Methane activation and exchange by titanium-carbon multiple bonds

被引：67

作者：

Flores, Jaime A. ^{[1
]}

Cavaliere, Vincent N. ^{[1
]}

Buck, Dominik ^{[1
]}

Pinter, Balazs ^{[1
]}

Chen, George ^{[2
]}

Crestani, Marco G. ^{[1
]}

Baik, Mu-Hyun ^{[1
]}

Mindiola, Daniel J. ^{[1
]}

机构：

[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

[2] CALTECH, Div Chem & Chem Engn, Pasadena, CA 91125 USA

来源：

CHEMICAL SCIENCE | 2011年 / 2卷 / 08期

基金：

美国国家科学基金会;

关键词：

C-H ACTIVATION; TUNGSTEN ALKYLIDENE COMPLEXES; ALKANE METATHESIS; COMPUTATIONAL PERSPECTIVE; HYDROCARBON ACTIVATION; AMBIENT-TEMPERATURES; AGOSTIC INTERACTIONS; THERMAL-ACTIVATION; BENZENE ACTIVATION; OLEFIN METATHESIS;

D O I：

10.1039/c1sc00138h

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We demonstrate that a titanium-carbon multiple bond, specifically an alkylidyne ligand in the transient complex, (PNP) Ti equivalent to(CBu)-Bu-t (A) (PNP- = N[2-P(CHMe2)(2)-4-methylphenyl](2)), can cleanly activate methane at room temperature with moderately elevated pressures to form (PNP)Ti=(CHBu)-Bu-t(CH3). Isotopic labeling and theoretical studies suggest that the alkylidene and methyl hydrogens exchange, either via tautomerization invoking a methylidene complex, (PNP)Ti=CH2((CH2Bu)-Bu-t), or by forming the methane adduct (PNP)Ti equivalent to(CBu)-Bu-t(CH4). The thermal, fluxional and chemical behavior of (PNP)Ti=(CHBu)-Bu-t(CH3) is also presented in this study.

引用

收藏

页码：1457 / 1462

页数：6

相关论文

共 67 条

[1] C-H activation of substituted arenes by tungsten alkylidene complexes: Products, selectivity, and mechanism [J].

Adams, CS ;

Legzdins, P ;

Tran, E .

ORGANOMETALLICS, 2002, 21 (07) :1474-1486

[2] Thermal activation of hydrocarbon C-H bonds by tungsten alkylidene complexes [J].

Adams, CS ;

Legzdins, P ;

Tran, E .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (04) :612-624

[3] Intermolecular C-H activation of hydrocarbons by tungsten alkylidene complexes: An experimental and computational mechanistic study [J].

Adams, CS ;

Legzdins, P ;

McNeil, WS .

ORGANOMETALLICS, 2001, 20 (23) :4939-4955

[4] Intermolecular C-H bond activation of benzene and pyridines by a vanadium(III) alkylidene including a stepwise conversion of benzene to a vanadium-benzyne complex [J].

Andino, Jose G. ;

Kilgore, Uriah J. ;

Pink, Maren ;

Ozarowski, Andrew ;

Krzystek, J. ;

Telser, Joshua ;

Baik, Mu-Hyun ;

Mindiola, Daniel J. .

CHEMICAL SCIENCE, 2010, 1 (03) :351-356

[5] Reactions of methane with titanium atoms:: CH3TIH, CH2=TiH2, agostic bonding, and (CH3)2TiH2 [J].

Andrews, L ;

Cho, HG ;

Wang, X .

INORGANIC CHEMISTRY, 2005, 44 (13) :4834-4842

[6] Catalysis research of relevance to carbon management: Progress, challenges, and opportunities [J].

Arakawa, H ;

Aresta, M ;

Armor, JN ;

Barteau, MA ;

Beckman, EJ ;

Bell, AT ;

Bercaw, JE ;

Creutz, C ;

Dinjus, E ;

Dixon, DA ;

Domen, K ;

DuBois, DL ;

Eckert, J ;

Fujita, E ;

Gibson, DH ;

Goddard, WA ;

Goodman, DW ;

Keller, J ;

Kubas, GJ ;

Kung, HH ;

Lyons, JE ;

Manzer, LE ;

Marks, TJ ;

Morokuma, K ;

Nicholas, KM ;

Periana, R ;

Que, L ;

Rostrup-Nielson, J ;

Sachtler, WMH ;

Schmidt, LD ;

Sen, A ;

Somorjai, GA ;

Stair, PC ;

Stults, BR ;

Tumas, W .

CHEMICAL REVIEWS, 2001, 101 (04) :953-996

[7] Synthesis and reactions of tungsten alkylidene complexes that contain the 2,6-dichlorophenylimido ligand [J].

Arndt, Stefan ;

Schrock, Richard R. ;

Muller, Peter .

ORGANOMETALLICS, 2007, 26 (05) :1279-1290

[8] UNUSUALLY MILD AND SELECTIVE HYDROCARBON C-H BOND ACTIVATION WITH POSITIVELY CHARGED IRIDIUM(III) COMPLEXES [J].

ARNDTSEN, BA ;

BERGMAN, RG .

SCIENCE, 1995, 270 (5244) :1970-1973

[9] Intermolecular C-H bond activation promoted by a titanium alkylidyne [J].

Bailey, BC ;

Fan, HJ ;

Baum, EW ;

Huffman, JC ;

Baik, MH ;

Mindiola, DJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (46) :16016-16017

[10]

BAILEY BC, 2006, THESIS INDIANA U BLO

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