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从涉及氢键、四元键、膦键、硫属键和卤键的复合物 B⋯A 的离解能确定路易斯碱 B 和路易斯酸 A 的亲核性和亲电性。

Nucleophilicities of Lewis Bases B and Electrophilicities of Lewis Acids A Determined from the Dissociation Energies of Complexes B⋯A Involving Hydrogen Bonds, Tetrel Bonds, Pnictogen Bonds, Chalcogen Bonds and Halogen Bonds.

机构信息

Instituto de Química Médica (IQM-CSIC), Juan de la Cierva, 3, E-28006 Madrid, Spain.

School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.

出版信息

Molecules. 2017 Oct 23;22(10):1786. doi: 10.3390/molecules22101786.

Abstract

It is shown that the dissociation energy D e for the process B⋯A = B + A for 250 complexes B⋯A composed of 11 Lewis bases B (N₂, CO, HC≡CH, CH₂=CH₂, C₃H₆, PH₃, H₂S, HCN, H₂O, H₂CO and NH₃) and 23 Lewis acids (HF, HCl, HBr, HC≡CH, HCN, H₂O, F₂, Cl₂, Br₂, ClF, BrCl, H₃SiF, H₃GeF, F₂CO, CO₂, N₂O, NO₂F, PH₂F, AsH₂F, SO₂, SeO₂, SF₂, and SeF₂) can be represented to good approximation by means of the equation D e = c ' N B E A , in which N B is a numerical nucleophilicity assigned to B, E A is a numerical electrophilicity assigned to A, and c ' is a constant, conveniently chosen to have the value 1.00 kJ mol here. The 250 complexes were chosen to cover a wide range of non-covalent interaction types, namely: (1) the hydrogen bond; (2) the halogen bond; (3) the tetrel bond; (4) the pnictogen bond; and (5) the chalcogen bond. Since there is no evidence that one group of non-covalent interaction was fitted any better than the others, it appears the equation is equally valid for all the interactions considered and that the values of N B and E A so determined define properties of the individual molecules. The values of N B and E A can be used to predict the dissociation energies of a wide range of binary complexes B⋯A with reasonable accuracy.

摘要

研究表明,对于由 11 个路易斯碱(N₂、CO、HC≡CH、CH₂=CH₂、C₃H₆、PH₃、H₂S、HCN、H₂O、H₂CO 和 NH₃)和 23 个路易斯酸(HF、HCl、HBr、HC≡CH、HCN、H₂O、F₂、Cl₂、Br₂、ClF、BrCl、H₃SiF、H₃GeF、F₂CO、CO₂、N₂O、NO₂F、PH₂F、AsH₂F、SO₂、SeO₂、SF₂ 和 SeF₂)组成的 250 个复合物 B⋯A,过程 B⋯A = B + A 的离解能 De 可以很好地用方程 De = c 'NB EA 表示,其中 NB 是分配给 B 的数值亲核性,EA 是分配给 A 的数值电负性,c '是一个常数,这里方便地选择为 1.00 kJ mol。选择这 250 个复合物是为了涵盖广泛的非共价相互作用类型,即:(1)氢键;(2)卤键;(3)四键;(4)膦键;和(5)硫键。由于没有证据表明一组非共价相互作用比其他相互作用拟合得更好,因此似乎该方程对所考虑的所有相互作用都同样有效,并且如此确定的 NB 和 EA 值定义了单个分子的性质。NB 和 EA 值可用于以合理的精度预测广泛的二元复合物 B⋯A 的离解能。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/176e/6151704/a9cefd9ee4f7/molecules-22-01786-g001.jpg

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