Facile Aerobic Alkylation of Rhodium Porphyrins with Alkyl Halides

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 RhIII(por) species, including those
with tertiary alkyl, were synthesized. Mechanistic investigations
suggest a parallel SN2 via [RhI(ttp)]− with halogen atom transfer pathway via [RhII(ttp)]•.

铑卟啉的烷基化反应可在空气与水共存的条件下以中等至高产率完成。依托该简便烷基化方法，我们成功合成了多种烷基化三价铑卟啉配合物（RhIII(por)），其中涵盖带有叔烷基的物种。机理研究表明，该反应存在两条并行路径：一条为经由[RhI(ttp)]−的SN2反应路径，另一条为经由[RhII(ttp)]•的卤素原子转移路径。