Synthesis, Reactivity, and Properties of N-Fused Porphyrin Rhenium(I) Tricarbonyl Complexes

The thermal reactions of N-fused tetraarylporphyrins or N-confused tetraarylporphyrins with Re2(CO)10 gave the
rhenium(I) tricarbonyl complexes bearing N-fused porphyrinato ligands (4) in moderate to good yields. The rhenium
complexes 4 are characterized by mass, IR, 1H, and 13C NMR spectroscopy, and the structures of tetraphenylporphynato complex 4a and its nitro derivative 15 are determined by X-ray single crystal analysis. The rhenium complexes
4 show excellent stability against heat, light, acids, bases, and oxidants. The aromatic substitution reactions of 4
proceed without a loss of the center metal to give the nitro (15), formyl (16), benzoyl (17), and cyano derivatives
(19), regioselectively. In the electrochemical measurements for 4, one reversible oxidation wave and two reversible
reduction waves are observed. Their redox potentials imply narrow HOMO−LUMO band gaps of 4 and are consistent
with their electronic absorption spectra, in which the absorption edges exceed 1000 nm. Theoretical study reveals
that the HOMO and LUMO of the rhenium complexes are exclusively composed of the N-fused porphyrin skeleton.
Protonation of 4 takes place at the 21-position regioselectively, reflecting the high coefficient of the C21 atom in
the HOMO orbital. The skeletal rearrangement reaction from N-confused porphyrin Re(I) complex (8) to N-fused
porphyrin Re(I) complex (4) is suggested from the mechanistic study as well as DFT calculations.