Methyl abstraction kinetics of CpFe(CO)2Me using the benzyl radical clock

Thiam Seong Chong; Tsz Sian Chwee; Weng Kee Leong; Ming Wah Wong; Wai Yip Fan

doi:10.1016/j.jorganchem.2005.10.010

Methyl abstraction kinetics of CpFe(CO)₂Me using the benzyl radical clock

Thiam Seong Chong, Tsz Sian Chwee, Weng Kee Leong, Ming Wah Wong, Wai Yip Fan^*

^*Corresponding author for this work

National University of Singapore

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

4 Citations (Scopus)

Abstract

The rate constant for the methyl abstraction reaction of CpFe(CO) ₂Me has been measured with the benzyl radical clock as (1.1 ± 0.2) × 10⁵ M^-1 s^-1 at room temperature. Time-resolved Fourier-transform Infrared (FTIR) absorption spectroscopy pointed towards the formation of the CpFe(CO)₂ radical upon benzyl abstraction. The main stable product has been established by a linear scan of the reaction mixture as Cp₂Fe₂(CO)₄ produced by the dimerization of the CpFe(CO)₂ radicals. The transition state structure for the abstraction process was also found at UB3LYP/6-311+G* level of theory to contain a planar CH₃ group.

Original language	English
Pages (from-to)	687-692
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	691
Issue number	4
DOIs	https://doi.org/10.1016/j.jorganchem.2005.10.010
Publication status	Published - Feb 1 2006
Externally published	Yes

ASJC Scopus Subject Areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

IR spectroscopy
Methyl abstraction
Radical clock

Access to Document

10.1016/j.jorganchem.2005.10.010

Cite this

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title = "Methyl abstraction kinetics of CpFe(CO)2Me using the benzyl radical clock",

abstract = "The rate constant for the methyl abstraction reaction of CpFe(CO) 2Me has been measured with the benzyl radical clock as (1.1 ± 0.2) × 105 M-1 s-1 at room temperature. Time-resolved Fourier-transform Infrared (FTIR) absorption spectroscopy pointed towards the formation of the CpFe(CO)2 radical upon benzyl abstraction. The main stable product has been established by a linear scan of the reaction mixture as Cp2Fe2(CO)4 produced by the dimerization of the CpFe(CO)2 radicals. The transition state structure for the abstraction process was also found at UB3LYP/6-311+G* level of theory to contain a planar CH3 group.",

keywords = "IR spectroscopy, Methyl abstraction, Radical clock",

author = "Chong, {Thiam Seong} and Chwee, {Tsz Sian} and Leong, {Weng Kee} and Wong, {Ming Wah} and Fan, {Wai Yip}",

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journal = "Journal of Organometallic Chemistry",

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T1 - Methyl abstraction kinetics of CpFe(CO)2Me using the benzyl radical clock

AU - Chong, Thiam Seong

AU - Chwee, Tsz Sian

AU - Leong, Weng Kee

AU - Wong, Ming Wah

AU - Fan, Wai Yip

PY - 2006/2/1

Y1 - 2006/2/1

N2 - The rate constant for the methyl abstraction reaction of CpFe(CO) 2Me has been measured with the benzyl radical clock as (1.1 ± 0.2) × 105 M-1 s-1 at room temperature. Time-resolved Fourier-transform Infrared (FTIR) absorption spectroscopy pointed towards the formation of the CpFe(CO)2 radical upon benzyl abstraction. The main stable product has been established by a linear scan of the reaction mixture as Cp2Fe2(CO)4 produced by the dimerization of the CpFe(CO)2 radicals. The transition state structure for the abstraction process was also found at UB3LYP/6-311+G* level of theory to contain a planar CH3 group.

AB - The rate constant for the methyl abstraction reaction of CpFe(CO) 2Me has been measured with the benzyl radical clock as (1.1 ± 0.2) × 105 M-1 s-1 at room temperature. Time-resolved Fourier-transform Infrared (FTIR) absorption spectroscopy pointed towards the formation of the CpFe(CO)2 radical upon benzyl abstraction. The main stable product has been established by a linear scan of the reaction mixture as Cp2Fe2(CO)4 produced by the dimerization of the CpFe(CO)2 radicals. The transition state structure for the abstraction process was also found at UB3LYP/6-311+G* level of theory to contain a planar CH3 group.

KW - IR spectroscopy

KW - Methyl abstraction

KW - Radical clock

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