Abstract

Alkylation of rhodium porphyrins was achieved in moderate to high yields in the presence of air and water. With this facile alkylation method, various alkyl Rh<sup>III</sup>(por) species, including those with tertiary alkyl, were synthesized. Mechanistic investigations suggest a parallel S<sub>N</sub>2 via [Rh<sup>I</sup>(ttp)]<sup>−</sup> with halogen atom transfer pathway via [Rh<sup>II</sup>(ttp)]<sup>•</sup>

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