Mechanistic analysis of iridium heteroatom C-H activation: Evidence for an internal electrophilic substitution mechanism

被引：133

作者：

Oxgaard, Jonas ^{[1
]}

Tenn, William J., III

Nielsen, Robert J.

Periana, Roy A.

Goddard, William A., III

机构：

[1] CALTECH, Mat & Proc Simulat Ctr, Beckman Inst 139 74, Pasadena, CA 91125 USA

[2] Univ So Calif, Loker Hydrocarbon Res Inst, Dept Chem, Los Angeles, CA 90089 USA

来源：

ORGANOMETALLICS | 2007年 / 26卷 / 07期

关键词：

D O I：

10.1021/om061189b

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The mechanism responsible for C-H activation in Ir(acac)(2)(OCH3)(C6H6) has been identified and described as an internal electrophilic substitution (IES) mechanism, on the basis of orbital changes and predicted reactivity. In this IES mechanism, the lone pair on a M-X ligand forms an X-H bond, while the orbital making up the M-X bond turns into a coordinating lone pair.

引用

页码：1565 / 1567

页数：3

共 23 条

[1] Selectivities in hydrocarbon activation: Kinetic and thermodynamic investigations of reversible 1,2-RH-elimination from (silox)(2)((Bu3SiNH)-Bu-t)TiR (silox = (Bu3SiO)-Bu-t) [J].

Bennett, JL ;

Wolczanski, PT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (44) :10696-10719

[2] ENERGETICS OF C-H BOND ACTIVATION AND ETHYLENE BINDING TO D(0) TRANSIENT (SILOX)(2)TI=NSI(T)BU(3) [J].

BENNETT, JL ;

WOLCZANSKI, PT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (05) :2179-2180

[3] Synthesis and reactivity of a coordinatively unsaturated ruthenium(II) parent amido complex: Studies of X-H activation (X = H or C) [J].

Conner, D ;

Jayaprakash, KN ;

Cundari, TR ;

Gunnoe, TB .

ORGANOMETALLICS, 2004, 23 (11) :2724-2733

[4] METHANE AND BENZENE ACTIVATION VIA TRANSIENT (TERT-BU3SINH)2ZR=NSI-TERT-BU3 [J].

CUMMINS, CC ;

BAXTER, SM ;

WOLCZANSKI, PT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (26) :8731-8733

[5] Carbon-hydrogen bond activation by titanium imido complexes. Computational evidence for the role of alkane adducts in selective C-H activation [J].

Cundari, TR ;

Klinckman, TR ;

Wolczanski, PT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (07) :1481-1487

[6] Evidence for the net addition of arene C-H bonds across a Ru(II)-hydroxide bond [J].

Feng, Y ;

Lail, M ;

Barakat, KA ;

Cundari, TR ;

Gunnoe, TB ;

Petersen, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (41) :14174-14175

[7] Hydrogen-deuterium exchange between TpRu( PMe3)(L)X (L) = PMe3 and X = OH, OPh, Me, Ph, or NHPh;: L = NCMe and X = Ph) and deuterated arene solvents:: Evidence for metal-mediated processes [J].

Feng, Yuee ;

Lail, Marty ;

Foley, Nicholas A. ;

Gunnoe, T. Brent ;

Barakat, Khaldoon A. ;

Cundari, Thomas R. ;

Petersen, Jeffrey L. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (24) :7982-7994

[8] SYNTHESIS AND REACTIVITY OF RUTHENIUM AMIDE PHOSPHINE COMPLEXES - FACILE CONVERSION OF A RUTHENIUM AMIDE TO A RUTHENIUM AMINE VIA DIHYDROGEN ACTIVATION AND ORTHO METALATION - X-RAY STRUCTURE OF RUCL(C6H4PPH2)[NH(SIME2CH2PPH2)2] [J].

FRYZUK, MD ;

MONTGOMERY, CD ;

RETTIG, SJ .

ORGANOMETALLICS, 1991, 10 (02) :467-473

[9] ACTIVATION OF DIHYDROGEN BY ORGANO IRIDIUM PHOSPHIDO COMPLEXES - EVIDENCE FOR ALPHA-HYDROGEN ABSTRACTION BY A TERMINAL PHOSPHIDE LIGAND [J].

FRYZUK, MD ;

BHANGU, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (03) :961-963

[10] Formation, reactivity, and properties of nondative late transition metal-oxygen and -nitrogen bonds [J].

Fulton, JR ;

Holland, AW ;

Fox, DJ ;

Bergman, RG .

ACCOUNTS OF CHEMICAL RESEARCH, 2002, 35 (01) :44-56

← 1 2 3 →