The effects of substitutions on structure, electron density, resonance and intramolecular hydrogen bonding strength in 3-mercapto-propenethial

Heidar Raissi , Emad Saleh Nadim , Mehdi Yoosefian , Farzaneh Farzad , Ebrahim Ghiamati , Ali Reza Nowroozi , Mustapha Fazli , Ali Amoozadeh
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引用次数: 39

Abstract

We are presenting a density functional calculation utilizing Beck three parameters hybrid, correlation functional of Lee, Yang and Parr (B3LYP), MP2 and G2MP2 levels of theory to probe the influence of R1, R2 and R3 substitutions on 3-mercapto-propenethial, estimating (i) The π-electron delocalization parameter (Q) as a geometrical indicator of a local aromaticity, (ii) the geometry-based HOMA index and (iii) intramolecular hydrogen-bond strength. The effects of F, H, Cl, CH3, OH, and NH2 as substituents are examined. Furthermore the topological properties of the electron density distributions for S–H⋯intramolecular bridges are analyzed in terms of the Bader theory of atoms in molecules (AIM). The electron density (ρ) and Laplacian (∇2ρ) properties, estimated by AIM calculations, indicate that S⋯H bond possesses low ρ and positive ∇2ρ values which are in agreement with electrostatic character of the HBs, whereas S–H bonds have covalent character (∇2ρ < 0). Natural population analysis data, the electron density and Laplacian properties, as well as, υ(S–H) and γ(S–H) have been used to evaluate the hydrogen bonding interactions.

取代对3-巯基丙烯的结构、电子密度、共振和分子内氢键强度的影响
我们利用Beck三参数杂化,Lee, Yang和Parr的相关函数(B3LYP), MP2和G2MP2理论水平,提出密度泛函计算,探讨R1, R2和R3取代对3-巯基-丙烯的影响,估计(i) π-电子离域参数(Q)作为局部芳香性的几何指标,(ii)基于几何的HOMA指数和(iii)分子内氢键强度。考察了F、H、Cl、CH3、OH和NH2作为取代基的影响。此外,根据分子中原子的Bader理论(AIM),分析了S-H⋯⋯分子内桥的电子密度分布的拓扑性质。通过AIM计算估计的电子密度(ρ)和拉普拉斯(∇2ρ)性质表明,S⋯H键具有低ρ和正的∇2ρ值,这符合HBs的静电特性,而S - H键具有共价特性(∇2ρ <利用自然居群分析数据、电子密度和拉普拉斯性质以及υ(S-H)和γ(S-H)来评价氢键相互作用。
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