Significant O-H bond weakening in CpMn(CO)2(CH3OH): Evidence for the generation of the CpMn(CO)2(CH3O) radical upon H atom abstraction by O2

Jun Wei Kee; Tsz Sian Chwee; Xiang Yeow Tan; Richard D. Webster; Wai Yip Fan

doi:10.1021/om400504c

Significant O-H bond weakening in CpMn(CO)₂(CH₃OH): Evidence for the generation of the CpMn(CO)₂(CH₃O) radical upon H atom abstraction by O₂

Jun Wei Kee, Tsz Sian Chwee, Xiang Yeow Tan, Richard D. Webster, Wai Yip Fan^*

^*Corresponding author for this work

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

7 Citations (Scopus)

Abstract

The UV-visible photolysis of CpMn(CO)₃ in methanol generates CpMn(CO)₂(CH₃OH), which upon H atom abstraction using either O₂, dpph, or H₂O₂ gives the CpMn(CO)₂(CH₃O) radical complex. The radical with a lifetime of 10 to 20 min has been mainly characterized using FTIR and ESR spectroscopy and chemical oxidation studies. Together with density functional theory calculations, it is shown that the O-H bond is significantly weakened in the CpMn(CO)₂(CH₃OH) complex compared to free methanol. NBO spin density analysis suggests that the bond cleavage is facilitated by the formation of the CpMn(CO)₂(CH₃O) radical in which the electron spin is localized at the metal center rather than at the oxygen atom.

Original language	English
Pages (from-to)	4359-4365
Number of pages	7
Journal	Organometallics
Volume	32
Issue number	15
DOIs	https://doi.org/10.1021/om400504c
Publication status	Published - Aug 12 2013
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Significant O-H bond weakening in CpMn(CO)2(CH3OH): Evidence for the generation of the CpMn(CO)2(CH3O) radical upon H atom abstraction by O2",

abstract = "The UV-visible photolysis of CpMn(CO)3 in methanol generates CpMn(CO)2(CH3OH), which upon H atom abstraction using either O2, dpph, or H2O2 gives the CpMn(CO)2(CH3O) radical complex. The radical with a lifetime of 10 to 20 min has been mainly characterized using FTIR and ESR spectroscopy and chemical oxidation studies. Together with density functional theory calculations, it is shown that the O-H bond is significantly weakened in the CpMn(CO)2(CH3OH) complex compared to free methanol. NBO spin density analysis suggests that the bond cleavage is facilitated by the formation of the CpMn(CO)2(CH3O) radical in which the electron spin is localized at the metal center rather than at the oxygen atom.",

author = "Kee, \{Jun Wei\} and Chwee, \{Tsz Sian\} and Tan, \{Xiang Yeow\} and Webster, \{Richard D.\} and Fan, \{Wai Yip\}",

year = "2013",

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doi = "10.1021/om400504c",

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TY - JOUR

T1 - Significant O-H bond weakening in CpMn(CO)2(CH3OH)

T2 - Evidence for the generation of the CpMn(CO)2(CH3O) radical upon H atom abstraction by O2

AU - Kee, Jun Wei

AU - Chwee, Tsz Sian

AU - Tan, Xiang Yeow

AU - Webster, Richard D.

AU - Fan, Wai Yip

PY - 2013/8/12

Y1 - 2013/8/12

N2 - The UV-visible photolysis of CpMn(CO)3 in methanol generates CpMn(CO)2(CH3OH), which upon H atom abstraction using either O2, dpph, or H2O2 gives the CpMn(CO)2(CH3O) radical complex. The radical with a lifetime of 10 to 20 min has been mainly characterized using FTIR and ESR spectroscopy and chemical oxidation studies. Together with density functional theory calculations, it is shown that the O-H bond is significantly weakened in the CpMn(CO)2(CH3OH) complex compared to free methanol. NBO spin density analysis suggests that the bond cleavage is facilitated by the formation of the CpMn(CO)2(CH3O) radical in which the electron spin is localized at the metal center rather than at the oxygen atom.

AB - The UV-visible photolysis of CpMn(CO)3 in methanol generates CpMn(CO)2(CH3OH), which upon H atom abstraction using either O2, dpph, or H2O2 gives the CpMn(CO)2(CH3O) radical complex. The radical with a lifetime of 10 to 20 min has been mainly characterized using FTIR and ESR spectroscopy and chemical oxidation studies. Together with density functional theory calculations, it is shown that the O-H bond is significantly weakened in the CpMn(CO)2(CH3OH) complex compared to free methanol. NBO spin density analysis suggests that the bond cleavage is facilitated by the formation of the CpMn(CO)2(CH3O) radical in which the electron spin is localized at the metal center rather than at the oxygen atom.

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Significant O-H bond weakening in CpMn(CO)₂(CH₃OH): Evidence for the generation of the CpMn(CO)₂(CH₃O) radical upon H atom abstraction by O₂

Abstract

ASJC Scopus Subject Areas

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