Dicarbonylrhodium(I) complexes of polypyrrole macrocycles. Part 1. Preparation and oxidative addition reactions with alkyl halides and carboxylic acid anhydrides

Abstract

The reaction of polypyrrole macrocycles with di-µ-chloro-bisdicarbonylrhodium gives rise to out-of-plane mono-(with corroles and thiaphlorins) or bis-dicarbonylrhodium (with porphyrins and azaporphyrins) complexes, depending on the number of imino- and amino-groups present in the central macrocycle cavity. The tautomeric oxophlorins give both mono- and bis-dicarbonylrhodium complexes and the cobalt(III) complex of aetio-oxophlorin is shown by n.m.r. to exist as the aromatic zwitterion in benzene solution. The dicarbonylrhodium(I) complexes undergo oxidative addition reactions with alkyl halides and carboxylic acid anhydrides to give the corresponding alkyl- and acyl-rhodium(III) complexes of the polypyrrole macrocycles.