Citation: ZHOU Xia-Yu, RONG Chun-Ying, LU Tian, LIU Shu-Bin. Hirshfeld Charge as a Quantitative Measure of Electrophilicity and Nucleophilicity: Nitrogen-Containing Systems[J]. Acta Physico-Chimica Sinica, ;2014, 30(11): 2055-2062. doi: 10.3866/PKU.WHXB201409193 shu

Hirshfeld Charge as a Quantitative Measure of Electrophilicity and Nucleophilicity: Nitrogen-Containing Systems

1.
1. Department of Pharmacy, Changde Vocational Technical College, Changde 415000, Hunan Province, P. R. China;
2. Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research Ministry of Education of China and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, P. R. China;
3. Beijing Kein Research Center for Natural Sciences, Beijing 100022, P. R. China;
4. Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, U.S.A.

Received Date: 7 August 2014
Available Online: 19 September 2014
Fund Project: 湖南省高校科技创新团队支持计划(湘教通[2012]318 号) (湘教通[2012]318 号) 湖南省自然科学基金(12JJ2029) (12JJ2029) 湖南省高校创新平台开放基金(12K030) (12K030) 常德市科技局重点项目(2014JF15) (2014JF15)湖南省省级科技计划项目(2013FJ4220)资助 (2013FJ4220)

To accurately predict the capability and possible reaction site for atoms in molecules to donate or accept electrons in chemical processes, i.e., to quantitatively determine electrophilicity, nucleophilicity, and regioselectivity, is an important yet incomplete task. Earlier, we proposed using the Hirshfeld charge and information gain as two equivalent descriptors for this purpose, based on the Information Conservation Principle we recently proposed. This idea was successfully applied to two series of molecular systems to confirm its validity. However, our previous work is hindered by the fact that the involved element is carbon. It is unclear if stockit applies to other elements and to different valence states of the same element. In this study, to address these issues, the method was applied to nitrogen-containing systems. Five different cate ries of compounds were studied, including benzenediazonium, azodicarboxylate, diazo, and primary and secondary amines, with a total of 40 molecules. The results show that there are strong linear correlations between the Hirshfeld charge and their experimental scales of electrophilicity and nucleophilicity. However, these correlations depend on the valence state and bonding environment of the nitrogen element. The linear relationship only holds within the same cate ry. Possible reasons for this observation are discussed.
- Hirshfeld charge,
- Information gain,
- Electrophilicity,
- Nucleophilicity,
- Regioselectivity
1. [1]
  
  (1) March, J. Advanced Organic Chemistry: Reactions, Mechanisms, and Structure;Wiley: New York, USA, 1985.
2. [2]
  (2) Swain, C. G.; Scott, C. B. J. Am. Chem. Soc. 1953, 75, 141. doi: 10.1021/ja01097a041
3. [3]
  (3) Ritchie, C. D. Accounts Chem. Res. 1972, 5, 348. doi: 10.1021/ar50058a005
4. [4]
  (4) Mayr, H.; Patz, M. Angew. Chem. Int. Edit. 1994, 33, 938.
5. [5]
  (5) Parr, R. G.; Yang,W. Density-Functional Theory of Atoms and Molecules. In International Series of Monographs on Chemistry; Clarendon Press: Oxford, England, 1989.
6. [6]
  (6) Geerlings, P.; DeProft, F.; Langenaeker,W. Chem. Rev. 2003, 103, 1793. doi: 10.1021/cr990029p
7. [7]
  (7) Chattaraj, P. K.; Sarkar, U.; Roy, D. R. Chem. Rev. 2006, 106, 2065. doi: 10.1021/cr040109f
8. [8]
  (8) Liu, S. B. Acta Phys. -Chim. Sin. 2009, 25, 590. [刘述斌. 物理化学学报, 2009, 25, 590.] doi: 10.3866/PKU.WHXB20090332
9. [9]
  (9) Parr, R. G.; Yang,W. J. Am. Chem. Soc. 1984, 106, 4049. doi: 10.1021/ja00326a036
10. [10]
  (10) Parr, R. G.; von Szentpaly, L.; Liu, S. B. J. Am. Chem. Soc. 1999, 121, 1922. doi: 10.1021/ja983494x
11. [11]
  (11) Jaramillo, P.; Perez, P.; Contreras, R.; Tiznado,W.; Fuentealba, P. J. Phys. Chem. A 2006, 110, 8181. doi: 10.1021/jp057351q
12. [12]
  (12) Ayers, P.W.; Anderson, J. S. M.; Rodriguez, J. I.; Jawed, Z. Phys. Chem. Chem. Phys. 2005, 7, 1918. doi: 10.1039/b500996k
13. [13]
  (13) Morell, C.; Grand, A.; Toro-Labbe, A. J. Phys. Chem. A 2005, 109, 205. doi: 10.1021/jp046577a
14. [14]
  (14) Ayers, P.W.; Morell, C.; De Proft, D.; Geerlings, P. Chem. Eur. J. 2007, 13, 8240.
15. [15]
  (15) Liu, S. B.; Ess, D. H.; Schauer, C. K. J. Phys. Chem. A 2011, 115, 4738. doi: 10.1021/jp112319d
16. [16]
  (16) Kumar, N.; Liu, S. B.; Kozlowski, P. M. J. Phys. Chem. Lett. 2012, 3, 1035.
17. [17]
  (17) Markownikoff,W. Ann. Pharm. (Lem , Ger.) 1870, 153, 228.
18. [18]
  (18) Baldwin, J. E. J. Chem. Soc. Chem. Commun. 1976, 1976, 734.
19. [19]
  (19) Fürst, A.; Plattner, P. A. Helv. Chim. Acta 1949, 32, 275.
20. [20]
  (20) Liu, S. B.; Rong, C. Y.; Lu, T. J. Phys. Chem. A 2014, 118, 3698. doi: 10.1021/jp5032702
21. [21]
  (21) Hirshfeld, F. Theor. Chim. Acc. 1977, 44, 129. doi: 10.1007/BF00549096
22. [22]
  (22) Shannon, C. E. Bell Syst. Tech. J. 1948, 27, 379. doi: 10.1002/bltj.1948.27.issue-3
23. [23]
  (23) Liu, S. B. J. Chem. Phys. 2007, 126, 191107. doi: 10.1063/1.2741244
24. [24]
  (24) Kullback, S.; Leibler, R.A. Ann. Math. Stat. 1951, 22, 79.
25. [25]
  (25) Bader, R. F.W. Atoms in Molecules: A Quantum Theory; Oxford University Press: Oxford, England, 1990.
26. [26]
  (26) Rong, C. Y.; Lu, T.; Liu, S. B. J. Chem. Phys. 2014, 140, 024109. doi: 10.1063/1.4860969
27. [27]
  (27) Lu, T.; Chen, F.WActa Phys. -Chim. Sin. 2012, 28, 1. [卢天, 陈正武. 物理化学学报, 2012, 28, 1.] doi: 10.3866/PKU.WHXB2012281
28. [28]
  (28) Nalewajski, R. F.; Parr, R. G. Proc. Natl. Acad. Sci. U. S. A. 2000, 97, 8879. doi: 10.1073/pnas.97.16.8879
29. [29]
  (29) Nalewajski, R. F.; Parr, R. G. J. Phys. Chem. A 2001, 105, 7391. doi: 10.1021/jp004414q
30. [30]
  (30) Parr, R. G.; Ayers, P.W.; Nalewajski, R. F. J. Phys. Chem. A 2005, 109, 3957. doi: 10.1021/jp0404596
31. [31]
  (31) Ayers, P.W. Theor. Chem. Acc. 2006, 115, 370. doi: 10.1007/s00214-006-0121-5
32. [32]
  (32) Mayr, H.; Bug, T.; tta, M. F.; Hering, N.; Irrgang, B.; Janker, B.; Kempf, B.; Loos, R.; Ofial, A. R.; Remennikov, G.; Schimmel, H. J. Am. Chem. Soc. 2001, 123, 9500. doi: 10.1021/ja010890y
33. [33]
  (33) Lucius, R.; Loos, R.; Mayr, H. Angew. Chem. Int. Edit. 2002, 41, 91. doi: 10.1002/1521-3773(20020104)41:1<>1.0.CO;2-5
34. [34]
  (34) Mayr, H.; Kempf, B.; Ofial, A. R. Accounts Chem. Res. 2003, 36, 66. doi: 10.1021/ar020094c
35. [35]
  (35) (a) Pérez, P. J. Org. Chem. 2003, 68, 5886.(b) Mayr, H.; Hartnagel, M.; Grimm, K. Liebigs Ann. /Recl.1997, 55.
36. [36]
  (36) Kanzian, T.; Mayr, H. Chem. Eur. J. 2010, 16, 11670. doi: 10.1002/chem.v16:38
37. [37]
  (37) Bug, T.; Hartnagel, M.; Schlierf, C.; Mayr, H. Chem. Eur. J. 2003, 9, 4068.
38. [38]
  (38) Brotzel, F.; Chu, Y. C.; Mayr, H. J. Org. Chem. 2007, 72, 3679. doi: 10.1021/jo062586z
39. [39]
  (39) Ditchfield, R.; Hehre,W. J.; Pople, J. J. Chem. Phys. 1971, 54, 724. doi: 10.1063/1.1674902
40. [40]
  (40) Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215. doi: 10.1007/s00214-007-0310-x
41. [41]
  (41) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al. Gaussian 09, Revision D.01; Gaussian Inc.:Wallingford, CT, 2009.
42. [42]
  (42) Cossi, M.; Rega, N.; Scalmani, G.; Baronem, V. J. Comput. Chem. 2003, 24, 669. doi: 10.1002/jcc.10189
43. [43]
  (43) Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.v33.5
44. [44]
  (44) Liu, S. B. J. Chem. Phys. 2007, 126, 244103. doi: 10.1063/1.2747247
45. [45]
  (45) Liu, S. B. J. Phys. Chem. A 2013, 117, 962. doi: 10.1021/jp312521z
46. [46]
  (46) Liu, S. B.; Pedersen, L. G. J. Phys. Chem. A 2009, 113, 3648. doi: 10.1021/jp811250r
47. [47]
  (47) Liu, S. B.; Schauer, C. K.; Pedersen, L. G. J. Chem. Phys. 2009, 131, 164107. doi: 10.1063/1.3251124
48. [48]
  (48) Huang, Y.; Liu, L.; Liu,W.; Liu, S. G.; Liu, S. B. J. Phys. Chem. A 2011, 115, 14697. doi: 10.1021/jp209540p
49. [49]
  (49) Liu, S. B.; Hu, H.; Pedersen, L. G. J. Phys. Chem. A 2010, 114, 5913. doi: 10.1021/jp101329f
50. [50]
  (50) Huang, Y.; Zhong, A. G.; Yang, Q. S.; Liu, S. B. J. Chem. Phys. 2011, 134, 084103. doi: 10.1063/1.3555760
1. [1]
  Lei Shi . Nucleophilicity and Electrophilicity of Radicals. University Chemistry, 2024, 39(11): 131-135. doi: 10.3866/PKU.DXHX202402018
2. [2]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
3. [3]
  Yuyao Chen , Qirui Zou , Bowen Liu , Fuyun Li , Ao Zhang , Xiuwei Fan . NBO分析在研究取代芳烃亲电取代反应区域选择性和活性中的应用. University Chemistry, 2026, 41(9): 442-448. doi: 10.12461/PKU.DXHX202509012
4. [4]
  Zhi Chai , Huashan Huang , Xukai Shi , Yujing Lan , Zhentao Yuan , Hong Yan . Wittig反应的立体选择性. University Chemistry, 2025, 40(8): 192-201. doi: 10.12461/PKU.DXHX202410046
5. [5]
  Xinyu Xu , Jiale Lu , Bo Su , Jiayi Chen , Xiong Chen , Sibo Wang . Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂. Acta Physico-Chimica Sinica, 2025, 41(11): 100153-0. doi: 10.1016/j.actphy.2025.100153
6. [6]
  Shuhong Xiang , Lv Yang , Yingsheng Xu , Guoxin Cao , Hongjian Zhou . Selective electrosorption of Cs(Ⅰ) from high-salinity radioactive wastewater using CNT-interspersed potassium zinc ferrocyanide electrodes. Acta Physico-Chimica Sinica, 2025, 41(9): 100097-0. doi: 10.1016/j.actphy.2025.100097
7. [7]
  Peiran ZHAO , Yuqian LIU , Cheng HE , Chunying DUAN . A functionalized Eu³⁺ metal-organic framework for selective fluorescent detection of pyrene. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 713-724. doi: 10.11862/CJIC.20230355
8. [8]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
9. [9]
  Yunhao Zhang , Yinuo Wang , Siran Wang , Dazhen Xu . Progress in Selective Construction of Functional Aromatics from Nitrogenous Cycloalkanes. University Chemistry, 2024, 39(11): 136-145. doi: 10.3866/PKU.DXHX202401083
10. [10]
  Yi Huang , Yansong Xiao , Xingxing Ma , Qiuling Song . Zweifel olefination: an innovative approach to highly efficient stereoselective alkene synthesis. University Chemistry, 2026, 41(7): 119-125. doi: 10.12461/PKU.DXHX202506046
11. [11]
  Zhengjie Miao , Chuanqiang Zhou , Yuanyuan Ren , Xiangping Xu , Ju Xie , Jie Han . Hierarchical chiral nanoribbons of achiral oligoaniline: temperature induced helicity inversion and enantioselective crystallization application. Acta Physico-Chimica Sinica, 2026, 42(10): 100256-0. doi: 10.1016/j.actphy.2026.100256
12. [12]
  Wentao Lin , Wenfeng Wang , Yaofeng Yuan , Chunfa Xu . Concerted Nucleophilic Aromatic Substitution Reactions. University Chemistry, 2024, 39(6): 226-230. doi: 10.3866/PKU.DXHX202310095
13. [13]
  Jiakun BAI , Ting XU , Lu ZHANG , Jiang PENG , Yuqiang LI , Junhui JIA . A red-emitting fluorescent probe with a large Stokes shift for selective detection of hypochlorous acid. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1095-1104. doi: 10.11862/CJIC.20240002
14. [14]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
15. [15]
  Feifei Yang , Wei Zhou , Chaoran Yang , Tianyu Zhang , Yanqiang Huang . Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst. Acta Physico-Chimica Sinica, 2024, 40(7): 2308017-0. doi: 10.3866/PKU.WHXB202308017
16. [16]
  Guanghuan Chen , Yinghua Wang , Jinhui Ming , Jian Ling , Zhihui Shao , Chongdao Lu , Yong Shi . 香芹酮β硼化：一个可用于展示反应选择性的教学实验. University Chemistry, 2026, 41(5): 101-108. doi: 10.12461/PKU.DXHX202510042
17. [17]
  Kaixin Lai , Ke Wang , Xinwei Tang , Tian Sun , Yan Li , Zhiwei Hu , Wei Li , Wei Hong , Wenkai Chen , Xinyi Jiang , Zicheng Wang , Tianxi Liu . Selective thermal radiation polyimide composite fabric for efficient infrared stealth and electromagnetic protection. Acta Physico-Chimica Sinica, 2026, 42(7): 100272-. doi: 10.1016/j.actphy.2026.100272
18. [18]
  Jun LUO , Baoshu LIU , Yunchang ZHANG , Bingkai WANG , Beibei GUO , Lan SHE , Tianheng CHEN . Europium(Ⅲ) metal-organic framework as a fluorescent probe for selectively and sensitively sensing Pb²⁺ in aqueous solution. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2438-2444. doi: 10.11862/CJIC.20240240
19. [19]
  Yu Wang , Haiyang Shi , Zihan Chen , Feng Chen , Ping Wang , Xuefei Wang . 具有富电子Pt^δ−壳层的空心AgPt@Pt核壳催化剂：提升光催化H₂O₂生成选择性与活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100081-0. doi: 10.1016/j.actphy.2025.100081
20. [20]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385

Get Citation

PDF

XML

Metrics

PDF Downloads(744)
Abstract views(2366)
HTML views(192)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142