John D. Harvey

N-H tautomerization in triaryl corroles

Two high resolution single X-ray crystal structures of meso-substituted free-base corroles are presented: 5,10,15-triphenylcorrole (1) and 5,10,15-tris(pentafluorophenyl)corrole (2). The internal NH protons are clearly assignable to different nitrogens, which represents the two tautomer limits of corrole.

Dimeric and monomeric forms of manganese N-confused porphyrin

The synthesis and structural characterization of a manganese adduct of N-confused tetraphenylporphyrin (NCTPP) is presented; in the absence of coordinating ligands this complex forms a novel dimer structure and demonstrates a potential manganese agostic interaction with the interior pyrrolic CH as seen in other first row transition metal NCTPP compounds.

The synthesis of isostructural Mo2+ porphyrin and N-confused porphyrin complexes

We have synthesized the first early transition metal N-confused porphyrin complex Mo(NCTPP)(pip)2; this species is isostructural to its normal porphyrin analog Mo(TPP)(pip)2 but exhibits significant electronic differences arising from the inversion of a single pyrrolic group.

Manganese N-confused porphyrin reactivity: CH bond activation and meso carbon reduction

Manganese N-confused porphyrins activate C-C and C-H bonds upon heating or air oxidation; the dimer complex [Mn(NCTPP)]2 is reduced at two meso positions, and the pyridine coordinated monomer breaks the internal C-H bond upon heating or exposure to oxygen.

Dianionic and trianionic macrocycles in cobalt N-confused porphyrin complexes

We report the syntheses of cobalt N-confused porphyrins; this work completes the series of the late first-row transition metals that have been incorporated into the core of N-confused porphyrin, and in these compounds the macrocycles can act as either a -2 or -3 anion.