氢键与氢化氢的氢键——实验低温红外和计算研究：氢键的修订定义是否合适？,Journal of the American Chemical Society

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氢键与氢化氢的氢键——实验低温红外和计算研究：氢键的修订定义是否合适？
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-04-10 , DOI: 10.1021/jacs.3c00802
Svatopluk Civiš _{1,

2} , Maximilián Lamanec _{1,

3,

4} , Vladimír Špirko ₁ , Jiří Kubišta ₂ , Matej Špet'ko ₃ , Pavel Hobza _{1,

3}

Affiliation

Me ₃ Si–H···Y配合物的光谱特征(Y = ICF ₃, BrCN, and HCN) containing a hydridic hydrogen is experimentally determined by low-temperature IR experiments based on the direct spectral measurement of ultrasonic expanded intermediates on a cold substrate or by the technique of argon-matrix isolation as well as computationally at harmonic and one -维度非谐波水平。计算基于使用各种扩展 AO 基组的 DFT-D、MP2、MP2-F12 和 CCSD(T)-F12 水平。所有与复合物形成时 Si-H 伸缩频率红移相关的复合物的形成都伴随着其强度的增加。对于另外 10 个不同类型的电子受体、正 σ-、π- 和 p-空穴和阳离子，也获得了类似的结果。HBe-H···Y 配合物的形成，仅通过计算研究并再次包含氢，其特征是 Be-H 伸缩频率在络合时发生蓝移，并伴随着强度的增加。目前研究的所有氢氢键合配合物的光谱偏移和稳定能量都与质子氢键配合物相当，这促使我们提出修改现有的 IUPAC 氢键定义，除了经典的质子形式，非经典的氢和二氢形式。

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Hydrogen Bonding with Hydridic Hydrogen–Experimental Low-Temperature IR and Computational Study: Is a Revised Definition of Hydrogen Bonding Appropriate?

Spectroscopic characteristics of Me₃Si–H···Y complexes (Y = ICF₃, BrCN, and HCN) containing a hydridic hydrogen were determined experimentally by low-temperature IR experiments based on the direct spectral measurement of supersonically expanded intermediates on a cold substrate or by the technique of argon-matrix isolation as well as computationally at harmonic and one-dimensional anharmonic levels. The computations were based on DFT-D, MP2, MP2-F12, and CCSD(T)-F12 levels using various extended AO basis sets. The formation of all complexes related to the redshift of the Si–H stretching frequency upon complex formation was accompanied by an increase in its intensity. Similar results were obtained for another 10 electron acceptors of different types, positive σ-, π-, and p-holes and cations. The formation of HBe–H···Y complexes, studied only computationally and again containing a hydridic hydrogen, was characterized by the blueshift of the Be–H stretching frequency upon complexation accompanied by an increase in its intensity. The spectral shifts and stabilization energies obtained for all presently studied hydridic H-bonded complexes were comparable to those in protonic H-bonded complexes, which has prompted us to propose a modification of the existing IUPAC definition of H-bonding that covers, besides the classical protonic form, the non-classical hydridic and dihydrogen forms.

更新日期：2023-04-10

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