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

页码：1457 / 1462

页数：6

共 67 条

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