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

文献类型：期刊论文

作者Zheng, Anmin3; Chen, Zhongfang2; Yi, Xianfeng3; Zhao, Yinghe2; Liu, Zhiqiang3; Chen, Wei1,3
刊名JOURNAL OF PHYSICAL CHEMISTRY LETTERS
出版日期2018-12-20
卷号9期号:24页码:7137-7145
ISSN号1948-7185
DOI10.1021/acs.jpclett.8b02841
英文摘要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.
WOS关键词CORRELATED MOLECULAR CALCULATIONS ; GAUSSIAN-BASIS SETS ; PENTAZOLATE ANION ; ATOMS ; ENERGY
资助项目National Natural Science Foundation of China[21522310] ; National Natural Science Foundation of China[21473244] ; National Natural Science Foundation of China[91645112] ; Natural Science Foundation of Hubei Province of China[2018CFA009] ; Key Research Program of Frontier Sciences, CAS[QYZDB-SSW-SLH026] ; National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N)[HRD-1736093] ; NASA[80NSSC17M0047]
WOS研究方向Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics
语种英语
WOS记录号WOS:000454752000033
出版者AMER CHEMICAL SOC
资助机构National Natural Science Foundation of China ; National Natural Science Foundation of China ; Natural Science Foundation of Hubei Province of China ; Natural Science Foundation of Hubei Province of China ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N) ; National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N) ; NASA ; NASA ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Natural Science Foundation of Hubei Province of China ; Natural Science Foundation of Hubei Province of China ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N) ; National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N) ; NASA ; NASA ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Natural Science Foundation of Hubei Province of China ; Natural Science Foundation of Hubei Province of China ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N) ; National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N) ; NASA ; NASA ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Natural Science Foundation of Hubei Province of China ; Natural Science Foundation of Hubei Province of China ; Key Research Program of Frontier Sciences, CAS ; Key Research Program of Frontier Sciences, CAS ; National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N) ; National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N) ; NASA ; NASA
源URL[http://ir.wipm.ac.cn/handle/112942/14002]  
专题中国科学院武汉物理与数学研究所
通讯作者Zheng, Anmin; Chen, Zhongfang
作者单位1.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
2.Univ Puerto Rico, Dept Chem, Rio Piedras Campus, San Juan, PR 00931 USA
3.Chinese Acad Sci, State Key Lab Magnet Resonance & Atom & Mol Phys, Natl Ctr Magnet Resonance Wuhan, Wuhan Inst Phys & Math, Wuhan 430071, Hubei, Peoples R China
推荐引用方式
GB/T 7714		 Zheng, Anmin,Chen, Zhongfang,Yi, Xianfeng,et al. To Be or Not To Be Protonated: cyclo-N-5(-) in Crystal and Solvent[J]. JOURNAL OF PHYSICAL CHEMISTRY LETTERS,2018,9(24):7137-7145.
APA Zheng, Anmin,Chen, Zhongfang,Yi, Xianfeng,Zhao, Yinghe,Liu, Zhiqiang,&Chen, Wei.(2018).To Be or Not To Be Protonated: cyclo-N-5(-) in Crystal and Solvent.JOURNAL OF PHYSICAL CHEMISTRY LETTERS,9(24),7137-7145.
MLA Zheng, Anmin,et al."To Be or Not To Be Protonated: cyclo-N-5(-) in Crystal and Solvent".JOURNAL OF PHYSICAL CHEMISTRY LETTERS 9.24(2018):7137-7145.

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来源：武汉物理与数学研究所

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