Advanced Search

Citation: LI Jin-Xia, ZHANG Cong-Jie. Structures and Properties of BX[(CH2)n]3 and BX(CH2)[CH(CH2)nCH] (X=N, P) with the [n.n.n]propellane Configuration[J]. Acta Physico-Chimica Sinica, ;2014, 30(3): 423-430. doi: 10.3866/PKU.WHXB201312251 shu

Structures and Properties of BX[(CH2)n]3 and BX(CH2)[CH(CH2)nCH] (X=N, P) with the [n.n.n]propellane Configuration

  • 1.

    Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an 710062, P. R. China

  • Received Date: 26 September 2013
    Available Online: 25 December 2013

    Fund Project: 国家自然科学基金(21373133)资助项目 (21373133)

  • We have designed a family of novel molecules BX[(CH2)n]3 and BX(CH2)[CH(CH2)nCH] (X=N, P) with the [n.n.n]propellane configuration (n=1-6). The structures, stabilities, chemical bonds, and electronic spectra of these structures were investigated using density functional theory (DFT). The calculated results indicate that all of these compounds are situated at minima on the potential energy surfaces. The energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of BN[(CH2)n]3 and BP[(CH2)n]3 (n=1-6) were in the range of 5.24-7.07 eV and 5.47-7.33 eV, respectively, and the energy gap of BX[CH2]3 is close to that of C5H6. In addition, the energy gaps of BN(CH2) [CH(CH2)nCH] and BP(CH2) [CH(CH2)nCH] (n=1-6) are around 6.80 eV. To compare the relative stabilities of these compounds, we investigated the second-order differences of energies. The results indicate that BN[(CH2)3]3, BP[(CH2)4]3, and BX(CH2)[CH(CH2)2CH] (X=N, P) are more stable than the other structures. Moreover, based on the bond lengths, Wiberg bond indices, and charges of the two"inverted"atoms, it can be concluded that the bridgehead B and N(P) atoms in BN[(CH2)n]3 (n=2, 6) and BP[(CH2)2]3 do not form chemical bonds, while the two bridgehead atoms in the other compounds studied formed chemical bonds. Additionally, topological analysis of the electron density using the theory of atoms-in-molecules shows that the inverted N―B bonds in BN[(CH2)n]3 (n=3-5) are ionic bonds whereas the B―P bonds in BP[(CH2)n]3 (n=3-6) have covalent character. The vertical transition energies of BN[(CH2)n]3, BP[(CH2)n]3, BN(CH2) [CH(CH2)nCH], and BP(CH2) [CH(CH2)nCH] (n=1-6) range from 191.1 to 284.8 nm, 191.8 to 270.1 nm, 190.5 to 199.7 nm, and 209.0 to 221.3 nm, respectively.

  • 加载中
    1. [1]

      (1) Wiberg, K. B. Chem. Rev. 1989, 89, 975. doi: 10.1021/cr00095a001

    2. [2]

      (2) Wiberg, K. B.;Walker, F. H. J. Am. Chem. Soc. 1982, 104, 5239. doi: 10.1021/ja00383a046

    3. [3]

      (3) Wiberg, K. B.;Walker, S. T.; Rosenberg, R. E. J. Am. Chem. Soc. 1990, 112, 2184. doi: 10.1021/ja00162a021

    4. [4]

      (4) Jackson, J. E.; Allen, L. C. J. Am. Chem. Soc. 1984, 106, 591. doi: 10.1021/ja00315a022

    5. [5]

      (5) Feller, D.; Davidson, E. R. J. Am. Chem. Soc. 1987, 109, 4133. doi: 10.1021/ja00248a001

    6. [6]

      (6) Mcgarry, P. F.; Johnsoton, L. J.; Scaiano, J. C. J. Org. Chem. 1989, 54, 6133. doi: 10.1021/jo00287a033

    7. [7]

      (7) Wiberg, K. B. Accounts Chem. Res. 1984, 17, 379. doi: 10.1021/ar00107a001

    8. [8]

      (8) Wiberg, K. B. J. Am. Chem. Soc. 1983, 105, 1227. doi: 10.1021/ja00343a025

    9. [9]

      (9) Epiotis, N. D. J. Am. Chem. Soc. 1984, 106, 3170. doi: 10.1021/ja00323a018

    10. [10]

      (10) Zhao, C. Y.;Wei, T. S.; Qiu,W. Y. Acta Chim. Sin. 1991, 49, 546. [赵存元, 韦统帅, 邱文元. 化学学报, 1991, 49, 546.]

    11. [11]

      (11) Honegger, E.; Huber, H.; Heilbronner, E.; Dailey,W. P.;Wiberg, K. B. J. Am. Chem. Soc. 1985, 107, 7172. doi: 10.1021/ja00310a068

    12. [12]

      (12) Messmer, R. P.; Schultz, P. A. J. Am. Chem. Soc. 1986, 108, 7407. doi: 10.1021/ja00283a045

    13. [13]

      (13) Riggs, N. V.; Zoller, U.; Nguyen, M. T.; Radom, L. J. Am. Chem. Soc. 1992, 114, 4354. doi: 10.1021/ja00037a048

    14. [14]

      (14) Wu,W.; Gu, J.; Song, J.; Shaik, S.; Hiberty, P. C. Angew. Chem. Int. Edit. 2009, 48, 1407. doi: 10.1002/anie.v48:8

    15. [15]

      (15) Danovich, S. D.;Wu,W.; Hiberty, P. C. Nat. Chem. 2009, 1, 443. doi: 10.1038/nchem.327

    16. [16]

      (16) Shaik, S.; Chen, Z. H.;Wu,W.; Stanger, A.; Danovich, D.; Hiberty, P. C. ChemPhysChem 2009, 10, 2658. doi: 10.1002/cphc.v10:15

    17. [17]

      (17) Gershoni-Poranne, R.; Stanger, A. ChemPhysChem 2012, 13, 2377. doi: 10.1002/cphc.v13.9

    18. [18]

      (18) Eaton, P. E.; Temme, G. H. J. Am. Chem. Soc. 1973, 95, 7508. doi: 10.1021/ja00803a052

    19. [19]

      (19) Wiberg, K. B.;Walker, F. H.; Michl, J. J. Am. Chem. Soc. 1982, 104, 2056. doi: 10.1021/ja00371a059

    20. [20]

      (20) Hamon, D. P. G.; Trenerry, V. C. J. Am. Chem. Soc. 1981, 103, 4962. doi: 10.1021/ja00406a059

    21. [21]

      (21) Szeimies, S. U.; Szeimies, G. J. Am. Chem. Soc. 1978, 100, 3966. doi: 10.1021/ja00480a072

    22. [22]

      (22) Gassman, P. G.; Proehl, G. S. J. Am. Chem. Soc. 1980, 102, 6862. doi: 10.1021/ja00542a040

    23. [23]

      (23) Mlinaric-Majerski, K.; Majerski, Z. J. Am. Chem. Soc. 1980, 102, 1418. doi: 10.1021/ja00524a033

    24. [24]

      (24) Wiberg, K. B.; Burgmaier, G. J. Am. Chem. Soc. 1972, 94, 7396. doi: 10.1021/ja00776a022

    25. [25]

      (25) Aue, D. H.; Reynolds, R. N. J. Org. Chem. 1974, 39, 2315. doi: 10.1021/jo00929a051

    26. [26]

      (26) Schleyer, P. v. R.; Janoschek, R. P. Angew. Chem. 1987, 26, 1267.

    27. [27]

      (27) Nagase, S.; Kudo, T. Organometallics 1987, 6, 2456. doi: 10.1021/om00154a034

    28. [28]

      (28) Tsumuraya, T.; Batcheller, S. A.; Masamune, S. Angew. Chem. 1991, 30, 902.

    29. [29]

      (29) Galle -Planas, N.; Whitehead, M. A. J. Mol. Struct. -Theochem 1992, 260, 419. doi: 10.1016/0166-1280(92)87057-7

    30. [30]

      (30) Holder, A. J.; Earley, C.W. J. Mol. Struct. -Theochem 1993,281, 131. doi: 10.1016/0166-1280(93)87070-T

    31. [31]

      (31) Karni, M.; Apeloig, Y.; Kapp, J.; Schleyer, P. v. R. In The Chemistry of Organic Silicon Compounds; JohnWiley & Sons: New York, 2001; pp 1-163.

    32. [32]

      (32) Nied, D.; Koppe, R;. Klopper,W.; Schnockel, H.; Breher, F. S. J. Am. Chem. Soc. 2010, 132, 10264. doi: 10.1021/ja104810u

    33. [33]

      (33) Nied, D.; Oña-Bur s, P.; Klopper,W.; Breher, F. Organometallics 2011, 30, 1419. doi: 10.1021/om100977z

    34. [34]

      (34) Richards, A. F.; Brynda, M.; Power, P. P. Organometallics 2004, 23, 4009. doi: 10.1021/om0497137

    35. [35]

      (35) Ito, Y.; Lee, V. Y.; rnitzka, H.; edecke, C.; Frenking, G.; Sekiguchi, A. J. Am. Chem. Soc. 2013, 135, 6770. doi: 10.1021/ja401650q

    36. [36]

      (36) Yoshida, H.; Takahara, Y.; Erata, T.; Ando,W. J. Am. Chem. Soc. 1992, 114, 1098. doi: 10.1021/ja00029a055

    37. [37]

      (37) Monakhov, K. Y.; urlaouen, C. Organometallics 2012, 31, 4415. doi: 10.1021/om300180e

    38. [38]

      (38) Daly, A. M.; Tanjaroon, C.; Marwitz, A. V.; Liu, S. Y.; Kukolich, S. G. J. Am. Chem. Soc. 2010, 132, 5501.

    39. [39]

      (39) Liu, Z. Q.; Marder, T. B. Angew. Chem. Int. Edit. 2008, 47, 242.

    40. [40]

      (40) Song, Y.; Chen, H. S.; Zhang, C. R.;Wang, G. H. Acta Phys. -Chim. Sin. 2005, 21, 735. [宋燕, 陈宏善, 张材荣, 王广厚. 物理化学学报, 2005, 21, 735.] doi: 10.3866/PKU. WHXB20050708

    41. [41]

      (41) Hohenberg, P.; Kohn,W. Phys. Rev. 1964, 136, B864.

    42. [42]

      (42) Kohn,W.; Sham, L. Phys. Rev. 1965, 140, A1133.

    43. [43]

      (43) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913

    44. [44]

      (44) Lee, C.; Yang,W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785

    45. [45]

      (45) Reed, A. E.; Curtiss, L. A.;Weinhold, F. Chem. Rev. 1988, 88, 899. doi: 10.1021/cr00088a005

    46. [46]

      (46) Casida, M. E.; Jamorski, C.; Casida, K. C.; Salahub, D. R. J. Chem. Phys. 1998, 108, 4439. doi: 10.1063/1.475855

    47. [47]

      (47) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et. al. Gaussian 03, Revision C.02; Gaussian Inc.:Wallingford, CT, 2003.

    48. [48]

      (48) Biegler-Koning, F. J.; Derdau, R.; Bayles, D.; Bader, R. F.W. AIM2000, Version1, 2000.

    49. [49]

      (49) Lei, X. L.; Zhu, H. J.;Wang, X. M.; Luo, Y. H. Acta Phys. -Chim. Sin. 2008, 24, 1655. [雷雪玲, 祝恒江, 王先明, 罗有华. 物理化学学报, 2008, 24, 1655.] doi: 10.3866/PKU.WHXB20080922


  • 加载中
    1. [1]

      Rui Li ,  Jiayu Zhang ,  Anyang Li . Two Levels of Understanding of Chemical Bonds: a Case of the Bonding Model of Hypervalent Molecules. University Chemistry, 2024, 39(2): 392-398. doi: 10.3866/PKU.DXHX202308051

    2. [2]

      Bo YANG , Gongxuan LÜ , Jiantai MA . Corrosion inhibition of nickel-cobalt-phosphide in water by coating TiO2 layer. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 365-384. doi: 10.11862/CJIC.20240063

    3. [3]

      Xuechen Hu , Qiuying Xia , Fan Yue , Xinyi He , Zhenghao Mei , Jinshi Wang , Hui Xia , Xiaodong Huang . Electrochemical Characteristics of LiNbO3 Anode Film and Its Applications in All-Solid-State Thin-Film Lithium-Ion Battery. Acta Physico-Chimica Sinica, 2024, 40(2): 2309046-0. doi: 10.3866/PKU.WHXB202309046

    4. [4]

      Shitao Fu ,  Jianming Zhang ,  Cancan Cao ,  Zhihui Wang ,  Chaoran Qin ,  Jian Zhang ,  Hui Xiong . Study on the Stability of Purple Cabbage Pigment. University Chemistry, 2024, 39(4): 367-372. doi: 10.3866/PKU.DXHX202401059

    5. [5]

      Jiaxi Xu ,  Yuan Ma . Influence of Hyperconjugation on the Stability and Stable Conformation of Ethane, Hydrazine, and Hydrogen Peroxide. University Chemistry, 2024, 39(11): 374-377. doi: 10.3866/PKU.DXHX202402049

    6. [6]

      Mingxuan Qi , Lanyu Jin , Honghe Yao , Zipeng Xu , Teng Cheng , Qi Chen , Cheng Zhu , Yang Bai . Recent progress on electrical failure and stability of perovskite solar cells under reverse bias. Acta Physico-Chimica Sinica, 2025, 41(8): 100088-0. doi: 10.1016/j.actphy.2025.100088

    7. [7]

      Wang Wang , Yucheng Liu , Shengli Chen . Use of NiFe Layered Double Hydroxide as Electrocatalyst in Oxygen Evolution Reaction: Catalytic Mechanisms, Electrode Design, and Durability. Acta Physico-Chimica Sinica, 2024, 40(2): 2303059-0. doi: 10.3866/PKU.WHXB202303059

    8. [8]

      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

    9. [9]

      Hui Li , Yanxing Qi , Jia Chen , Juanjuan Wang , Min Yang , Hongdeng Qiu . Synthesis of amine-pillar[5]arene porous adsorbent for adsorption of CO2 and selectivity over N2 and CH4. Chinese Chemical Letters, 2024, 35(11): 109659-. doi: 10.1016/j.cclet.2024.109659

    10. [10]

      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

    11. [11]

      Yihan Xue , Xue Han , Jie Zhang , Xiaoru Wen . NCQDs修饰FeOOH基复合材料的制备及其电容脱盐性能. Acta Physico-Chimica Sinica, 2025, 41(7): 100072-0. doi: 10.1016/j.actphy.2025.100072

    12. [12]

      Meng-Yin Wang , Ruo-Bei Huang , Jian-Feng Xiong , Jing-Hua Tian , Jian-Feng Li , Zhong-Qun Tian . Critical Role and Recent Development of Separator in Zinc-Air Batteries. Acta Physico-Chimica Sinica, 2024, 40(6): 2307017-0. doi: 10.3866/PKU.WHXB202307017

    13. [13]

      Xuewei BA , Cheng CHENG , Huaikang ZHANG , Deqing ZHANG , Shuhua LI . Preparation and luminescent performance of Sr1-xZrSi2O7∶xDy3+ phosphor with high thermal stability. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 357-364. doi: 10.11862/CJIC.20240096

    14. [14]

      Caixia Lin ,  Ting Liu ,  Zhaojiang Shi ,  Hong Yan ,  Keyin Ye ,  Yaofeng Yuan . Innovative Experiment of Electrochemical Dearomative Spirocyclization of N-Acyl Sulfonamides. University Chemistry, 2025, 40(4): 359-366. doi: 10.12461/PKU.DXHX202406107

    15. [15]

      Xiuzheng Deng , Changhai Liu , Xiaotong Yan , Jingshan Fan , Qian Liang , Zhongyu Li . Carbon dots anchored NiAl-LDH@In2O3 hierarchical nanotubes for promoting selective CO2 photoreduction into CH4. Chinese Chemical Letters, 2024, 35(6): 108942-. doi: 10.1016/j.cclet.2023.108942

    16. [16]

      Xiangyu Chen , Aihao Xu , Dong Wei , Fang Huang , Junjie Ma , Huibing He , Jing Xu . Atomic cerium-doped CuOx catalysts for efficient electrocatalytic CO2 reduction to CH4. Chinese Chemical Letters, 2025, 36(1): 110175-. doi: 10.1016/j.cclet.2024.110175

    17. [17]

      Shiyi WANG , Chaolong CHEN , Xiangjian KONG , Lansun ZHENG , Lasheng LONG . Polynuclear lanthanide compound [Ce4ⅢCe6Ⅳ(μ3-O)4(μ4-O)4(acac)14(CH3O)6]·2CH3OH for the hydroboration of amides to amine. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 88-96. doi: 10.11862/CJIC.20240342

    18. [18]

      Le Ye ,  Wei-Xiong Zhang . Structural phase transition in a new organic-inorganic hybrid post-perovskite: (N,N-dimethylpyrrolidinium)[Mn(N(CN)2)3]. Chinese Journal of Structural Chemistry, 2024, 43(6): 100257-100257. doi: 10.1016/j.cjsc.2024.100257

    19. [19]

      Min WANG , Dehua XIN , Yaning SHI , Wenyao ZHU , Yuanqun ZHANG , Wei ZHANG . Construction and full-spectrum catalytic performance of multilevel Ag/Bi/nitrogen vacancy g-C3N4/Ti3C2Tx Schottky junction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1123-1134. doi: 10.11862/CJIC.20230477

    20. [20]

      Ke-Ai Zhou ,  Lian Huang ,  Xing-Ping Fu ,  Li-Ling Zhang ,  Yu-Ling Wang ,  Qing-Yan Liu . Fluorinated metal-organic framework for methane purification from a ternary CH4/C2H6/C3H8 mixture. Chinese Journal of Structural Chemistry, 2023, 42(11): 100172-100172. doi: 10.1016/j.cjsc.2023.100172

Get Citation
PDF
XML
Metrics
  • PDF Downloads(616)
  • Abstract views(832)
  • 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

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索
Address：Zhongguancun North First Street 2,100190 Beijing, PR China Tel: +86-010-82449177-888
Powered By info@rhhz.net

/

DownLoad:  Full-Size Img  PowerPoint
Return