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Significant O–H Bond Weakening in CpMn(CO)<sub>2</sub>(CH<sub>3</sub>OH): Evidence for the Generation of the CpMn(CO)<sub>2</sub>(CH<sub>3</sub>O) Radical upon H Atom Abstraction by O<sub>2</sub>
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UV–visible photolysis of CpMnÂ(CO)<sub>3</sub> in methanol
generates CpMnÂ(CO)<sub>2</sub>(CH<sub>3</sub>OH), which upon H atom
abstraction using either O<sub>2</sub>, dpph, or H<sub>2</sub>O<sub>2</sub> gives the CpMnÂ(CO)<sub>2</sub>(CH<sub>3</sub>O) 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 CpMnÂ(CO)<sub>2</sub>(CH<sub>3</sub>OH) complex compared to free methanol. NBO spin density
analysis suggests that the bond cleavage is facilitated by the formation
of the CpMnÂ(CO)<sub>2</sub>(CH<sub>3</sub>O) radical in which the
electron spin is localized at the metal center rather than at the
oxygen atom
