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Novel triplet silavinylidenes via density functional theory
Journal of Physical Organic Chemistry ( IF 1.8 ) Pub Date : 2020-05-11 , DOI: 10.1002/poc.4074
Mojgan Ayoubi‐Chianeh 1 , Mohamad Z. Kassaee 1
Affiliation  

Following our quest for novel triplet silylenes, we have compared and contrasted electronic effects on 5‐silavinylidenyl‐1,4‐diX‐tetrazoles with XH, CH3, OCH3, NH2, NMe2, OH, CN, Cl, CF3, and F (110, respectively), at M06/6‐311++G** level of theory. Six structures with XH (1) and electron‐donating groups (EDGs, 26) appear triplet while the other four with electron‐withdrawing groups (EWGs, 710) show singlet ground states. The overall trend for triplet stability based on their ΔEs‐t is 1 > 2 > 3 > 4 > 5 > 6 > 7 > 8 > 9 > 10. The EWGs increase electrophilicity (ω) making 7 (7.09 eV) as the most electrophilic species. In contrast, EDGs increase nucleophilicity (N) showing 5 (5.47 eV) and 8 (3.18 eV) as the most and least nucleophilic silylenes, respectively. Moreover, 5 and 8 show the highest and lowest chemical potential (μ = −3.14 and −5.29 eV, respectively). In addition, 5 displays the highest energies of HOMO (EHOMO = −4.02 eV) and LUMO (ELUMO = −2.27 eV) and the lowest ω (2.82 eV) among the scrutinized species.

中文翻译:

基于密度泛函理论的新型三重态硅亚乙烯基

在我们寻求新型三线态亚甲硅基之后,我们比较并对比了具有XH,CH 3,OCH 3,NH 2,NMe 2,OH,CN,Cl,5 -silavinylidenyl-1,4-diX-四唑的电子效应。CF 3和F(分别为110),处于M​​06 / 6-311 ++ G **理论水平。具有XH(1)和给电子基团(EDGs,26)的六个结构显示三重态,而具有吸电子基团(EWGs,710)的其他四个显示单重态基态。根据他们的ΔE为三重稳定的总体趋势S-T1> 2 > 3 > 4 > 5 > 6 > 7 > 8 > 9 > 10。EWG增加了亲电性(ω),使7(7.09 eV)成为最亲电的物质。相反,EDG增加了亲核性(N),分别显示出5(5.47 eV)和8(3.18 eV)是最高和最低亲核性亚甲硅烷基。此外,58显示最高和最低化学势(分别为μ = -3.14和-5.29 eV)。此外,图5显示了在经仔细检查的物种中,HOMO(E HOMO = -4.02 eV)和LUMO(E LUMO = -2.27 eV)的最高能量和最低ω(2.82 eV)。
更新日期:2020-05-11
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