2-Thienylboronic Acid: A DFT Study For The Spectral, Structural And Molecular Orbital Analysis

Öz

2-Thienylboronic acid and its isomers were investigated for their structural properties and molecular orbitals. HOMO-LUMO frontier surfaces and FT-IR, FT-RAMAN analysis were carried out in an integrated approach. The molecule was investigated for its structural properties such as bond lengths, bond angles and torsion angles. The molecule was examined as isomers separately. For quantum chemical calculations, DFT was used in the B3LYP level and 6.31G* basis set. These calculations were carried out via SPARTAN-14 computational chemistry software. The calculated results were compared and found to be very close to some previous experimental ones.

Anahtar Kelimeler

• Boronic acid derivatives
• DFT
• Spectral analysis
• HOMO LUMO
• Molecular structure

2-Tienilboronik Asid: Spektroskopik, Yapısal ve Molekül Orbital Analizi Üzerine Bir DFT Çalışması

Öz

2-Tienilboronik asid ve izomerleri, Yapısal özellikler ve molekül orbitaller bakımından incelenmiştir. HOMO-LUMO sınır yüzeyleri ve FT-IR, FT-RAMAN analizleri tümleşik bir anlayışla gerçekleştirilmiştir.Molekül, bağ uzunluklar, bağ açıları ve burkulma açıları gibi yapısal özellikleri yönüyle araştırılmıştır. Molekülün izomerleri birbirinden ayrı olarak ele alınmıştır. Kuantum kimyasal hesaplamalarda, DFT yöntemi, B3LYP düzeyinde ve 6.31G* temel seti ile kullanılmıştır. Bu hesaplamalar, SPARTAN-14 hesapsal kimya paket programı kullanılarak gerçekleştirilmiştir. Hesaplanan sonuçların, literatürdeki deneysel değerlere çok yakın oldukları görülmüştür.

Anahtar Kelimeler

• Boronik asid türevleri
• DFT
• Spektroskopik analiz
• HOMO LUMO
• Molekül yapısı

Kaynakça

1. [1] Hall D.G., Boronic acids: preparation and applications in organic synthesis and medicine, DOI:10.1002/3527606548, Wiley‐VCH Verlag GmbH & Co. KGaA, 2006
2. [2] Kar A., Pharmacognosy and Pharmacobiotechnology 2nd Ed., New Age International (P) Ltd., Publishers New Delhi 2007
3. [3] Tjarks W., Anisuzzaman A.K., Liu L., Soloway S.H., Barth R.F., Perkins D.J., Adams D.M., Synthesis and in vitro evaluation of boronated uridine and glucose derivatives for boron neutron capture therapy. J. Med. Chem., 35, 1628-1633, 1992
4. [4] Zepeda-Velazquez L. C. Synthesis and characterızation of novel stimuli-responsive silicone-boronic acid materials Ph.D. thesis McMaster University Hamilton, Ontario, 2015
5. [5] Christophersen C., Begtrup M., Ebdrup S., Petersen H., Vedsø P., Synthesis of 2,3-Substituted Thienylboronic Acids and Esters. The Journal of organic chemistry, 68(24), 9513-9516, 2003
6. [6] Wang Y., Liao J., Wang B., Chen H., Zhao H., Peng M., Fan S., Synthesis and Properties of Novel Borondipyrromethene (BODIPY)-Tethered Triphenylamine Conjugates, Aust. J. Chem., 68(10), 1485-1491. 2015
7. [7] Fang Y., Zhang X., Targeting NEK2 as a Promising Therapeutic Approach for Cancer Treatment, Cell Cycle, 15(7), 895-907, 2016
8. [8] Fa-Bao L., Xun Y., Tong-Xin L., Guan-Wu W., Fullerenyl Boronic Esters: Ferric Perchlorate-Mediated Synthesis and Functionalization, Organic Letters, 14(7), 1800-1803, 2012

9. [9] Lu G.P., Voigtritter K. R., Cai C., Lipshutz B., H., Ligand effects on the stereochemical outcome of Suzuki-Miyaura couplings. The Journal of organic chemistry, 77(8), 3700-3703, 2012
10. [10] Karabacak M., Kose E., Sas E.B., Kurt M., Asiri A.M., Atac A., DFT calculations and experimental FT-IR, FT-Raman, NMR, UV–Vis spectral studies of 3-fluorophenylboronic acid, Spectrochim. Acta, Part A, 136, 306-320, 2015
11. [11] Zheng H., Ghanbari S., Nakamura S., Hall D.G., Boronic Acid Catalysis as a Mild and Versatile Strategy for Direct Carbo- And Heterocyclizations of Free Allylic Alcohols, Angewandte Chemie Int. Ed., 51(25), 6187-6190, 2012
12. [12] Zheng H., Lejkowski M., Hall D.G., Mild and selective boronic acid-catalyzed 1,3-transposition of allylic alcohols and Meyer–Schuster rearrangement of propargylic alcohols, Chem. Sci., 2(7), 1305-1310, 2011
13. [13] Sachan A. K., Pathak S. K., Sinha L., Prasad O., Karabacak M., Asiri A. M., A combined experimental and theoretical investigation of 2-Thienylboronic acid: Conformational search, molecular structure, NBO, NLO and FT-IR, FT-Raman, NMR and UV spectral analysis. Jour. of Molec. Struct., 1076, 639-650, 2014.
14. [14] Ghosh R., Simonsen S.H., Structure of 2-(2'-thienyl)pyridine at 193 K, Acta Crystallogr., Sect. C: Cryst. Struct. Commun., 49(5), 1031-1032, 1993.
15. [15] Rettig S.J., Trotter J., Crystal and molecular structure of phenylboronic acid (C6H5B(OH)2 Can. J. Chem. 55, 3071-3075, 1977
16. [16] Silverstein R. M., Webster F. X., Kiemle D.J. Spectrometric Identification of Organic Compounds 7th Ed. John Wiley Sons INC. 2005
17. [17] Ramachandran K. I., Deepa G., Namboori K., Computational Chemistry and Molecular Modeling: Principles and Applications, Springer-Verlag Heidelberg Berlin 2008.
18. [18] Jensen F., Introduction to Computational Chemistry, Wiley, 2016
19. [19] SPARTAN’14 Wavefunction Inc. Irvine CA, USA, 2014
20. [20] Hehre W. J., SPARTAN’14 Tutorial and User's Guide, Wavefunction, Inc 2014
21. [21] Peter K., Vollhardt C., Schore N. E.. Organic chemistry: structure and function, 6th ed. Freeman&Comp. NY-US 2011
22. [22] Rani U., Karabacak M., Tanrıverdi O., Kurt M., Sundaraganesan N., The spectroscopic (FTIR, FT-Raman, NMR and UV), first-order hyperpolarizability and HOMO-LUMO analysis of methyl boronic acid. Spectrochim. Acta, Part A, 92, 67-77, 2012.
23. [23] Karabacak M., Kose E., Atac A., M. Cipiloglu A., Kurt M., Molecular structure investigation and spectroscopic studies on 2,3-difluorophenylboronic acid: A combined experimental and theoretical analysis. Spectrochim. Acta, Part A, 97, 892-908, 2012
24. [24] https://www.sigmaaldrich.com/catalog/product/aldrich/436836?lang=en®ion=TR 04/23/2020