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A theoretical investigation on the complexes of B3O3H3 with acetylene and its substituted derivatives

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Abstract

The complexes of B3O3H3 with acetylene and its substituted derivatives C2HX (X=H, F, Cl, Br, CH3, NH2) are explored by theoretical calculations using MP2 and M06-2X methods with aug-cc-pVDZ as the basis set. The different molecular electrostatic potential features of B3O3H3 with benzene (C6H6) and borazine (B3N3H6) result in different stable structures of the complexes with C2HX. The geometric analysis indicates that the global minimum is the parallel stacked (PS) structure with the linear C–C triple bond lies on the top of B3O3H3, and this is much different from that of the B3N3H6...C2HX complex, in which the C–H bond directs towards the B3N3H6 ring (T-shaped). The H-bonded structure where the C–H interacts with the O atom of B3O3H3 is found to be a local minimum. Besides, there is an additional X…O halogen-bonded structures for the B3O3H3…C2HX (X=Cl, Br) complexes. As for the PS geometry, when one H atom in C2H2 is replaced by different X groups, the binding energies of the complexes increases in the order of F<H<Cl<Br<CH3<NH2, which is mainly determined by the strength of the π-hole bond. The nature of interaction in these complexes is further studied by the atoms-in-molecules (AIM) and noncovalent interaction (NCI) analysis. The natural bond orbital (NBO) analysis indicates that the main orbital interaction arises from LPX→BD*B‑O for B3O3H3…C2HX (X=Cl, Br, NH2), and BDC‑C→BD*B‑O for B3O3H3…C2HX (X=H, CH3) complexes.

Complexes of B3O3H3 with acetylene and its substituted derivatives.

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References

  1. Steudel R (1992) The chemistry of inorganic ring systems. Elsevier, New York

    Google Scholar 

  2. Costa A, Costa ER, Silva ALP, Tanaka AA, Varela JDG (2018) Theoretical study of the effects of substituents (F, Cl, Br, CH3, and CN) on the aromaticity of borazine. J Mol Model 24(1):11. https://doi.org/10.1007/s00894-017-3555-x

    Article  CAS  Google Scholar 

  3. Deshmukh V, Nagnathappa M, Kharat B, Chaudhari A (2014) Theoretical study of borazine and substituted borazines using density functional theory method. J Mol Liq 193:13–22. https://doi.org/10.1016/j.molliq.2013.12.011

    Article  CAS  Google Scholar 

  4. Kiran B, Phukan AK, Jemmis ED (2001) Is borazine aromatic? Unusual parallel behavior between hydrocarbons and corresponding B-N analogues. Inorg Chem 40(14):3615–3618. https://doi.org/10.1021/ic001394y

    Article  CAS  PubMed  Google Scholar 

  5. Kaldor A, Pines I, Porter RF (1969) Reactivity of boroxine. Reactions with azomethane and azoethane. Inorg Chem 8(7):1418–1423. https://doi.org/10.1021/ic50077a010

    Article  CAS  Google Scholar 

  6. Kalemos A (2018) The nature of the chemical bond in borazine (B3N3H6), boroxine (B3O3H3), carborazine (B2N2C2H6), and related species. Int J Quantum Chem 118(16):e25650. https://doi.org/10.1002/qua.25650

    Article  CAS  Google Scholar 

  7. Fowler PW, Steiner E (1997) Ring currents and aromaticity of monocyclic pi-electron systems C6H6, B3N3H6, B3O3H3, C3N3H3, C5H5 −, C7H7 +, C3N3F3, C6H3F3, and C6F6. J Phys Chem A 101(7):1409–1413. https://doi.org/10.1021/jp9637946

    Article  CAS  Google Scholar 

  8. Tossell JA, Lazzeretti P (1990) Calculation of the structure, vibrational-spectra, and polarizability of boroxine, H3B3O3, a model for boroxol rings in vitreous B2O3. J Phys Chem 94(5):1723–1724. https://doi.org/10.1021/j100368a004

    Article  CAS  Google Scholar 

  9. Korich AL, Iovine PM (2010) Boroxine chemistry and applications: a perspective. Dalton Trans 39(6):1423–1431. https://doi.org/10.1039/b917043j

    Article  CAS  PubMed  Google Scholar 

  10. Wason SK, Porter RF (1964) Gaseous boroxine: infrared spectrum and structure. J Phys Chem 68(6):1443–1447. https://doi.org/10.1021/j100788a029

    Article  CAS  Google Scholar 

  11. Chang CH, Porter RF, Bauer SH (1969) Molecular structure of boroxine, H3B3O3, determined by electron diffraction. Inorg Chem 8(8):1689–1693. https://doi.org/10.1021/ic50078a024

    Article  CAS  Google Scholar 

  12. Miyaura N, Suzuki A (1995) Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem Rev 95(7):2457–2483. https://doi.org/10.1021/cr00039a007

    Article  CAS  Google Scholar 

  13. Alcaraz G, Euzenat L, Mongin O, Katan C, Ledoux I, Zyss J, Blanchard-Desce M, Vaultier M (2003) Improved transparency–nonlinearity trade-off with boroxine-based octupolar molecules. Chem Commun 22:2766–2767. https://doi.org/10.1039/B308664J

    Article  Google Scholar 

  14. Li DZ, Zhang SG, Liu JJ, Tang C (2014) Vanadium sandwich complexes with boroxine and boronyl boroxine ligands. Eur J Inorg Chem 21:3406–3410. https://doi.org/10.1002/ejic.201402258

    Article  CAS  Google Scholar 

  15. Sarmah N, Bhattacharyya PK, Bania KK (2014) Substituent and solvent effects on the absorption spectra of cation-pi complexes of benzene and borazine: a theoretical study. J Phys Chem A 118(21):3760–3774. https://doi.org/10.1021/jp5021966

    Article  CAS  PubMed  Google Scholar 

  16. Zhuo HY, Li QZ, Li WZ, Cheng JB (2014) Is pi halogen bonding or lone pair center dot center dot center dot pi interaction formed between borazine and some halogenated compounds? Phys Chem Chem Phys 16(1):159–165. https://doi.org/10.1039/c3cp54006e

    Article  CAS  PubMed  Google Scholar 

  17. Bagheri S, Masoodi HR (2015) Theoretical study of the influence of cation-π and anion-π interactions on some NMR data of borazine complexes. Chem Phys Lett 629:46–52. https://doi.org/10.1016/j.cplett.2015.04.017

    Article  CAS  Google Scholar 

  18. Lisovenko AS, Timoshkin AY (2015) Complexes of borazine and its analogs with Lewis acids and bases. Russ Chem B+ 64(11):2573–2585. https://doi.org/10.1007/s11172-015-1192-z

    Article  CAS  Google Scholar 

  19. Khanh PN, Ngan VT, Man NTH, Nhung NTA, Chandra AK, Trung NT (2016) An insight into Csp-H...π hydrogen bonds and stability of complexes formed by acetylene and its substituted derivatives with benzene and borazine. RSC Adv 6(108):106662–106670. https://doi.org/10.1039/c6ra21557b

    Article  CAS  Google Scholar 

  20. Mishra P, Verma K, Bawari D, Viswanathan KS (2016) Does borazine-water behave like benzene-water? A matrix isolation infrared and ab initio study. J Chem Phys 144(23):9. https://doi.org/10.1063/1.4953793

    Article  CAS  Google Scholar 

  21. Bauza A, Quinonero D, Deya PM, Frontera A (2012) Theoretical ab initio study of anion-π interactions in inorganic rings. Chem Phys Lett 530:145–150. https://doi.org/10.1016/j.cplett.2012.01.079

    Article  CAS  Google Scholar 

  22. Zhuo HY, Li QZ, Li WZ, Cheng JB (2014) Is π halogen bonding or lone pair...π interaction formed between borazine and some halogenated compounds? Phys Chem Chem Phys 16(1):159–165. https://doi.org/10.1039/c3cp54006e

    Article  CAS  PubMed  Google Scholar 

  23. Verma K, Viswanathan KS, Majumder M, Sathyamurthy N (2017) How different is the borazine-acetylene dimer from the benzene-acetylene dimer? A matrix isolation infrared and ab initio quantum chemical study. Mol Phys 115(21–22):2637–2648. https://doi.org/10.1080/00268976.2017.1284357

    Article  CAS  Google Scholar 

  24. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams DF, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery Jr JA, Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ (2016) Gaussian 16 revision. A.03. Gaussian Inc., Wallingford

    Google Scholar 

  25. Boys SF, Bernardi F (1970) Calculation of small molecular interactions by differences of separate total energies - some procedures with reduced errors. Mol Phys 19(4):553–566. https://doi.org/10.1080/00268977000101561

    Article  CAS  Google Scholar 

  26. Burns LA, Marshall MS, Sherrill CD (2014) Comparing counterpoise-corrected, uncorrected, and averaged binding energies for benchmarking noncovalent interactions. J Chem Therory Comput 10(1):49–57. https://doi.org/10.1021/ct400149j

    Article  CAS  Google Scholar 

  27. Bulat FA, Toro-Labbe A, Brinck T, Murray JS, Politzer P (2010) Quantitative analysis of molecular surfaces: areas, volumes, electrostatic potentials and average local ionization energies. J Mol Model 16(11):1679–1691. https://doi.org/10.1007/s00894-010-0692-x

    Article  CAS  PubMed  Google Scholar 

  28. Lu T, Chen FW (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33(5):580–592. https://doi.org/10.1002/jcc.22885

    Article  CAS  PubMed  Google Scholar 

  29. Humphrey W, Dalke A, Schulten K (1996) VMD: Visual molecular dynamics. J Mol Graph Model 14(1):33–38. https://doi.org/10.1016/0263-7855(96)00018-5

    Article  CAS  Google Scholar 

  30. Glendening ED, Reed AE, Carpenter JE, Weinhold F NBO Version 3.1

  31. Wang H, Wang W, Jin WJ (2016) σ-Hole bond vs π-hole bond: a comparison based on halogen bond. Chem Rev 116(9):5072–5104. https://doi.org/10.1021/acs.chemrev.5b00527

    Article  CAS  PubMed  Google Scholar 

  32. Thi Hong Man N, Le Nhan P, Vo V, Tuan Quang D, Tien Trung N (2017) An insight into C□H···N hydrogen bond and stability of the complexes formed by trihalomethanes with ammonia and its monohalogenated derivatives. Int J Quantum Chem 117(6):e25338. https://doi.org/10.1002/qua.25338

    Article  CAS  Google Scholar 

  33. Mishra BK, Karthikeyan S, Ramanathan V (2012) Tuning the C-H...pi interaction by different substitutions in benzene-acetylene complexes. J Chem Therory Comput 8(6):1935–1942. https://doi.org/10.1021/ct300100h

    Article  CAS  Google Scholar 

  34. Shibasaki K, Fujii A, Mikami N, Tsuzuki S (2007) Magnitude and nature of interactions in benzene-X (X = ethylene and acetylene) in the gas phase: significantly different CH/pi interaction of acetylene as compared with those of ethylene and methane. J Phys Chem A 111(5):753–758. https://doi.org/10.1021/jp065076h

    Article  CAS  PubMed  Google Scholar 

  35. Bader RFW (2000) Atoms in molecules. A Quantum Theory. Clarendon Press, Oxford

    Google Scholar 

  36. Bader RFW (1991) A quantum theory of molecular structure and its applications. Chem Rev 91(5):893–928. https://doi.org/10.1021/cr00005a013

    Article  CAS  Google Scholar 

  37. Arnold WD, Oldfield E (2000) The chemical nature of hydrogen bonding in proteins via NMR: J-couplings, chemical shifts, and AIM theory. J Am Chem Soc 122(51):12835–12841. https://doi.org/10.1021/ja0025705

    Article  CAS  Google Scholar 

  38. Koch U, Popelier PLA (1995) Characterization of C-H...O hydrogen-bonds on the basis of the charge density. J Phys Chem 99(24):9747–9754. https://doi.org/10.1021/j100024a016

    Article  CAS  Google Scholar 

  39. Lipkowski P, Grabowski SJ, Robinson TL, Leszczynski J (2004) Properties of the C-H...H dihydrogen bond: an ab initio and topological analysis. J Phys Chem A 108(49):10865–10872. https://doi.org/10.1021/jp048562i

    Article  CAS  Google Scholar 

  40. Hassan A, Dinadayalane TC, Grabowski SJ, Leszczynski J (2013) Structural, energetic, spectroscopic and QTAIM analyses of cation-π interactions involving mono- and bi-cyclic ring fused benzene systems. Phys Chem Chem Phys 15(48):20839–20856. https://doi.org/10.1039/C3CP53927J

    Article  CAS  PubMed  Google Scholar 

  41. Espinosa E, Molins E, Lecomte C (1998) Hydrogen bond strengths revealed by topological analyses of experimentally observed electron densities. Chem Phys Lett 285(3):170–173. https://doi.org/10.1016/S0009-2614(98)00036-0

    Article  CAS  Google Scholar 

  42. Johnson ER, Keinan S, Mori-Sanchez P, Contreras-Garcia J, Cohen AJ, Yang WT (2010) Revealing noncovalent interactions. J Am Chem Soc 132(18):6498–6506. https://doi.org/10.1021/ja100936w

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  43. Wu Q, Su H, Wang H, Wang H (2018) Ab initio calculations, structure, NBO and NCI analyses of XH⋯π interactions. Chem Phys Lett 693:202–209. https://doi.org/10.1016/j.cplett.2018.01.015

    Article  CAS  Google Scholar 

  44. Michalczyk M, Zierkiewicz W, Scheiner S (2018) Triel-bonded complexes between TrR3 (Tr=B, Al, Ga; R=H, F, cl, Br, CH3) and Pyrazine. ChemPhysChem 19(22):3122–3133. https://doi.org/10.1002/cphc.201800774

    Article  CAS  PubMed  Google Scholar 

  45. Zhang L, Li D (2019) An insight into intramolecular blue-shifting CH⋯π hydrogen bonds in 1,3-hexadien-5-yne and its halogen-substituted derivatives. Chem Phys 518:58–68. https://doi.org/10.1016/j.chemphys.2018.11.001

    Article  CAS  Google Scholar 

  46. Alabugin IV, Manoharan M, Peabody S, Weinhold F (2003) Electronic basis of improper hydrogen bonding: a subtle balance of hyperconjugation and rehybridization. J Am Chem Soc 125(19):5973–5987. https://doi.org/10.1021/Ja034656e

    Article  CAS  PubMed  Google Scholar 

  47. Mukhopadhyay A, Pandey P, Chakraborty T (2010) Blue- and Red-Shifting CH...O Hydrogen Bonded Complexes between Haloforms and Ethers: Correlation of Donor ν(C-H) Spectral Shifts with C-O-C Angular Strain of the Acceptors. J Phys Chem A 114(14):5026–5033. https://doi.org/10.1021/Jp100524q

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

This work was supported by the Natural Science Foundation of Shandong Province under Grant No. ZR2017MB023 and No. ZR2016BL09 and the Research Fund of Binzhou University under Grant No. BZXYLG1919.

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  1. College of Chemical Engineering and Safety Engineering, Binzhou University, Binzhou, 256600, Shandong, People’s Republic of China

    Lijuan Zhang & Dazhi Li

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Zhang, L., Li, D. A theoretical investigation on the complexes of B3O3H3 with acetylene and its substituted derivatives. J Mol Model 25, 332 (2019). https://doi.org/10.1007/s00894-019-4223-0

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