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Comparison of bis(alkylthio)carbenes by density functional and Second‐order Møller–Plesset perturbation theory
Journal of Physical Organic Chemistry ( IF 1.8 ) Pub Date : 2020-08-15 , DOI: 10.1002/poc.4122
Keywan Rahmi 1 , Mohammad Z. Kassaee 2 , Neda Khorshidvand 1, 2
Affiliation  

Thermodynamic parameters (including steric effects) of 15 new pairs of singlet and triplet bis(alkylthio)carbenes, R1 − S1−C¨−S2 − R2, (1R1,R2 and 3R1,R2, respectively), are compared and contrasted by B3LYP and MP2/AUG‐CC‐PVTZ; where R1 (or R2) = H, Me, Et, i‐Pr, and t‐Bu. Among the 30 carbenes scrutinized, the lowest nucleophilicity (N) and the highest electrophilicity (ω) are displayed by singlet 1H,H. In contract, triplet 3i‐Pr,t‐Bu exhibits the highest N, while the lowest ω is demonstrated by 3Me,Et. The maximum and minimum carbenic bond angles (S1−C¨−S2) are displayed by singlets 1H,H and 1Me,Me and triplets 3t‐Bu,t‐Bu and 3H,Et, respectively. The highest and lowest stability (∆Es‐t) are exhibited by 1Me,t‐Bu and 1H,H, respectively. The former may be stabilized primarily through lone pair donations from their sulfur atom into the empty pπ carbenic orbital, plus the formation of a five‐membered ring between hydrogen of methyl groups and the carbenic carbons. The highest and lowest band gaps (∆EH‐L) are exhibited by 3H,H and 1t‐Bu,t‐Bu, respectively. The highest and lowest chemical potentials (μ) are exhibited by 3Et,i‐Pr and 1H,H, respectively. Moreover, second‐order Møller–Plesset perturbation theory (MP2) provided a better discrimination between the scrutinized carbenes than density functional theory (DFT).

中文翻译:

用密度泛函和二阶Møller-Plesset微扰理论比较双(烷硫基)卡宾

热力学参数(包括位阻效应)的15个新的双单峰的重态和三重双(烷硫基)卡宾,R 1 - S 1 -C ¨ -S 2 - R的2,(1 R1R23 R1R2,分别地),通过B3LYP和MP2 / AUG-CC-PVTZ进行比较和对比; 其中R 1(或R 2)= H,Me,Et,i- Pr和t- Bu。在经过仔细检查的30种碳烯中,单线态1 H显示出最低的亲核性(N)和最高的亲电子性(ω)。H相反,三重态3 i- Prt- Bu具有最高的N,而最低的ω3 MeEt呈现。的最大和最小carbenic键角(S 1 -C ¨ -S 2)由单峰显示1 ħħ1和三胞胎3-Bu-Bu3 ħ的Et, 分别。最高和最低稳定性(∆ E s‐t)分别以1 Met ‐Bu1 HH表示。前者的稳定主要是通过将硫原子中的孤对捐赠给空的羧基轨道,以及在甲基的氢和羧基碳之间形成五元环来实现的。最高和最低带隙(∆E H‐L)显示为3 HH1 t ‐But ‐Bu, 分别。最高和最低化学势(μ)分别由3 Eti Pr1 HH表示。此外,与密度泛函理论(DFT)相比,二阶Møller-Plesset微扰理论(MP2)更好地区分了被检查的卡宾。
更新日期:2020-08-15
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