Dicarbonylrhodium(I) complexes of polypyrrole macrocycles. Part 3. Synthesis and crystal structures of complexes of N-methylcorroles, N-methylporphyrins, and acyclic polypyrroles

Abstract

The reaction of di-µ-chloro-bis(dicarbonylrhodium) with N-methylcorroles gives stable out-of-plane complexes involving adjacent nitrogen atoms. An analogous complex is formed by a 21,24-dioxacorrole. The N-22-methylcorrole complex undergoes thermal equilibration with an isomeric complex involving non-adjacent nitrogen atoms. The X-ray crystal structures of two N-methylcorrolebis[dicarbonylrhodium(I)] complexes are reported. Reaction of di-µ-chloro-bis(dicarbonylrhodium) with N-methyletioporphyrin I gives rise to methylrhodium(III)–etioporphyrin and a similar reaction was observed with N-methylazaporphyrins. In the presence of an alkyl iodide, competitive alkylation of the rhodium occurs. Several examples of bis(dicarbonylrhodium) complexes of acyclic pyrrolic systems are reported including the first stable transition-metal complex of a 1, 19-dideoxy-1, 19-diunsubstituted biladiene-a, c.