meso-Aryl-substituted pentaphyrins were isolated in the modified Rothemund-Lindsey porphyrin synthesis as a 22-pi-electron N-fused pentaphyrin ([22]NFP5) and a 24-pi-electron N-fused pentaphyrin ([24]NFP5), which were reversibly interconvertible by means of two-electron reduction with NaBH4 or two-electron oxidation with dichlorodicyanobenzoquinone (DDQ). Judging from 1H NMR data, [22]NFP5 is aromatic and possesses a diatropic ring current, while [24]NFP5 exhibits partial anti-aromatic character. Metalation of [22]NFP5 1 with a rhodium(I) salt led to isolation of rhodium complexes 9 and 10, whose structures were unambiguously characterized by X-ray diffraction analyses and were assigned as conjugated 24-pi and 22-pi electronic systems, respectively. In the rhodium(I) metalation of 1, the complex 9 was a major product at 20 degrees C, but the complex 10 became preferential at 55 degrees C. Upon treatment with DDQ, compound 9 was converted to 10 with an unprecedented rearrangement of the rhodium atom.