Coordination chemistry of stable radicals: Homolysis of a titanium-oxygen bond

Kuo Wei Huang; Robert M. Waymouth

doi:10.1021/ja0264854

Coordination chemistry of stable radicals: Homolysis of a titanium-oxygen bond

Kuo Wei Huang, Robert M. Waymouth^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

42 Scopus citations

Abstract

Thermolysis of Cp₂TiCl(TEMPO) (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl) at 60 °C in a benzene/CCl₄ mixture generates Cp₂TiCl₂. Kinetic studies implicate a mechanism involving the reversible cleavage of a Ti-O bond to generate the TEMPO radical and Cp₂TiCl, which is trapped by CCl₄ to give Cp₂TiCl₂. The rate of this reaction is strongly inhibited by added TEMPO and increases with increasing CCl₄ concentration, indicating that the coupling of TEMPO to Cp₂TiCl is faster than chloride atom abstraction from CCl₄.

Original language	English (US)
Pages (from-to)	8200-8201
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	124
Issue number	28
DOIs	https://doi.org/10.1021/ja0264854
State	Published - Jul 17 2002
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Coordination chemistry of stable radicals: Homolysis of a titanium-oxygen bond",

abstract = "Thermolysis of Cp2TiCl(TEMPO) (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl) at 60 °C in a benzene/CCl4 mixture generates Cp2TiCl2. Kinetic studies implicate a mechanism involving the reversible cleavage of a Ti-O bond to generate the TEMPO radical and Cp2TiCl, which is trapped by CCl4 to give Cp2TiCl2. The rate of this reaction is strongly inhibited by added TEMPO and increases with increasing CCl4 concentration, indicating that the coupling of TEMPO to Cp2TiCl is faster than chloride atom abstraction from CCl4.",

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T2 - Homolysis of a titanium-oxygen bond

AU - Huang, Kuo Wei

AU - Waymouth, Robert M.

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N2 - Thermolysis of Cp2TiCl(TEMPO) (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl) at 60 °C in a benzene/CCl4 mixture generates Cp2TiCl2. Kinetic studies implicate a mechanism involving the reversible cleavage of a Ti-O bond to generate the TEMPO radical and Cp2TiCl, which is trapped by CCl4 to give Cp2TiCl2. The rate of this reaction is strongly inhibited by added TEMPO and increases with increasing CCl4 concentration, indicating that the coupling of TEMPO to Cp2TiCl is faster than chloride atom abstraction from CCl4.

AB - Thermolysis of Cp2TiCl(TEMPO) (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxyl) at 60 °C in a benzene/CCl4 mixture generates Cp2TiCl2. Kinetic studies implicate a mechanism involving the reversible cleavage of a Ti-O bond to generate the TEMPO radical and Cp2TiCl, which is trapped by CCl4 to give Cp2TiCl2. The rate of this reaction is strongly inhibited by added TEMPO and increases with increasing CCl4 concentration, indicating that the coupling of TEMPO to Cp2TiCl is faster than chloride atom abstraction from CCl4.

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Coordination chemistry of stable radicals: Homolysis of a titanium-oxygen bond

Abstract

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