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Investigation of fused remote N-heterocyclic silylenes (frNHSis), at DFT

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Abstract

We compared and contrasted the ΔΕs-t, band gap (ΔΕHOMO-LUMO), aromaticity, charge distribution, and reactivity of singlet (s) and triplet (t) benzopyridine-4-ylidene as the fused remote N-heterocyclic carbene (frNHC) and frNHSis with different fused aromatic rings, at (U)B3LYP/AUG-cc-pVTZ and (U)M06-2X/AUG-cc-pVTZ levels of theory. In this investigation, we found (1) all s and t divalent states appear as minimum structures, for having no negative force constant. Nonetheless, only singlets present more thermodynamic stability than their triplet analogous; (2) the trend of ΔΕs-t in kcal/mol is ortho-pyrrole (52.94) > ortho-furan (51.84) > ortho-thiophene (50.38) > para-furan (49.36) > para-pyrrole (49.00) > para-phosphole (48.67) ≥ para-thiophene (48.64) > benzene (44.33) > ortho-phosphole frNHSi (27.50), while ΔΕs-t of frNHC is 15.65 kcal/mol; (3) apart from phosphole frNHSis, the order of ΔΕs-t in a “ortho position or zigzag array” about 1.8–4.0 kcal/mol is more than that of in a “para position or chair array”; (4) the highest ΔΕHOMO-LUMO is demonstrated by ortho-pyrrole frNHSi (95.65 kcal/mol) while the lowest ΔΕHOMO-LUMO is verified by the reference frNHC (63.44 kcal/mol); (5) in contradiction of frNHC, all singlet frNHSis reveal higher band gap and lower global reactivity than their triplet congeners; (6) charge distribution along with MEP maps indicate differentially electronic cloud in middle of rings frNHSis vs. frNHC; (7) we anticipate higher nucleophilicity and lower electrophilicity of triplet frNHSis than singlet congeners, will make them worthy of synthetic surveys.

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

    Esmail Vessally, Mohammad Reza Poor Heravi, Sepideh Habibzadeh & Zahra Rostami

  2. Department of Agriculture, Jouybar Branch, Islamic Azad University, Jouybar, Iran

    Abdol Ghaffar Ebadi

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Vessally, E., Ebadi, A.G., Heravi, M.R.P. et al. Investigation of fused remote N-heterocyclic silylenes (frNHSis), at DFT. J Mol Model 27, 299 (2021). https://doi.org/10.1007/s00894-021-04899-7

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