Abstract
Carbonyl carbon centered radical reactivity in organo-transition-metal complexes has been previously observed only for transient 19-electron species. Abstraction of hydrogen from metal hydrides by (Fe(CO){sub 5}){sup {minus}} to form an intermediate 18-electron formyl complex, (Fe(CO){sub 4}CHO){sup {minus}}, is a prominent example of this type of reactivity. Studies of rhodium porphyrins with CO that produce metalloformyl, dimetal ketones, and dimetal {alpha}-diketons have suggested that a 17-electron metalloorganic radical, (por)Rh-CO, may function as an intermediate, but this type of species has eluded direct observation. This article reports on the reversible reaction of tetramesitylporphyrinrhodium(II), (TMP)Rh{center dot}, with CO to form (TMP)Rh-CO, 2 which dimerizes by C-C bond formation. EPR and reactivity studies of 2 indicate the presence of a bent CO fragment with a partially rehybridized CO unit that facilitates one-electron reactions at the carbonyl carbon center.
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