Synthesis of N,N'-1,2-Vinylidene and 1,2-Phenylene Bridged Porphyrins. X-ray Crystal and Molecular Structure of an N,N'-(Diphenyl-1,2-vinylidene)-meso-tetraphenylporphyrin

Article abstract of DOI:10.1021/ja00244a016

The synthesis of N,N'-1,2-vinylidene and 1,2-phenylene bridged porphyrins, which are models of the inactivation products of cytochrome P-450 in the presence of 1-aminobenzotriazole (ABT) has been accomplished.They are prepared from N-aryl- or N-styrylporphyrins either by oxidation with amine cation radicals or electrochemically.Alternatively the direct reaction of a cobalt(III) porphyrin with ABT gave an N,N'-1,2-phenyleneporphyrin and an N-phenylporphyrin.The structure of an N,N'-(diphenyl-1,2-vinylidene)-meso-tetraphenylporphyrin, as its hydroperchlorate, was determined by X-ray crystallography.It showed (i) a considerable folding of the new seven-membered ring formed by the introduction of the 1,2-vinylidene group, (ii) that the protonated nitrogen atoms are the unsubstituted ones, and (iii) that the ?-electron delocalization in the porphinato core is only moderately affected by the insertion of the two-carbon bridge.