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Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ to gain a deeper insight into the nature of the N—Br halogen bonding. For the small complexes, H3C—Br…NH3 and H2N—Br…NH3, the primary calculation has demonstrated that the N—Br in H2N—Br…NH3 can form a much stronger halogen-bonding complex than the C—Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N>O>S; O(sp3)>O(sp2), which is adequate for the C—Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.
Ab initio calculations of complexes forming between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2 / Lanl2DZ to gain a deeper insight into the nature of the N-Br halogen bonding. For the small complexes, H3C- Br ... NH3 and H2N-Br ... NH3, the primary calculation has demonstrated that the N-Br in H2N-Br ... NH3 can form a much stronger halogen-bonding complex than the C-Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N> O> S; O (sp3)> O (sp2), which is adequate for the C-Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyzes further confirmed the above results.