2023
DOI: 10.1039/d2cc06648c
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Oxidative insertion of amines into conjugated macrocycles: transformation of antiaromatic norcorrole into aromatic azacorrole

Abstract: A new group of aromatic porphyrinoids was obtained by an oxidative insertion of primary amines into the antiaromatic ring of 5,14-dimesityl-norcorrolatonickel(ii) activated by iodosobenzene.

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Cited by 12 publications
(8 citation statements)
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“…Surprisingly, we find that the total ring current in the S 1 and T 1 states can be reversed from aromatic to antiaromatic by movement along the Kekulé vibration (∼2300 cm –1 ), i.e., by changing the amount of bond-length alternation . These aromaticity reversals require a relatively small amount of energy, in contrast with previous reports which require a change in the electronic state, molecular charge or composition, , or involve a high-lying transition state , or a highly strained geometry . To our knowledge, the only comparable low-energy aromaticity reversal involves a conformational equilibrium between Hückel antiaromatic and Möbius aromatic conformers in a hexaphyrin derivative. , …”
Section: Introductioncontrasting
confidence: 83%
“…Surprisingly, we find that the total ring current in the S 1 and T 1 states can be reversed from aromatic to antiaromatic by movement along the Kekulé vibration (∼2300 cm –1 ), i.e., by changing the amount of bond-length alternation . These aromaticity reversals require a relatively small amount of energy, in contrast with previous reports which require a change in the electronic state, molecular charge or composition, , or involve a high-lying transition state , or a highly strained geometry . To our knowledge, the only comparable low-energy aromaticity reversal involves a conformational equilibrium between Hückel antiaromatic and Möbius aromatic conformers in a hexaphyrin derivative. , …”
Section: Introductioncontrasting
confidence: 83%
“…In a previous paper 45 we reported the syntheses and characterisation of various azacorrole derivatives that differed in the substituents at meso -N but otherwise indicated very similar structural, electrochemical, and spectroscopic properties. The spectral and redox properties of the current systems indicate considerably more pronounced alteration to the electronic structure introduced by the substitution at the β-pyrrole positions, although very different substitution patterns of the derivatives prevent a more detailed analysis of the effects.…”
Section: Resultsmentioning
confidence: 99%
“…Synthesis of the precursor 10-Azacorrole 1 was synthesized according to the literature method. 45 General synthesis and characterization of 2a-b…”
Section: General Methodsmentioning
confidence: 99%
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“…The aromaticity of various porphyrinoids has been actively investigated. Porphyrinoids are excellent scaffolds for achieving effective macrocyclic π-conjugation, thus enabling aromaticity in Möbius π-systems, , large macrocycles, and macrocycles that contain metallocene units. Among various porphyrinoids, the macrocyclic aromaticity and antiaromaticity of 10-heterocorroles are sensitive to the heteroatoms incorporated at the 10-position, thus highlighting the important role that the heteroatoms play in the cyclic conjugation (Figure ). While a lone pair on either nitrogen (X = N), , oxygen (X = O), , sulfur (X = S), , phosphorus (X = P), or selenium (X = Se) in conjunction with the 16π-conjugation of the bis­(dipyrrin) unit leads to macrocyclic 18π-conjugated aromatic systems, 10-boracorrole (X = B) exhibits a unique form of global antiaromaticity due to the vacant p orbital on the boron atom, which affords a 16π-conjugated system. 10-Silacorrole (X = Si) shows no global antiaromaticity because the sp 3 -hybridized silicon atom disrupts the macrocyclic π-conjugation.…”
Section: Introductionmentioning
confidence: 99%