Methane activation and exchange by titanium-carbon multiple bonds

Jaime A. Flores; Vincent N. Cavaliere; Dominik Buck; Balázs Pintér; George Chen; Marco G. Crestani; Mu Hyun Baik; Daniel J. Mindiola

doi:10.1039/c1sc00138h

Methane activation and exchange by titanium-carbon multiple bonds

Jaime A. Flores, Vincent N. Cavaliere, Dominik Buck, Balázs Pintér, George Chen, Marco G. Crestani, Mu Hyun Baik, Daniel J. Mindiola

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67 Scopus citations

Abstract

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

Original language	English (US)
Pages (from-to)	1457-1462
Number of pages	6
Journal	Chemical Science
Volume	2
Issue number	8
DOIs	https://doi.org/10.1039/c1sc00138h
State	Published - Aug 2011
Externally published	Yes

ASJC Scopus subject areas

General Chemistry

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title = "Methane activation and exchange by titanium-carbon multiple bonds",

abstract = "We demonstrate that a titanium-carbon multiple bond, specifically an alkylidyne ligand in the transient complex, (PNP)TiCtBu (A) (PNP - = N[2-P(CHMe2)2-4-methylphenyl]2), can cleanly activate methane at room temperature with moderately elevated pressures to form (PNP)TiCHtBu(CH3). Isotopic labeling and theoretical studies suggest that the alkylidene and methyl hydrogens exchange, either via tautomerization invoking a methylidene complex, (PNP)TiCH 2(CH2tBu), or by forming the methane adduct (PNP)TiCtBu(CH4). The thermal, fluxional and chemical behavior of (PNP)TiCHtBu(CH3) is also presented in this study.",

author = "Flores, {Jaime A.} and Cavaliere, {Vincent N.} and Dominik Buck and Bal{\'a}zs Pint{\'e}r and George Chen and Crestani, {Marco G.} and Baik, {Mu Hyun} and Mindiola, {Daniel J.}",

year = "2011",

month = aug,

doi = "10.1039/c1sc00138h",

language = "English (US)",

volume = "2",

pages = "1457--1462",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Methane activation and exchange by titanium-carbon multiple bonds

AU - Flores, Jaime A.

AU - Cavaliere, Vincent N.

AU - Buck, Dominik

AU - Pintér, Balázs

AU - Chen, George

AU - Crestani, Marco G.

AU - Baik, Mu Hyun

AU - Mindiola, Daniel J.

PY - 2011/8

Y1 - 2011/8

N2 - We demonstrate that a titanium-carbon multiple bond, specifically an alkylidyne ligand in the transient complex, (PNP)TiCtBu (A) (PNP - = N[2-P(CHMe2)2-4-methylphenyl]2), can cleanly activate methane at room temperature with moderately elevated pressures to form (PNP)TiCHtBu(CH3). Isotopic labeling and theoretical studies suggest that the alkylidene and methyl hydrogens exchange, either via tautomerization invoking a methylidene complex, (PNP)TiCH 2(CH2tBu), or by forming the methane adduct (PNP)TiCtBu(CH4). The thermal, fluxional and chemical behavior of (PNP)TiCHtBu(CH3) is also presented in this study.

AB - We demonstrate that a titanium-carbon multiple bond, specifically an alkylidyne ligand in the transient complex, (PNP)TiCtBu (A) (PNP - = N[2-P(CHMe2)2-4-methylphenyl]2), can cleanly activate methane at room temperature with moderately elevated pressures to form (PNP)TiCHtBu(CH3). Isotopic labeling and theoretical studies suggest that the alkylidene and methyl hydrogens exchange, either via tautomerization invoking a methylidene complex, (PNP)TiCH 2(CH2tBu), or by forming the methane adduct (PNP)TiCtBu(CH4). The thermal, fluxional and chemical behavior of (PNP)TiCHtBu(CH3) is also presented in this study.

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DO - 10.1039/c1sc00138h

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JO - Chemical Science

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Methane activation and exchange by titanium-carbon multiple bonds

Abstract

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