Preparation of [meso-tetraphenylchlorophinato]nickel(II) by stepwise deformylation of [meso-tetraphenyl-2,3-diformyl-secochlorinato]nickel(II); conformational consequences of breaking the structural integrity of nickel porphyrins
Bruckner, C., Hyland, M.A., Sternberg, E.D., MacAlpine, J.K., Rettig, S.J., Patrick, B.O., David Dolphin
Inorg. Chim. Acta, 358
The stepwise, Wilkinson's catalyst-induced decarbonylation of [meso-tetraphenyl-2,3-diformylsecochlorinato]Ni(II) to produce the monoformylated pigment [meso-tetraphenyl-2-formylsecochlorinato] and [meso-tetraphenylchlorophinato]Ni(II) is described. Thus, we have shown how to degrade one pyrrolic unit of the starting material, [meso-tetraphenylporphyrinato]Ni(II) in three steps to an aldimine linkage. The conformational changes of the porphyrinic macrocycle during the course of this degradation, as determined by comparison of the X-ray crystal structures of the compounds, are discussed. A comparative study delineates the UV–Vis spectroscopical consequences. In addition, the chemical reactivity of [meso-tetraphenyl-chlorophinato]Ni(II) suggests the existence of an azepine-derived pyrrole-modified porphyrins.