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Issue 8, 2011
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Methane activation and exchange by titanium-carbon multiple bonds

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Abstract

We demonstrate that a titanium-carbon multiple bond, specifically an alkylidyne ligand in the transient complex, (PNP)Ti[triple bond, length as m-dash]CtBu (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[double bond, length as m-dash]CHtBu(CH3). Isotopic labeling and theoretical studies suggest that the alkylidene and methyl hydrogens exchange, either viatautomerization invoking a methylidene complex, (PNP)Ti[double bond, length as m-dash]CH2(CH2tBu), or by forming the methane adduct (PNP)Ti[triple bond, length as m-dash]CtBu(CH4). The thermal, fluxional and chemical behavior of (PNP)Ti[double bond, length as m-dash]CHtBu(CH3) is also presented in this study.

Graphical abstract: Methane activation and exchange by titanium-carbon multiple bonds

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Article information


Submitted
09 Mar 2011
Accepted
28 Apr 2011
First published
02 Jun 2011

Chem. Sci., 2011,2, 1457-1462
Article type
Edge Article

Methane activation and exchange by titanium-carbon multiple bonds

J. A. Flores, V. N. Cavaliere, D. Buck, B. Pintér, G. Chen, M. G. Crestani, M. Baik and D. J. Mindiola, Chem. Sci., 2011, 2, 1457
DOI: 10.1039/C1SC00138H

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