Aminosilanes in organic synthesis. Preparation of new expanded porphyrin ligands and bimetallic transition-metal complexes. Crystal structure of a tetrapyrrole macrocycle dirhodium complex

Article abstract of DOI:10.1021/om00031a018

The synthesis of pyrrole via carbocupration of γ-amino-α,β-acetylene esters, followed by reaction with acid chlorides, was shown to provide facile routes to new polyheterocyclic compounds and tetrapyrrolic macrocycles. New expanded porphyrins were obtained in two steps from the reaction of diacid dichlorides. The new tetrapyrrole macrocycle formed bimetallic complexes of Pd, Ni, and Rh. The X-ray crystal structure of the dirhodium complex revealed that the two rhodium atoms (Rh-Rh interatomic distance 4.38 A?) lie on the same side of the macrocycle. The latter adopted an overall saddle shape conformation to relieve strain within the molecule.