Substituent effects on the stability of cyclic - unsaturated remote N-heterocyclic Hammick carbenes using density functional theory

被引：11
|
作者：
Sogutlu, Inci [1 ]
Soltanzadeh, Mehdi [2 ]
Mert, Handan [3 ]
Mert, Nihat [3 ]
Vessally, Esmail [4 ]
机构：
[1] Republ Turkey Minist Agr & Forestry, Ankara, Turkey
[2] Univ Tabriz, Sch Engn Emerging Technol, Tabriz, Iran
[3] Van Yuzuncu Yil Univ, Fac Vet, Dept Biochem, Van, Turkey
[4] Payame Noor Univ, Dept Chem, POB 19395-4697, Tehran, Iran
来源：
JOURNAL OF MOLECULAR STRUCTURE | 2021年 / 1230卷
关键词：
Hammick carbene; DFT; Stability; NHCs; Nucleophilicity; TRANSITION-METAL-COMPLEXES; MOLECULAR-ORBITAL METHODS; ELECTRONIC-STRUCTURE; STABLE CARBENES; BASIS-SETS; CYCLONONA-3,5,7-TRIENYLIDENES; THERMOCHEMISTRY; ELEMENTS;
D O I：
10.1016/j.molstruc.2020.129821
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
We investigated the structure, stability and chemical properties of novel singlet (s) and triplet (t) Hammick carbenes with different fused aromatic rings, at (U)B3LYP/6-311+G*, (U)M06-2X/6-311+G*, (U)B3LYP/AUG-cc-pVTZ and (U)M06-2X/AUG-cc-pVTZ levels of theory. It is observed that: (1) All singlet and triplet structures appear as minima on their energy surfaces and each singlet carbene displays more thermodynamic stability than its corresponding triplet state; (2) Regarding to the relationship among carbenic center and substituted heteroatom, the order of thermodynamic stability based on singlet-triplet energy differences (Delta Es-t) for fused rings is ortho-pyrrole > furan > thiophene > phosphole in a "W" arrangement; (3) The highest kinetic stability based on band gap (Delta EHOMO-LUMO) is demonstrated by substituted ortho-pyrrole carbene in a "W" arrangement; (4) Regardless of how orchestrated, the order of stabilization for fused rings is pyrrole > furan > thiophene > phosphole; (5) The ortho-phosphole ring in a "W" arrangement destabilizes carbene more than benzene ring. (C) 2020 Elsevier B.V. All rights reserved.
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页数：9
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