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A DFT quest for effects of fused rings on the stability of remote N-heterocyclic carbenes

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Abstract

Assuming aromaticity (cyclic continuous conjugation, planarity, and obeying the Hückel 4n + 2 rule), effects of one and two fused six-membered heterocyclic rings are investigated on the energy lowering (stabilization) of 22 novel singlet (s) and triplet (t) carbenes, at B3LYP/AUG-cc-pVTZ and M06-2X/AUG-cc-pVTZ. Results display that (1) exclusive of triplet pyridine-4-ylidene, and s and t states, other species appear as ground state, so every s Hammick carbene exhibits more stability than its corresponding t state; (2) the highest stability is demonstrated by unsubstituted pyridine-4-ylidene as reference carbene, and the lowest stability is shown by carbene situated between two nitrogen heteroatoms of two fused rings, in a “W” arrangement; (3) regarding the relationship between carbenic center (CC) and substituted heteroatom, the order of stabilization for fused rings is meta > para > ortho; (4) regardless of how organized, fusion of one six-membered ring, in a given arrangement, has more stabilizing effect than two six-membered rings; (5) contrary to our expectation, t Hammick carbenes show higher band gap (ΔΕHOMO-LUMO) than their corresponding s species; (6) based on the NICS (nuclear independent chemical shift) results, the least stable carbene has the most aromaticity in its pyridine ring; and (7) according to proposed homomolecular isodesmotic reactions, all s states are stabilized via π-donor/σ-acceptor substitution more than the t states.

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Authors and Affiliations

  1. Department of Chemistry, Payame Noor University, Tehran, Iran

    Parvaneh Delir Kheirollahi Nezhad, Sheida Ahmadi & Esmail Vessally

  2. Department of Organic Chemistry, Faculty of Pharmaceutical Chemistry, Tehran Medical Sciences, Islamic Azad University, Tehran, Iran

    Leila Youseftabar-Miri

  3. Department of Chemistry, Ahar Branch, Islamic Azad University, Ahar, Iran

    Saeideh Ebrahimiasl

  4. Industrial Nanotechnology Research Center, Tabriz Branch, Islamic Azad University, Tabriz, Iran

    Saeideh Ebrahimiasl

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  1. Parvaneh Delir Kheirollahi Nezhad
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Correspondence to Sheida Ahmadi.

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Nezhad, P.D.K., Youseftabar-Miri, L., Ahmadi, S. et al. A DFT quest for effects of fused rings on the stability of remote N-heterocyclic carbenes. Struct Chem 32, 787–798 (2021). https://doi.org/10.1007/s11224-020-01650-5

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