Journal
ORGANOMETALLICS
Volume 32, Issue 15, Pages 4359-4365Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om400504c
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- NUS [143-000-430-112]
- NUS
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The UV visible photolysis of CpMn(CO)(3) in methanol generates CpMn(CO)(2)(CH3OH), which upon H atom abstraction using either O-2, 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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