Methane metathesis at a Cationic Iridium Center [J].

Strout, DL ;

Zaric, S ;

Niu, SQ ;

Hall, MB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (25) :6068-6069

[56] An energetically feasible mechanism for the activation of the C-H bond by the 16-electron CpM(PH3)(CH3)(+) (M=Rh, Ir) complex. A theoretical study [J].

Su, MD ;

Chu, SY .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (23) :5373-5383

[57] Synthesis and investigation of [Cp*(PMe3)Rh(H)(H2)]+ and its partially deuterated and tritiated isotopomers:: Evidence for a hydride/dihydrogen structure [J].

Taw, FL ;

Mellows, H ;

White, PS ;

Hollander, FJ ;

Bergman, RG ;

Brookhart, M ;

Heinekey, DM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (18) :5100-5108

[58] Electronic and medium effects on the rate of arene C-H bond activation by cationic Ir(III) complexes [J].

Tellers, DM ;

Yung, CM ;

Arndtsen, BA ;

Adamson, DR ;

Bergman, RG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (07) :1400-1410

[59] CHEMISTRY OF 2-NAPHTHYL BIS[BIS(DIMETHYLPHOSPHINO)ETHANE] HYDRIDE COMPLEXES OF FE, RU, AND OS .1. CHARACTERIZATION AND REACTIONS WITH H-2 AND LEWIS BASE LIGANDS [J].

TOLMAN, CA ;

ITTEL, SD ;

ENGLISH, AD ;

JESSON, JP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (13) :4080-4089

[60] CHEMISTRY OF 2-NAPHTYYL BIS[BIS(DIMETHYLPHOSPHINO)ETHANE] HYDRIDE COMPLEXES OF IRON, RUTHENIUM, AND OSMUIM .3. CLEAVAGE OF SP2 C-H BONDS [J].

TOLMAN, CA ;

ITTEL, SD ;

ENGLISH, AD ;

JESSON, JP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (07) :1742-1751

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