Pub No:
406
Title:
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
Authors:
Bruckner, C., Hyland, M.A., Sternberg, E.D., MacAlpine, J.K., Rettig, S.J., Patrick, B.O., David Dolphin
Journal:
Inorg. Chim. Acta, 358
Year:
2005
Pages:
2943-2953
Abstract:
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.

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