The UV−visible photolysis of CpMn(CO) 3 in methanol generates CpMn(CO) 2 (CH 3 OH), which upon H atom abstraction using either O 2 , dpph, or H 2 O 2 gives the CpMn(CO) 2 (CH 3 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 CpMn(CO) 2 (CH 3 OH) complex compared to free methanol. NBO spin density analysis suggests that the bond cleavage is facilitated by the formation of the CpMn(CO) 2 (CH 3 O) radical in which the electron spin is localized at the metal center rather than at the oxygen atom.
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