A Pincer Motif Etched into a meta-Benziporphyrin Frame
The incorporation of a meta-phenylene moiety into a β-alkylated or meso-tetraarylporphyrin framework resulted in the formation of m-benziporphyrins. Their molecular design preserves all the essential virtues of the original tetrapyrrolic architecture of r
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A Pincer Motif Etched into a meta-Benziporphyrin Frame Karolina Hurej and Lechosław Latos-Grażyński
Contents 1 The Convolution of Pincer Ligands and m-Benziporphyrins: Outlook 2 The Synthesis of m-Benziporphyrin and Aza-m-Benziporphyrins: Toward a Pincer-Like Macrocyclic Ligand Library 2.1 m-Benziporphyrins 2.2 m-Benziporphodimethenes 2.3 meso-Alkylidenyl-m-Benziporphyrins 2.4 22-Alkyl-m-Benziporphyrins 2.5 Aza-m-Benziporphyrins 3 m-Benziporphyrins: Transformations of m-Phenylene Unit 3.1 Inner Core Transformations 3.2 Perimeter Modifications: Hydroxy and Alkoxy Substituents 4 m-Benziporphyrins and Aza-m-Benziporphyrins: Coordination Chemistry 4.1 Coordination Motifs 4.2 Inner Core Reactivity 4.3 C–H Bond Activation 4.4 C–C Bond Activation 4.5 Contraction of m-Phenylene 4.6 Contraction: General Remarks 5 Conclusion and Perspectives References
Abstract The incorporation of a meta-phenylene moiety into a β-alkylated or mesotetraarylporphyrin framework resulted in the formation of m-benziporphyrins. Their molecular design preserves all the essential virtues of the original tetrapyrrolic architecture of regular porphyrin, including the perfect match between the ionic radii of the inserted metal cation and the size of the macrocyclic (CNNN) core, and steric protection provided by thoughtfully chosen β-alkyl or meso-aryl substituents.
K. Hurej and L. Latos-Grażyński (*) Department of Chemistry, University of Wrocław, Wrocław, Poland e-mail: [email protected]; [email protected]; http://llg.chem.uni.wroc.pl/
K. Hurej and L. Latos-Grażyński
The analogous incorporation of a pyridine moiety yielded a class of pyriporphyrins. The organometallic derivatives of m-benziporphyrins and pyriporphyrins are reminiscent of the large family of pincer ligand complexes, in which the metal–arene bond is supported by two amine or phosphine arms. This chapter relates the chemistry of the pincer ligand and that of the m-benziporphyrin (aza-mbenziporphyrin) emphasizing the fact that both groups have been structurally and functionally based on common dominators, i.e., on m-phenylene (aza-m-phenylene) rings. Keywords Carbaporphyrin · Contraction · Metalloporphyrins · Pincer ligand · Porphyrin
1 The Convolution of Pincer Ligands and m-Benziporphyrins: Outlook The multiple biochemical roles played by iron protoporphyrin IX have inspired many diverse studies of fundamental scientific significance, triggering a search for suitable porphyrins and metalloporphyrins prearranged to act as biomimetic models. The activation of dioxygen, oxygen atom transfer, and the direct functionalization of C–H bonds via metal-catalyzed atom/group transfer reactions are ground-breaking, attractive areas of exploration. All of them require porphyrin or metalloporphyrin participation. In general, advances in metalloporphyrin chemistry are evidently convoluted with developments in porphyrin synthetic methods. In light of these, it is quite clear why chemists in sophisticated explorations in principle mostly apply meso-arylsubstit
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