A theoretical investigation on the complexes of B3O3H3 with acetylene and its substituted derivatives
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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.
KeywordsBoroxine Acetylene π-Hole bonding AIM NCI NBO
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.
- 1.Steudel R (1992) The chemistry of inorganic ring systems. Elsevier, New YorkGoogle 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 CrossRefGoogle 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 CrossRefGoogle 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., WallingfordGoogle Scholar
- 30.Glendening ED, Reed AE, Carpenter JE, Weinhold F NBO Version 3.1Google 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 CrossRefGoogle 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 CrossRefPubMedGoogle Scholar
- 35.Bader RFW (2000) Atoms in molecules. A Quantum Theory. Clarendon Press, OxfordGoogle 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 CrossRefPubMedGoogle 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 CrossRefPubMedGoogle Scholar