A study of porphyrins with metal-carbon and metal-metal bonds : the influence of the axial and equatorial ligands on their redox properties

Electrochemical, spectroelectrochemical, and ESR techniques were used to evaluate the electron transfer reactions of several synthetic porphyrins. These metalloporphyrins included complexes of galliumClII), indium(III) and iron(III) which were a bonded with alkyl or aryl groups. This latter series of iron complexes existed in either a high, or low spin state depending on the type of porphyrin ring and the nature of the bound aryl ligand. For the case of indium(III) and gallium(III), all oxidations and reductions involved the ir ring system. This was not true for the a bonded iron complexes where reduction and possibly oxidation of the metal center occurred. Other complexes investigated as part of this dissertation were tin and germanium porphyrins which were metal-metal bonded to iron tetracarbonyl. [...]