Perimeter Coordinated Diastereomeric Rh(I) Complex of Helically Twisted Weakly Aromatic Hybrid Singly N‑Confused β−β Fused Ferrocenoporphyrinoids.

Nyancy, Halder and Krushna Chandra, Sahoo and Gourav, Kumar and Usharani, D. and Harapriya, Rath (2021) Perimeter Coordinated Diastereomeric Rh(I) Complex of Helically Twisted Weakly Aromatic Hybrid Singly N‑Confused β−β Fused Ferrocenoporphyrinoids. Journal of Organic Chemistry, 86. pp. 8015-8026.

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Abstract

Expedient synthesis, spectroscopic, solid state structural proof, and theoretical study of helically twisted weakly aromatic hybrid singly Nconfused ferrocenoporphyrinoids and the peripheral coordinated Rh(I) complex are reported. The X-ray crystal structure of the macrocycles reveals an ambiguously inverted pyrrole ring reinforcing regioselective β,β-linkage with the spatially adjacent N-confused N-methyl pyrrole ring leading to endocyclic extension of macrocyclic π-conjugation via tricyclic [5.5.5] moiety. The three-dimensional structure with built-in fused tricyclic [5.5.5] moiety has paved way to three-dimensional weak diatropicity with vis−NIR absorptions. The peripheral coordinated Rh(I) complex owing to helical chirality about the macrocyclic ring and planar chirality about the square planar Rh coordination site exists as a mixture of diastereomers (5:3) with well resolved 1H NMR spectra anticipating weak aromaticity. The experimental spectroscopic measurements are in agreement with theoretically determined electronic structure and properties strongly elucidating sustained weak diatropic ring currents in twisted macrocycles both in neutral form and in the metalated complex. Further fragment molecular orbital approach and molecular orbital theory gave insights on the stability of N-confused β−β fused oxoferrocenoporphyrinoids and formation of the selective peripheral coordinated Rh(I) complex.

Item Type:	Article
Uncontrolled Keywords:	N-confused porphyrinoids
Subjects:	500 Natural Sciences and Mathematics > 04 Chemistry and Allied Sciences > 24 Organic Chemistry
Divisions:	Food Safety Analytical Quality Control Lab
Depositing User:	Food Sci. & Technol. Information Services
Date Deposited:	29 Mar 2022 06:38
Last Modified:	29 Mar 2022 06:38
URI:	http://ir.cftri.res.in/id/eprint/15148

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