meso-Aryl-substituted pentaphyrins were isolated in the modified Rothemund-Lindsey porphyrin synthesis as a 22-π-electron N-fused pentaphyrin (NFP5) and a 24-π-electron N-fuscd pentaphyrin (NFP 5), which were reversibly interconvertible by means of two-electron reduction with NaBH4 or two-electron oxidation with dichlorodicyanobenzoquinone (DDQ). Judging from 1H NMR data, NFP5 is aromatic and possesses a diatropic ring current, while NFP5 exhibits partial anti-aromatic character. Metalation of 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-π and 22-π electronic systems, respectively. In the rhodium(I) metalation of 1, the complex 9 was a major product at 20 °C, but the complex 10 became preferential at 55 °C. Upon treatment with DDQ, compound 9 was converted to 10 with an unprecedented rearrangement of the rhodium atom.
All Science Journal Classification (ASJC) codes
- Organic Chemistry