TR-FTIR absorption spectroscopy of transition metal carbonyl radicals generated by photodissociation of metal-metal bonds, by halogen abstraction or by radical ligand substitution

Thiam Seong Chong; Peng Li; Weng Kee Leong; Wai Yip Fan

doi:10.1016/j.jorganchem.2005.06.015

TR-FTIR absorption spectroscopy of transition metal carbonyl radicals generated by photodissociation of metal-metal bonds, by halogen abstraction or by radical ligand substitution

Thiam Seong Chong, Peng Li, Weng Kee Leong, Wai Yip Fan^*

^*Corresponding author for this work

National University of Singapore

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

13 Citations (Scopus)

Abstract

Three methods of obtaining time-resolved Fourier-Transform infrared (TR-FTIR) absorption spectra of transition metal carbonyl radicals in hexane are reported here. For the first method, CpM(CO)₂L and Cp*M(CO)₂L (M = Mo, W; L = CO, PR₃) radicals have been generated by photodissociation of the corresponding metal-metal bonded dimers. Radicals of formula M(CO)₄L (M = Mn, Re; L = CO, PR ₃, AsPh₃, SbPh₃) and CpM(CO)_n (M = Fe, Mo; n = 2, 3) have been produced via the second method which is halogen abstraction of the transition metal carbonyl halides using CpMo(CO)₃ radical. For the third method, fast radical ligand substitution kinetics has been exploited to generate CpMo(CO)₂PR₃ radicals from CpMo(CO)₃ in the presence of free phosphines. An assessment of the three methods with respect to TR-FTIR spectroscopic detection of radicals was also discussed.

Original language	English
Pages (from-to)	4132-4138
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	690
Issue number	18
DOIs	https://doi.org/10.1016/j.jorganchem.2005.06.015
Publication status	Published - Sept 15 2005
Externally published	Yes

ASJC Scopus Subject Areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

Halide abstraction
Ligand substitution kinetics
Metal-metal bond dissociation
TR-FTIR radical spectra

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10.1016/j.jorganchem.2005.06.015

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@article{f87ee865b22d4e0890c91ab6c19a9f25,

title = "TR-FTIR absorption spectroscopy of transition metal carbonyl radicals generated by photodissociation of metal-metal bonds, by halogen abstraction or by radical ligand substitution",

abstract = "Three methods of obtaining time-resolved Fourier-Transform infrared (TR-FTIR) absorption spectra of transition metal carbonyl radicals in hexane are reported here. For the first method, CpM(CO)2L and Cp*M(CO)2L (M = Mo, W; L = CO, PR3) radicals have been generated by photodissociation of the corresponding metal-metal bonded dimers. Radicals of formula M(CO)4L (M = Mn, Re; L = CO, PR 3, AsPh3, SbPh3) and CpM(CO)n (M = Fe, Mo; n = 2, 3) have been produced via the second method which is halogen abstraction of the transition metal carbonyl halides using CpMo(CO)3 radical. For the third method, fast radical ligand substitution kinetics has been exploited to generate CpMo(CO)2PR3 radicals from CpMo(CO)3 in the presence of free phosphines. An assessment of the three methods with respect to TR-FTIR spectroscopic detection of radicals was also discussed.",

keywords = "Halide abstraction, Ligand substitution kinetics, Metal-metal bond dissociation, TR-FTIR radical spectra",

author = "Chong, {Thiam Seong} and Peng Li and Leong, {Weng Kee} and Fan, {Wai Yip}",

year = "2005",

month = sep,

day = "15",

doi = "10.1016/j.jorganchem.2005.06.015",

language = "English",

volume = "690",

pages = "4132--4138",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "18",

}

TR-FTIR absorption spectroscopy of transition metal carbonyl radicals generated by photodissociation of metal-metal bonds, by halogen abstraction or by radical ligand substitution. / Chong, Thiam Seong; Li, Peng; Leong, Weng Kee et al.
In: Journal of Organometallic Chemistry, Vol. 690, No. 18, 15.09.2005, p. 4132-4138.

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

TY - JOUR

T1 - TR-FTIR absorption spectroscopy of transition metal carbonyl radicals generated by photodissociation of metal-metal bonds, by halogen abstraction or by radical ligand substitution

AU - Chong, Thiam Seong

AU - Li, Peng

AU - Leong, Weng Kee

AU - Fan, Wai Yip

PY - 2005/9/15

Y1 - 2005/9/15

N2 - Three methods of obtaining time-resolved Fourier-Transform infrared (TR-FTIR) absorption spectra of transition metal carbonyl radicals in hexane are reported here. For the first method, CpM(CO)2L and Cp*M(CO)2L (M = Mo, W; L = CO, PR3) radicals have been generated by photodissociation of the corresponding metal-metal bonded dimers. Radicals of formula M(CO)4L (M = Mn, Re; L = CO, PR 3, AsPh3, SbPh3) and CpM(CO)n (M = Fe, Mo; n = 2, 3) have been produced via the second method which is halogen abstraction of the transition metal carbonyl halides using CpMo(CO)3 radical. For the third method, fast radical ligand substitution kinetics has been exploited to generate CpMo(CO)2PR3 radicals from CpMo(CO)3 in the presence of free phosphines. An assessment of the three methods with respect to TR-FTIR spectroscopic detection of radicals was also discussed.

AB - Three methods of obtaining time-resolved Fourier-Transform infrared (TR-FTIR) absorption spectra of transition metal carbonyl radicals in hexane are reported here. For the first method, CpM(CO)2L and Cp*M(CO)2L (M = Mo, W; L = CO, PR3) radicals have been generated by photodissociation of the corresponding metal-metal bonded dimers. Radicals of formula M(CO)4L (M = Mn, Re; L = CO, PR 3, AsPh3, SbPh3) and CpM(CO)n (M = Fe, Mo; n = 2, 3) have been produced via the second method which is halogen abstraction of the transition metal carbonyl halides using CpMo(CO)3 radical. For the third method, fast radical ligand substitution kinetics has been exploited to generate CpMo(CO)2PR3 radicals from CpMo(CO)3 in the presence of free phosphines. An assessment of the three methods with respect to TR-FTIR spectroscopic detection of radicals was also discussed.

KW - Halide abstraction

KW - Ligand substitution kinetics

KW - Metal-metal bond dissociation

KW - TR-FTIR radical spectra

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DO - 10.1016/j.jorganchem.2005.06.015

M3 - Article

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SN - 0022-328X

VL - 690

SP - 4132

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 18

ER -

TR-FTIR absorption spectroscopy of transition metal carbonyl radicals generated by photodissociation of metal-metal bonds, by halogen abstraction or by radical ligand substitution

Abstract

ASJC Scopus Subject Areas

Keywords

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