Organometallic Chemistry within the Structured Environment Provided by the Macrocyclic Cores of Carbaporphyrins and Related Systems.

Publisher: MDPI Country of Publication: Switzerland NLM ID: 100964009 Publication Model: Electronic Cited Medium: Internet ISSN: 1420-3049 (Electronic) Linking ISSN: 14203049 NLM ISO Abbreviation: Molecules Subsets: PubMed not MEDLINE; MEDLINE

Original Publication: Basel, Switzerland : MDPI, c1995-

The unique environment within the core of carbaporphyrinoid systems provides a platform to explore unusual organometallic chemistry. The ability of these structures to form stable organometallic derivatives was first demonstrated for N-confused porphyrins but many other carbaporphyrin-type systems were subsequently shown to exhibit similar or complementary properties. Metalation commonly occurs with catalytically active transition metal cations and the resulting derivatives exhibit widely different physical, chemical and spectroscopic properties and range from strongly aromatic to nonaromatic and antiaromatic species. Metalation may trigger unusual, highly selective, oxidation reactions. Alkyl group migration has been observed within the cavity of metalated carbaporphyrins, and in some cases ring contraction of the carbocyclic subunit takes place. Over the past thirty years, studies in this area have led to multiple synthetic routes to carbaporphyrinoid ligands and remarkable organometallic chemistry has been reported. An overview of this important area is presented.

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CHE-1855240 National Science Foundation

Keywords: aromaticity; azuliporphyrins; benziporphyrins; carbaporphyrins; organometallic complexes; oxidations; porphyrinoids; rearrangements

Date Created: 20230211 Date Completed: 20230213 Latest Revision: 20230214

20240829

PMC9920839

10.3390/molecules28031496

36771158