OXIDATIVE COUPLING OF RHODIUM PHENYL IMIDO/AMIDO COMPLEXES
1994
In previous work, we found that tautomeric mixtures of the late transition metal imido and amido complexes Rh{sub 2}({mu}-NPh)(CO){sub 2} ({mu}-dppm){sub 2} (1) and Rh{sub 2}({mu}-NHPh)(CO){sub 2}({mu}-dppm)({mu}-dppm-H){sup 2} (2) (hereafter designated as 1/2) undergo electrophilic ring addition reactions at the NPh group. A single electron transfer mechanism was considered. Such a mechanism would require oxidation of the imido/amido complex to a radical cation. To establish this possibility, we investigated the oxidation chemistry of this system. We found a rich chemistry consistent with formation and coupling of an amido radical cation. This chemistry, described here, is closely related to the well-studied oxidation chemistry of aniline and its derivatives. 16 refs.
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