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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

TitlePreparation 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
Publication TypeJournal Article
Year of Publication2005
AuthorsBruckner, C, Hyland, MA, Sternberg, ED, Macalpine, JK, Rettig, SJ, Patrick, BO, Dolphin, D
JournalInorganica Chimica Acta
Volume358
Pagination2943-2953
Date PublishedJun
Type of ArticleArticle
ISBN Number0020-1693
KeywordsCHEMISTRY, CHIRALITY-MEMORY MOLECULE, CHLORIN, CHLOROPHIN, chlorophins, COMPLEXES, ELECTRONIC-SPECTRA, macrocycle, METHYLCOENZYME-M REDUCTASE, nickel(II) porphyrin conformations ruffling, porphyrins, secochlorins, SYSTEM, TUNICATE TRIDIDEMNUM-SOLIDUM, Wilkinson’s catalyst
Abstract

The stepwise, Wilkinson’s catalyst-induced decarbonylation of [meso-tetraphenyl-2,3-diformylsecochlorinato]Ni(II) (4) to produce the monoformylated pigment [meso-tetraphenyl-2-formylsecochlorinato] (5) and [meso-tetrapheiiylchlorophinato]Ni(II) (6) is described. Thus, we have shown how to degrade one pyrrolic unit of the starting material, [meso-tetraphetiylporphyrinato]Ni(II) (2) 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-tetraphenylchlorophinato]Ni(II) (6) suggests the existence of an azepine-derived pyrrole-modified porphyrins (11, 12). (c) 2004 Elsevier B.V. All rights reserved.

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