Bonding and Reactivity in RB-AsR Systems (R=H, F, OH, CH3, CMe3, CF3, SiF3, BO):Substituent Effects

引用本文: GHARA Manas, CHATTARAJ Pratim K. Bonding and Reactivity in RB-AsR Systems (R=H, F, OH, CH₃, CMe₃, CF₃, SiF₃, BO):Substituent Effects[J]. 物理化学学报, 2018, 34(2): 201-207. doi: 10.3866/PKU.WHXB201707131 shu

Citation: GHARA Manas, CHATTARAJ Pratim K. Bonding and Reactivity in RB-AsR Systems (R=H, F, OH, CH₃, CMe₃, CF₃, SiF₃, BO):Substituent Effects[J]. Acta Physico-Chimica Sinica, 2018, 34(2): 201-207. doi: 10.3866/PKU.WHXB201707131 shu

Bonding and Reactivity in RB-AsR Systems (R=H, F, OH, CH₃, CMe₃, CF₃, SiF₃, BO):Substituent Effects

Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology, Kharagpur 721302, India

摘要: Density functional theory-based calculations have been carried out to study the bonding and reactivity in RB-AsR (R=H, F, OH, CH₃, CMe₃, CF₃, SiF₃, BO) systems. Our calculations demonstrated that all the studied systems adopted bent geometry (∠R-B-As ≈ 180° and ∠B-As-R ≈ 90° or less). The reason for this bending was explained with the help of a valence-orbital model. The potential energy surfaces for three possible isomers of RB-AsR systems were also generated, indicating that the RB-AsR isomer was more stable than R₂B-AsR when R=SiF₃, CMe₃, and H. The B-As bond character was analyzed using natural bond orbital (NBO) and Wiberg bond index (WBI) calculations. The WBI values for B-As bonds in F₃SiB-AsSiF₃ and HB-AsH were 2.254 and 2.209, respectively, indicating that this bond has some triple-bond character in these systems. While the B centers prefer nucleophilic attack, the As centers prefer electrophilic attack.

关键词:

English

Bonding and Reactivity in RB-AsR Systems (R=H, F, OH, CH₃, CMe₃, CF₃, SiF₃, BO):Substituent Effects

Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology, Kharagpur 721302, India
Received Date: 22 June 2017
Revised Date: 10 July 2017

Abstract: Density functional theory-based calculations have been carried out to study the bonding and reactivity in RB-AsR (R=H, F, OH, CH₃, CMe₃, CF₃, SiF₃, BO) systems. Our calculations demonstrated that all the studied systems adopted bent geometry (∠R-B-As ≈ 180° and ∠B-As-R ≈ 90° or less). The reason for this bending was explained with the help of a valence-orbital model. The potential energy surfaces for three possible isomers of RB-AsR systems were also generated, indicating that the RB-AsR isomer was more stable than R₂B-AsR when R=SiF₃, CMe₃, and H. The B-As bond character was analyzed using natural bond orbital (NBO) and Wiberg bond index (WBI) calculations. The WBI values for B-As bonds in F₃SiB-AsSiF₃ and HB-AsH were 2.254 and 2.209, respectively, indicating that this bond has some triple-bond character in these systems. While the B centers prefer nucleophilic attack, the As centers prefer electrophilic attack.

Key words:

1. [1]
 (1) Power, P. P. Chem. Rev. 1999, 99, 3463. doi: 10.1021/cr9408989
2. [2]
 (2) Bino, A.; Ardon, M.; Shirman, E. Science 2005, 308, 234. doi: 10.1126/science.1109965
3. [3]
 (3) Seidu, I.; Seth, M.; Ziegler, T. Inorg. Chem. 2013, 52, 8378. doi: 10.1021/ic401149h
4. [4]
 (4) Danovich, D.; Bino, A.; Shaik, S. J. Phys. Chem. Lett. 2013, 4, 58. doi: 10.1021/jz3016765
5. [5]
 (5) Lein, M.; Krapp, A.; Frenking, G.; J. Am. Chem. Soc. 2005, 127, 6290. doi: 10.1021/ja042295c
6. [6]
 (6) Sekiguchi, A.; Kinjo, R.; Ichinohe, M. Science 2004, 305, 1755. doi: 10.1126/science.1102209
7. [7]
 (7) Sasamori, T.; Hironaka, K.; Sugiyama, T.; Takagi, N.; Nagase, S.; Hosoi, Y.; Furukawa, Y.; Tokitoh, N. J. Am. Chem. Soc. 2008, 130, 13856. doi: 10.1021/ja8061002
8. [8]
 (8) Stender, M.; Phillips, A. D.; Wright, R. J.; Power, P. P. Angew. Chem., Int. Ed. 2002, 41, 1785. doi: 10.1002/1521-3773(20020517) 41:10<1785::AID-ANIE1785>3.0.CO;2-6
9. [9]
 (9) Sugiyama, Y.; Sasamori, T.; Hosoi, Y.; Furukawa, Y.; Takagi, N.; Nagase, S.; Tokitoh, N. J. Am. Chem. Soc. 2006, 128, 1023. doi: 10.1021/ja057205y
10. [10]
 (10) Phillips, A. D.; Wright, R. J.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc. 2002, 124, 5930. doi: 10.1021/ja0257164
11. [11]
 (11) Pu, L.; Twamley, B.; Power, P. P. J. Am. Chem. Soc. 2000, 122, 3524. doi: 10.1021/ja993346m
12. [12]
 (12) Wu, P. C.; Su, M. D. Dalton Trans. 2011, 40, 4253. doi: 10.1039/C0DT00800A
13. [13]
 (13) Wu, P. C.; Su, M. D. Inorg. Chem. 2011, 50, 6814. doi: 10.1021/ic200930v
14. [14]
 (14) Paetzold, P. Adv. Inorg. Chem. 1987, 31, 123. doi: 10.1016/S0898-8838(08)60223-8
15. [15]
 (15) Petrie, M. A.; Shoner, S. C.; Dias, H. V. R.; Power, P. P. Angew. Chem., Int. Ed. Engl. 1990, 29, 1033. doi: 10.1002/anie.199010331
16. [16]
 (16) Rivard, E.; Merrill, W. A.; Fettinger, J. C.; Power, P. P. Chem. Commun. 2006, 3800. doi: 10.1039/b609748k
17. [17]
 (17) Mardones, M. A.; Cowley, A. H.; Contreras, L.; Jones, R. A. J. Organomet. Chem. 1993, 455. doi: 10.1016/0022-328X(93)80411-4
18. [18]
 (18) Kerins, M. C.; Fitzpatrick N. J.; Nguyen, M. T. Polyhedron 1989, 8, 969. doi: 10.1016/S0277-5387(00)86453-0
19. [19]
 (19) Watts, J. D.; Zant, L. C. V. Chem. Phys. Lett. 1996, 251, 119.
20. [20]
 (20) Lu, J. S.; Yanga, M. C.; Su, M. D. PhysChemChemPhys 2017, 19, 8026. doi: 10.1039/c7cp00421d
21. [21]
 (21) Lu, J. S.; Su, S. H.; Yanga, M. C.; Wen, X. T.; Xie, J. Z.; Su, M. D. Organometallics. 2016, 35, 3924. doi: 10.1021/acs.organomet.6b00659
22. [22]
 (22) Lu, J. S.; Yanga, M. C.; Su, M. D. ACS Omega. 2017, 2, 1172. doi: 10.1021/acsomega.7b00113
23. [23]
 (23) Chattaraj, P. K.; Rivas, N. G.; Matus, M. H.; Galvan, M. J. Phys. Chem. A 2005, 109, 25. doi: 10.1021/jp045319a
24. [24]
 (24) Parr, R. G.; Yang, W. Density Functional Theory of Atoms and Molecules; Oxford University Press: Oxford, 1989.
25. [25]
 (25) Geerlings, P.; De Proft, F.; Langenaeker, W. Chem. Rev. 2003, 103, 1793. doi: 10.1021/cr990029p
26. [26]
 (26) Parr, R. G.; Szentpaly, L. v.; Liu, S. J. Am. Chem. Soc. 1999, 121, 1922. doi: 10.1021/ja983494x
27. [27]
 (27) Chattaraj, P. K.; Sarkar, U.; Roy, D. R. Chem. Rev. 2006, 106, 2065. doi: 10.1021/cr078014b
28. [28]
 (28) Parr, R. G.; Donnelly, R. A.; Levy, M.; Palke, W. E. J. Chem. Phys. 1978, 68, 3801. doi: http://dx.doi.org/10.1063/1.436185
29. [29]
 (29) Parr, R. G.; Pearson, R. G. J. Am. Chem. Soc. 1983, 105, 7512. doi: 10.1021/ja00364a005
30. [30]
 (30) Chattaraj, P. K.; Parr, R. G. Density functional theory of Chemical Hardness in Chemical Hardness (Structure and Bonding) Vol. 80; Sen, K. D., Mingos, D. M. P. Eds.; Springer: Berlin, 1993.
31. [31]
 (31) Chattaraj, P. K.; Giri, S.; Duley, S. J. Phys. Chem. Lett. 2010, 1, 1064. doi: 10.1021/jz1001117
32. [32]
 (32) Sanderson, R. T. Science 1951, 114, 670. doi: 10.1126/science.114.2973.670
33. [33]
 (33) Datta, D. J. Phys. Chem. 1986, 90, 4216. doi: 10.1021/j100408a076
34. [34]
 (34) Szentpály, L. V. J. Phys. Chem. A. 2015, 119, 1715. doi: 10.1021/jp5084345
35. [35]
 (35) Szentpály, L. V. J. Mol. Model. 2017, 23, 217. doi: 10.1007/s00894-017-3383-z
36. [36]
 (36) Posthumus, K. Rec. Trav. Chim. 1933, 52, 25; 1933, 53, 308.
37. [37]
 (37) Parr, R. G.; Yang, W. J. Am. Chem. Soc. 1984, 106, 4049. doi: 10.1021/ja00326a036
38. [38]
 (38) Yang, W.; Mortier, W. J. J. Am. Chem. Soc. 1986, 108, 5708. doi: 10.1021/ja00279a008
39. [39]
 (39) Chattaraj, P. K.; Maiti, B.; Sarkar, U. J. Phys. Chem. A 2003, 107, 4973. doi: 10.1021/jp034707u
40. [40]
 (40) Roy, D. R.; Parthasarathi, R.; Padmanabhan, J.; Sarkar, U.; Subramanian, V.; Chattaraj, P. K. J. Phys. Chem. A. 2006, 110, 1084. doi: 10.1021/jp053641v
41. [41]
 (41) Morell, C.; Grand, A.; Toro-Labbé, A. J. Phys. Chem. A 2005, 109, 205. doi: 10.1021/jp046577a
42. [42]
 (42) Morell, C.; Grand, A.; Toro-Labbe, A. Chem. Phys. Lett. 2006, 425, 342. doi: 10.1016/j.cplett.2006.05.003
43. [43]
 (43) Padmanabhan, J.; Parthasarathi, R.; Elango, M.; Subramanian, V.; Krishnamoorthy, B. S.; Gutierrez-Oliva, S.; Toro-Labbé, A.; Roy, D. R.; Chattaraj, P. K. J. Phys. Chem. A 2007, 111, 37. doi: 10.1021/jp0718909
44. [44]
 (44) Chattaraj, P. K.; Chakraborty, A.; Giri, S. J. Phys. Chem. A. 2009, 113, 10068. doi: 10.1021/jp904674x
45. [45]
 (45) Zhao, Y.; Truhlar, D. G. Theor. Chem. Account. 2006, 120, 215. doi: 10.1007/s00214-007-0310-x
46. [46]
 (46) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 09, Revision C.01; Gaussian Inc.: Wallingford CT, 2010.
47. [47]
 (47) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899. doi: 10.1021/cr00088a005
48. [48]
 (48) Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735. doi: http://dx.doi.org/10.1063/1.449486
49. [49]
 (49) Wiberg, K. B. Tetrahedron 1968, 24, 1083. doi: 10.1016/0040-4020(68)88057-3
50. [50]
 (50) Bader, R. F. W. Atoms in Molecules: A Quantum Theory; Clarendon Press: Oxford, UK, 1990.
51. [51]
 (51) Lu, T.; Chen, F. W. J. Comput. Chem. 2012, 33, 580. doi: 10.1002/jcc.22885
52. [52]
 (52) Pyykko, P.; Desclaux, J. P. Acc. Chem. Res. 1979, 12, 276. doi: 10.1021/ar50140a002
53. [53]
 (53) Pyykko, P. Chem. Rev. 1988, 88, 563. doi: 10.1021/cr00085a006

扫一扫看文章

计量

PDF下载量: 6
文章访问数: 1053
HTML全文浏览量: 97

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

Bonding and Reactivity in RB-AsR Systems (R=H, F, OH, CH₃, CMe₃, CF₃, SiF₃, BO):Substituent Effects

English

Bonding and Reactivity in RB-AsR Systems (R=H, F, OH, CH₃, CMe₃, CF₃, SiF₃, BO):Substituent Effects

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处