Metalloporphyrins as chemical shift reagents: the unambiguous NMR characterization of the cis- and trans-isomers of meso-(bis)-4′-pyridyl-(bis)-4′-carboxymethylphenylporphyrins

The condensation of pyrrole with 4-pyridylcarboxyaldehyde and methyl 4-formyl benzoate under Adler-Longo conditions yielded the series of meso-(4′-pyridyl)/(4′-carboxymethylphenyl)porphyrins as a mixture. Careful column chromatography afforded each isomer in pure form. In this paper we focus on the two bis-substituted isomeric meso-porphyrins, 5,10-bis(4′-pyridyl)-15,20-bis(4′-carboxymethylphenyl)porphyrin and 5,15-bis(4′-pyridyl)-10,20-bis(4′-carboxymethylphenyl)porphyrin, respectively, 4′-cis and 4′-transDPyDMeP. The assignment of the geometry of the two isomers was performed by 1H NMR spectroscopy on the trinuclear adducts [(4′-cisDPyDMeP){Ru(TPP)(CO)}2] and [(4′-transDPyDMeP){Ru(TPP)(CO)}2], obtained by selective coordination of [Ru(TPP)(CO)(EtOH)] (TPP=tetraphenylporphyrin) to the peripheral nitrogen atoms. The axially bound ruthenium porphyrins act as chemical shift reagents on the central porphyrin, allowing a clear distinction of the pyrrole proton resonances and consequent unambiguous assignment of the geometry of each isomer based upon symmetry considerations.

Graphical abstractA new method to distinguish between the cis- and trans-isomers of meso-(bis)-4′-pyridyl-(bis)-4′-carboxymethylphenylporphyrins is described: selective coordination of [Ru(TPP)(CO)(EtOH)] to the pyridyl moieties allows the unambiguous assignment of the geometry of each isomer by 1H NMR spectroscopy.Download full-size image