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To Be or Not To Be Protonated: cyclo-N-5(-) in Crystal and Solvent

Author:
Chen, Wei  Liu, Zhiqiang  Zhao, Yinghe  Yi, Xianfeng  Chen, Zhongfang  Zheng, Anmin  


Journal:
JOURNAL OF PHYSICAL CHEMISTRY LETTERS


Issue Date:
2018


Abstract(summary):

Pentazole (HN5) and its anion (cyclo-N-5(-)) have been elusive for nearly a century because of the unstable N-5 ring. Recently, Zhang et al. reported the first synthesis and characterization of the pentazolate anion cyclo-N-5(-) in (N-5)(6)(H3O)(3)(NH4)(4)Cl salt at ambient conditions (Science 2017, 355, 374). However, whether the cyclo-N-5(-) in (N-5)(6)(H3O)(3)(NH4)(4)Cl salt is protonated or not has been debated (Huang and Xu, Science, 2018, 359, eaao3672; Jiang et al. Science, 2018, 359, aas8953). Herein, we employed ab initio molecular dynamics (AIMD) simulations, which can well present the dynamic behavior at realistic experimental conditions, to examine the potential protonated state of cyclo-N-5(-) in both crystal and dimethyl sulfoxide (DMSO) solvent. Our simulations revealed that the protonation reaction of (N-5)(6)(H3O)(3)(NH4)(4)Cl -> (N-5)(5)(N5H)(H2O)(H3O)(2)(NH4)(4)Cl is thermodynamically spontaneous according to Delta G < 0, and the small energy barrier of 12.6 kJ/mol is not enough to prevent the partial protonation of cyclo-N-5(-) due to the temperature effect; consequently, both deprotonated and protonated cyclo-N-5(-) exist in the crystal. In comparison, the DMSO solvent effect can remarkably reduce the difference of proton affinities among cyclo-N-5(-), H2O, and NH3, and the temperature effect can finally break these hydrogen bonds and lead to the deprotonated cyclo-N-5(-) in DMSO solvent. Our AIMD simulations reconcile the recent controversy.


Page:
7137---7145


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