Citation: WANG Yue-Hong, LI Xiao-Yan, ZENG Yan-Li, MENG Ling-Peng, ZHANG Xue-Ying. Topological Analyses of Electron Density on π-hole Pnicogen Bonds in PO₂X…PX₃/PH₂X (X = F, Cl, Br, CH₃, NH₂) Complexes[J]. Acta Physico-Chimica Sinica, ;2016, 32(3): 671-682. doi: 10.3866/PKU.WHXB201512293 shu

Topological Analyses of Electron Density on π-hole Pnicogen Bonds in PO₂X…PX₃/PH₂X (X = F, Cl, Br, CH₃, NH₂) Complexes

1.
Key Laboratory of Inorganic Nano-Materials of Hebei Province, College of Chemistry and Material Sciences, Hebei Normal University, Shijiazhuang 050024, P. R. China

Corresponding author: ZHANG Xue-Ying,
Received Date: 30 September 2015
Available Online: 23 December 2015
Fund Project: 国家自然科学基金(21371045,21372062) (21371045,21372062)河北省自然科学基金(B2014205109) (B2014205109)河北省教育厅重点项目(ZD20131037,ZD20131053)资助 (ZD20131037,ZD20131053)

Acting as a molecular linker, the pnicogen bond plays an important role in crystal engineering and supramolecular synthesis. The structures and properties of π-hole pnicogen-bonded complexes PO₂X…PX₃ and PO₂X…PH₂X (X = F, Cl, Br, CH₃, NH₂) were investigated by ab initio MP2/aug-cc-pVTZ calculations and topological analyses of electron density. Two sets of π-hole pnicogen-bonded complexes were found on the potential surfaces. Type-A complexes have P…P and type-B ones have P…X pnicogen bonds. The atoms-inmolecules (AIM) theory, electron localization function (ELF) theory, noncovalent interaction (NCI) index method as well as the adaptive natural density partitioning (AdNDP) approach were used to expand the nature of the interactions considered. The substituent groups strongly affect the properties of pnicogen bond interactions. Pnicogen bonds were covalent interactions for the electron-donating substituents (CH₃, NH₂), while they were noncovalent, partly covalent and covalent interactions when the substituents were electron-withdrawing groups. Natural bond orbital (NBO) analyses indicated that the larger the Wiberg bond order of the pnicogen-bonded interaction, the more covalent the bond and the greater its strength will be. In type-B conformations, charge transfer mainly occurs from an X lone pair of the PX3/PH₂X molecule to the π^*(P＝O) orbital of PO2X.
- Intermolecular interaction,
- Pnicogen bond,
- π-hole interaction,
- NCI analysis,
- Topological analysis of electron density,
- ELF analysis
1. [1]
  (1) Politzer, P.; Murray, J. S. ChemPhysChem 2013, 14, 278. doi: 10.1002/cphc.201200799
2. [2]
  (2) Metrangolo, P.; Meyer, F.; Pilati, T.; Resnati, G.; Terraneo, G.Angew Chem. Int. Edit. Engl. 2008, 47, 6114. doi: 10.1002/anie.v47: 33
3. [3]
  (3) Metrangolo, P.; Neukirch, H.; Pilati, T.; Resnati, G. Accounts Chem. Res. 2005, 38, 386. doi: 10.1021/ar0400995
4. [4]
  (4) Legon, A. C. Phys. Chem. Chem. Phys. 2010, 12, 7736. doi: 10.1039/c002129f
5. [5]
  (5) Scheiner, S. Accounts Chem. Res. 2013, 46, 280. doi: 10.1021/ar3001316
6. [6]
  (6) Zahn, S.; Frank, R.; Hey-Hawkins, E.; Kirchner, B. Chemistry2011, 17, 6034. doi: 10.1002/chem.v17.22
7. [7]
  (7) Carré, F.; Chuit, C.; Corriu, R. J. P.; Monforte, P.; Nayyar, N.K.; Reyé, C. J. Organomet. Chem. 1995, 499, 147. doi: 10.1016/0022-328X(95)00318-K
8. [8]
  (8) Scheiner, S. Phys. Chem. Chem. Phys. 2011, 13, 13860. doi: 10.1039/c1cp20427k
9. [9]
  (9) Solimannejad, M.; Gharabaghi, M.; Scheiner, S. J. Chem. Phys. 2011, 134, 024312. doi: 10.1063/1.3523580
10. [10]
  (10) Scheiner, S. J. Chem. Phys. 2011, 134, 094315. doi: 10.1063/1.3562209
11. [11]
  (11) Adhikari, U.; Scheiner, S. Chem. Phys. Lett. 2012, 536, 30. doi: 10.1016/j.cplett.2012.03.085
12. [12]
  (12) Adhikari, U.; Scheiner, S. J. Phys. Chem. A 2012, 116, 3487. doi: 10.1021/jp301288e
13. [13]
  (13) Scheiner, S.; Adhikari, U. J. Phys. Chem. A 2011, 115, 11101. doi: 10.1021/jp2082787
14. [14]
  (14) Scheiner, S. Int. J. Quantum Chem. 2013, 113, 1609. doi: 10.1002/qua.v113.11
15. [15]
  (15) Del Bene, J. E.; Alkorta, I.; Sanchez-Sanz, G.; Elguero, J.Chem. Phys. Lett. 2011, 512, 184. doi: 10.1016/j.cplett.2011.07.043
16. [16]
  (16) Del Bene, J. E.; Alkorta, I.; Sanchez-Sanz, G.; Elguero, J.J. Phys. Chem. A 2011, 115, 13724. doi: 10.1021/jp2094164
17. [17]
  (17) Del Bene, J. E.; Alkorta, I.; Sanchez-Sanz, G.; Elguero, J.J. Phys. Chem. A 2012, 116, 3056. doi: 10.1021/jp300763d
18. [18]
  (18) Alkorta, I.; Elguero, J.; Del Bene, J. E. J. Phys. Chem. A 2013, 117, 4981. doi: 10.1021/jp403651h
19. [19]
  (19) Del Bene, J. E.; Alkorta, I.; Elguero, J. J. Phys. Chem. A 2013, 117, 11592. doi: 10.1021/jp409016q
20. [20]
  (20) Del Bene, J. E.; Alkorta, I.; Elguero, J. J. Phys. Chem. A 2013, 117, 6893. doi: 10.1021/jp4063109
21. [21]
  (21) Del Bene, J. E.; Alkorta, I.; Elguero, J. Theor. Chem. Acc.2014, 133, 1464. doi: 10.1007/s00214-014-1464-y
22. [22]
  (22) Alkorta, I.; Sanchez-Sanz, G.; Elguero, J.; Del Bene, J. E.J. Phys. Chem. A 2014, 118, 1527. doi: 10.1021/jp411623h
23. [23]
  (23) An, X. L.; Li, R.; Li, Q. Z.; Liu, X. F.; Li, W. Z.; Cheng, J. B.J. Mol. Model. 2012, 18, 4325. doi: 10.1007/s00894-012-1445-9
24. [24]
  (24) Li, Q. Z.; Li, R.; Liu, X. F.; Li, W. Z.; Cheng, J. B.ChemPhysChem 2012, 13, 1205. doi: 10.1002/cphc.v13.5
25. [25]
  (25) Li, Q. Z.; Zhuo, H.; Yang, X.; Cheng, J. B.; Li, W. Z.; Loffredo, R. E. ChemPhysChem 2014, 15, 500. doi: 10.1002/cphc.v15.3
26. [26]
  (26) Del Bene, J. E.; Alkorta, I.; Elguero, J. J. Phys. Chem. A 2014, 118, 3386. doi: 10.1021/jp502667k
27. [27]
  (27) Del Bene, J. E.; Alkorta, I.; Elguero, J. J. Phys. Chem. A 2015, 119, 3125. doi: 10.1021/acs.jpca.5b00944
28. [28]
  (28) Li, Q. Z.; Li, R.; Liu, X. F.; Li, W. Z.; Cheng, J. B. J. Phys. Chem. A 2012, 116, 2547. doi: 10.1021/jp211435b
29. [29]
  (29) Alkorta, I.; Elguero, J.; Solimannejad, M. J. Phys. Chem. A2014, 118, 947. doi: 10.1021/jp412144r
30. [30]
  (30) Clark, T.; Hennemann, M.; Murray, J. S.; Politzer, P. J. Mol. Model. 2007, 13, 291. doi: 10.1007/s00894-006-0130-2
31. [31]
  (31) Murray, J. S.; Riley, K. E.; Politzer, P.; Clark, T. Aust. J. Chem.2010, 63, 1598. doi: 10.1071/CH10259
32. [32]
  (32) Politzer, P.; Murray, J. S.; Clark, T. Phys. Chem. Chem. Phys.2013, 15, 11178. doi: 10.1039/c3cp00054k
33. [33]
  (33) Murray, J. S.; Lane, P.; Clark, T.; Riley, K. E.; Politzer, P.J. Mol. Model. 2012, 18, 541. doi: 10.1007/s00894-011-1089-1
34. [34]
  (34) Esrafili, M. D.; Mohammadian-Sabet, F.; Solimannejad, M.Struct. Chem. 2014, 25, 1197. doi: 10.1007/s11224-014-0392-8
35. [35]
  (35) Solimannejad, M.; Ramezani, V.; Trujillo, C.; Alkorta, I.; Sanchez-Sanz, G.; Elguero, J. J. Phys. Chem. A 2012, 116, 5199. doi: 10.1021/jp300540z
36. [36]
  (36) Bauza, A.; Ramis, R.; Frontera, A. J. Phys. Chem. A 2014, 118, 2827. doi: 10.1021/jp502301n
37. [37]
  (37) Lang, T.; Li, X.; Meng, L.; Zheng, S.; Zeng, Y. Struct. Chem.2014, 26, 213. doi: 10.1007/s11224-014-0486-3
38. [38]
  (38) Bauza, A.; Mooibroek T. J.; Frontera, A. ChemPhysChem2015, 16, 2496. doi: 10.1002/cphc.v16.12
39. [39]
  (39) Brupbacher-Gatehouse, B. J. Am. Chem. Soc. 2000, 122, 4171. doi: 10.1021/ja9938534
40. [40]
  (40) Alkorta, I.; Elguero, J.; Del Bene, J. E. J. Phys. Chem. A 2013, 117, 10497. doi: 10.1021/jp407097e
41. [41]
  (41) Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553. doi: 10.1080/00268977000101561
42. [42]
  (42) Frisch, M.; Trucks, G.; Schlegel, H. B.; et al. Gaussian 09, Revision A. 02; Gaussian: Wallingford, CT, 2009.
43. [43]
  (43) Bader, R. F.W. Chem. Rev. 1991, 91, 893. doi: 10.1021/cr00005a013
44. [44]
  (44) Matta, C. F.; Boyd, R. J. The Quantum Theory of Atoms in Molecules; JohnWiley & Sons: New York, 2007.
45. [45]
  (45) Bone, R. G. A.; Bader, R. F.W. J. Phys. Chem. 1996, 100, 10892. doi: 10.1021/jp953512m
46. [46]
  (46) Becke, A. D.; Edgecombe, K. E. J. Chem. Phys. 1990, 92, 5397. doi: 10.1063/1.458517
47. [47]
  (47) Silvi, B.; Savin, A. Nature 1994, 371, 683. doi: 10.1038/371683a0
48. [48]
  (48) Savin, A.; Nesper, R.; Wengert, S.; Fässler, T. F. Angew. Chem. Int. Edit. 1997, 36, 1808.
49. [49]
  (49) Li, X. Y.; Huo, S. H.; Zeng, Y. L.; Sun, Z.; Zheng, S. J.; Meng, L. P. Organometallics 2013, 32, 1060. doi: 10.1021/om301110j
50. [50]
  (50) Bulat, F. A.; Toro-Labbé, A.; Brinck, T.; Murray, J. S.; Politzer, P. J. Mol. Model. 2010, 16, 1679. doi: 10.1007/s00894-010-0692-x
51. [51]
  (51) Biegler-Kôning, F. J.; Derdau, R.; Bayles, D.; Bader, R. F.W.AIM2000, Version 2.0, 2002.
52. [52]
  (52) Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.v33.5
53. [53]
  (53) Humphrey, W.; Dalke, A.; Schulten, K. J. Mol. Graph. 1996, 14, 33. doi: 10.1016/0263-7855(96)00018-5
54. [54]
  (54) Politzer, P.; Laurence, P. R.; Jayasuriya, K. Environ Health Perspect. 1985, 61, 191. doi: 10.1289/ehp.8561191
55. [55]
  (55) Politzer, P.; Murray, J. S. Theor. Chem. Acc. 2002, 108, 134. doi: 10.1007/s00214-002-0363-9
56. [56]
  (56) Koch, U.; Popelier, P. L. A. J. Phys. Chem. 1995, 99, 9747. doi: 10.1021/j100024a016
57. [57]
  (57) Delanoye, S. N.; Herrebout, W. A.; van der Veken, B. J. J. Am. Chem. Soc. 2002, 124, 11854. doi: 10.1021/ja027610e
58. [58]
  (58) Johnson, E. R.; Keinan, S.; Mori-Sanchez, P.; Contreras-Garcia, J.; Cohen, A. J.; Yang, W. J. Am. Chem. Soc. 2010, 132, 6498. doi: 10.1021/ja100936w
59. [59]
  (59) Contreras-Garcia, J.; Johnson, E. R.; Keinan, S.; Chaudret, R.; Piquemal, J. P.; Beratan, D. N.; Yang, W. J. Chem. Theory Comput. 2011, 7, 625. doi: 10.1021/ct100641a
60. [60]
  (60) Zubarev, D. Y.; Boldyrev, A. I. Phys. Chem. Chem. Phys. 2008, 10, 5207. doi: 10.1039/b804083d
61. [61]
  (61) Cheng, H.; Cheng, L. J. Comput. Theor. Chem. 2015, 1060, 36. doi: 10.1016/j.comptc.2015.02.020
62. [62]
  (62) Feng, Y. Q.; Cheng, L. J. RSC Adv. 2015, 5, 62543. doi: 10.1039/C5RA06137G
1. [1]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
2. [2]
  Huiying Xu , Minghui Liang , Zhi Zhou , Hui Gao , Wei Yi . Application of Quantum Chemistry Computation and Visual Analysis in Teaching of Weak Interactions. University Chemistry, 2025, 40(3): 199-205. doi: 10.12461/PKU.DXHX202407011
3. [3]
  Yuxin CHEN , Yanni LING , Yuqing YAO , Keyi WANG , Linna LI , Xin ZHANG , Qin WANG , Hongdao LI , Wenmin WANG . Construction, structures, and interaction with DNA of two Sm^Ⅲ₄ complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1141-1150. doi: 10.11862/CJIC.20240258
4. [4]
  Yanan Jiang , Yuchen Ma . Brief Discussion on the Electronic Exchange Interaction in Quantum Chemistry Computations. University Chemistry, 2025, 40(3): 10-15. doi: 10.12461/PKU.DXHX202402058
5. [5]
  Linhan Tian , Changsheng Lu . Discussion on Sextuple Bonding in Diatomic Motifs of Chromium Family Elements. University Chemistry, 2024, 39(8): 395-402. doi: 10.3866/PKU.DXHX202401056
6. [6]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Liu Fei . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 2408004-0. doi: 10.3866/PKU.WHXB202408004
7. [7]
  Yanan Fan , Jingjing Huang . Interactive Electronic Courseware Facilitates the Development of Integrated Undergraduate-Graduate Instrumental Analysis Laboratory Courses: A Case Study of UV-Vis Spectroscopy Analysis Experiment. University Chemistry, 2025, 40(10): 282-287. doi: 10.12461/PKU.DXHX202411009
8. [8]
  Wenyan Dan , Weijie Li , Xiaogang Wang . The Technical Analysis of Visual Software ShelXle for Refinement of Small Molecular Crystal Structure. University Chemistry, 2024, 39(3): 63-69. doi: 10.3866/PKU.DXHX202302060
9. [9]
  Jingyi Xie , Qianxi Lü , Weizhen Qiao , Chenyu Bu , Yusheng Zhang , Xuejun Zhai , Renqing Lü , Yongming Chai , Bin Dong . Enhancing Cobalt―Oxygen Bond to Stabilize Defective Co₂MnO₄ in Acidic Oxygen Evolution. Acta Physico-Chimica Sinica, 2024, 40(3): 2305021-0. doi: 10.3866/PKU.WHXB202305021
10. [10]
  Zhuomin Zhang , Hanbing Huang , Liangqiu Lin , Jingsong Liu , Gongke Li . Course Construction of Instrumental Analysis Experiment: Surface-Enhanced Raman Spectroscopy for Rapid Detection of Edible Pigments. University Chemistry, 2024, 39(2): 133-139. doi: 10.3866/PKU.DXHX202308034
11. [11]
  Zhenli Sun , Ning Wang , Kexin Lin , Qin Dai , Yufei Zhou , Dandan Cao , Yanfeng Dang . Visual Analysis of Hotspots and Development Trends in Analytical Chemistry Education Reform. University Chemistry, 2024, 39(11): 57-64. doi: 10.12461/PKU.DXHX202403095
12. [12]
  Zhaoyang Li , Haiyan Zhao , Yali Zhang , Yuan Zhang , Shiqiang Cui . Integration of Nobel Prize Achievements in Analytical Technology with College Instrumental Analysis Course. University Chemistry, 2025, 40(3): 269-276. doi: 10.12461/PKU.DXHX202405131
13. [13]
  Liqiang Huang , Peng Lin . 数-图分析法解释仪器分析实验课程教学中的难点. University Chemistry, 2025, 40(6): 353-359. doi: 10.12461/PKU.DXHX202407074
14. [14]
  Zhening Lou , Quanxing Mao , Xiaogeng Feng , Lei Zhang , Xu Xu , Yuyang Zhang , Xueyan Liu , Hongling Kang , Dongyang Feng , Yongku Li . Practice of Implementing Blended Teaching in Shared Analytical Chemistry Course. University Chemistry, 2024, 39(2): 263-269. doi: 10.3866/PKU.DXHX202308089
15. [15]
  Yan Zhang , Ping Wang , Tiebo Xiao , Futing Zi , Yunlong Chen . Measures for Ideological and Political Construction in Analytical Chemistry Curriculum. University Chemistry, 2024, 39(4): 255-260. doi: 10.3866/PKU.DXHX202401017
16. [16]
  Xiaofei Zhou , Yu-Qing Cao , Feng Zhu , Li Qi , Linhai Liu , Ni Yan , Zhiqiang Zhu . Missions and Challenges of Instrumental Analysis Course in the New Era. University Chemistry, 2024, 39(6): 174-180. doi: 10.3866/PKU.DXHX202310058
17. [17]
  . . Chinese Journal of Inorganic Chemistry, 2024, 40(12): 0-0.
18. [18]
  Yujuan Chen , Feiyan Yi . 中美通识教育课程的对比分析. University Chemistry, 2025, 40(6): 54-63. doi: 10.12461/PKU.DXHX202408046
19. [19]
  Zhentong Zhu , Peiyao Du , Chaoqin Zeng , Rui Zhou , Xiaoyan He , Bingzhang Lu , Xiaoquan Lu . Discussion on Teaching Methods for Bilingual Courses in Instrumental Analysis for Chemistry Majors. University Chemistry, 2025, 40(10): 39-45. doi: 10.12461/PKU.DXHX202411014
20. [20]
  Fang Mi , Furong Zhang , Zuotao Xu , Yushan Liu , Ming Guan . Visual Analysis of Dynamic Evolution and Development Trend of Analytical Chemistry Teaching Mode Research. University Chemistry, 2025, 40(9): 318-325. doi: 10.12461/PKU.DXHX202506072

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(475)
HTML views(19)

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

Topological Analyses of Electron Density on π-hole Pnicogen Bonds in PO2X…PX3/PH2X (X = F, Cl, Br, CH3, NH2) Complexes

Metrics

通讯作者: 陈斌, bchen63@163.com

Topological Analyses of Electron Density on π-hole Pnicogen Bonds in PO₂X…PX₃/PH₂X (X = F, Cl, Br, CH₃, NH₂) Complexes