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Synthesis And Metalation Of Internally Alkylated Porphyrinoids, Alissa Nicole Latham

Theses and Dissertations

The mechanism behind alkyl migration in palladium(II) benzocarbaporphyrins was investigated through the synthesis of a 23-methylcarbaporphyrin. It was found that palladium insertion led to methyl group migration to C21 and it is proposed that this occurs through an oxidative addition onto the palladium metal center, followed by a reductive elimination to transfer the methyl to the internal carbon. A similar rearrangement was observed when 23-methylcarbaporphyrin was reacted with [Rh(CO)2Cl]2 and resulted in the formation of a rhodium(III) complex containing a three-membered rhodacycle. The syntheses of rhodium(I) and rhodium(III) derivatives of other carbaporphyrins, including 21- and 22-methylbenzo-carbaporphyrins, were probed and four …