Methane activation and exchange by titanium-carbon multiple bonds

被引：65
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
  • [51] METALLORADICAL ACTIVATION OF METHANE
    SHERRY, AE
    WAYLAND, BB
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (03) : 1259 - 1261
  • [52] Activation of C-H bonds by metal complexes
    Shilov, AE
    Shul'pin, GB
    [J]. CHEMICAL REVIEWS, 1997, 97 (08) : 2879 - 2932
  • [53] Cross-metathesis of propane and methane:: A catalytic reaction of C-C bond cleavage of a higher alkane by methane
    Soulivong, D
    Copéret, C
    Thivolle-Cazat, J
    Basset, JM
    Maunders, BM
    Pardy, RBA
    Sunley, GJ
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (40) : 5366 - 5369
  • [54] Non-oxidative coupling reaction of methane to ethane and hydrogen catalyzed by the silica-supported tantalum hydride:: (SiO)2Ta-H
    Soulivong, Daravong
    Norsic, Sebastien
    Taoufik, Mostafa
    Coperet, Christophe
    Thivolle-Cazat, Jean
    Chakka, Sudhakar
    Basset, Jean-Marie
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (15) : 5044 - +
  • [55] Direct transformation of ethylene into propylene catalyzed by a tungsten hydride supported on alumina: Trifunctional single-site catalysis
    Taoufik, Mostafa
    Le Roux, Erwan
    Thivolle-Cazat, Jean
    Basset, Jean-Marie
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (38) : 7202 - 7205
  • [56] THIEULEUX C, 2004, ANGEW CHEM INT EDIT, V43, P5366
  • [57] Thermal alkane C-H bond activation by a tungsten alkylidene complex: The reversal of alpha-hydrogen elimination
    Tran, E
    Legzdins, P
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (21) : 5071 - 5072
  • [58] Facile and selective aliphatic c-h bond activation at ambient temperatures initiated by Cp*W(NO)(CH2CMe3)(η3-CH2CHCHMe)
    Tsang, Jenkins Y. K.
    Buschhaus, Miriam S. A.
    Graham, Peter M.
    Semiao, Christopher J.
    Semproni, Scott P.
    Kim, Simon J.
    Legzdins, Peter
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (11) : 3652 - 3663
  • [59] Ortho-selective C-Hactivation of substituted benzenes effected by a tungsten alkylidene complex without substituent coordination
    Tsang, Jenkins Y. K.
    Buschhaus, Miriam S. A.
    Legzdins, Peter
    Patrick, Brian O.
    [J]. ORGANOMETALLICS, 2006, 25 (17) : 4215 - 4225
  • [60] Ortho-selective C-H activation of substituted benzenes effected by a tungsten alkylidene complex without substituent coordination (vol 25, pg 4220, 2006)
    Tsang, Jenkins Y. K.
    Buschhaus, Miriam S. A.
    Legzdins, Peter
    Patrick, Brian O.
    [J]. ORGANOMETALLICS, 2006, 25 (21) : 5188 - 5188
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