Computational Study on the Unconventional Hydrogen‐Bonded F–H···C Systems |
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Authors: | Hsin‐Yi Liao |
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Institution: | Department of Science Education, National Taipei University of Education, Taipei 10659, Taiwan, R.O.C. |
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Abstract: | The F–H···YZ2 (Y = C, Si, BH, A1H;Z = H, PH3) systems were examined using density functional theory calculations. The main focus of this work is to demonstrate that the chemistry of Y(PH3)2 exhibits a novel feature which is a central Y atom with unexpected high basicity. Further, the hydrogen bond strength can be adjusted by the substitution of H atoms of YH2 by PH3 groups. The FH···C(PH3)2 system has the strongest hydrogen bond interaction, which is larger than a conventional hydrogen bond. In addition to electrostatic interaction, donor‐acceptor interaction also plays an important role in determining the hydrogen bond strength. Therefore, a carbon atom can not only be the hydrogen bond acceptor but also can create an unusual stabilized hydrogen bond complex. Also, X3B–YZ2 (X = H, F; Y = C, Si, BH, A1H;Z = PH3, NH3) systems were examined, and it was found that the bond strength is controlled predominately by the HOMO‐LUMO gap (ΔIP). The smaller the ΔIP, the larger the bond dissociation energy of the B–Y bond. In addition, NH3 is a better electron‐donating group than PH3, and thus forms the strongest donor‐acceptor interaction between X3B and Y(NH3)2. |
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Keywords: | Unconventional hydrogen bonds Density functional theory HOMO‐LUMO gap Donor‐acceptor interaction |
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