DFT studies and crystal structure of synthesized 1,3-bis(2-thiophenylmethyl)-4,5-dihydroimidazolidinium hexafluorophosphate salt
Synthesized compound 5, (C13H15N2S2)[PF6], was fully characterized with X-ray diffraction method. In this compound, the asymmetric unit contains a 1,3-(2-thiophenylmethyl)-4,5-dihydroimidazolidinium cation and a hexafluorophosphate anion. Due to an 180° rotation about the thiophene-CH2 bonds, the thiophene rings in the cation are disordered [site-occupancy factors = 0.903(4)/0.097(4) and 0.837(5)/0.163(5), respectively]. The short C—N bond lengths [1.303(4) and 1.287(4) Å] in the imidazolidine ring display partial electron delocalization within the N—C—N fragment. Anion and cations are connected through intermolecular C—H...F hydrogen bonds and three p-p stacking interactions [centroid-centroid distances = 3.890(3), 3.852(5) and 3.816(7) Å] between the thiophene rings of the adjacent cations, forming layers parallel to (011). Furthermore, we studied theoretical studies of this compound, too. Geometry optimization was carried out in gas phase by Density Functional Theory (DFT) method with B3LYP applying 6-311++G** basis set. The obtained results from experimental and theoretical structural properties of compound 5 had been compared to each other.
S. Akkoç, Y. Gök, Synthesis And Characterization of 1- Phenyl-3-Alkylbenzimidazol-2-ylidene Salts And Their Catalytic Activities in The Heck And Suzuki Cross-Coupling Reactions, J. Coord. Chem. 66 (2013) 1396-1404.
O.H. Winkelmann, A. Riekstins, S.P. Nolan, O. Navarro, A Comparative Study on (NHC)Pd(acac)Cl Complexes (NHC = N-heterocyclic carbene): Indications for the Origin of the Different Reactivity of Saturated and Unsaturated NHC in Cross-Coupling Reactions, Organometallics 28 (2009) 5809-5813.
S. Akkoç, Y. Gök, M. Akkurt, M. N. Tahir, Catalytic Activities in the Direct C5 Arylation of Novel Palladium N-Heterocyclic Carbene Complexes Containing Benzimidazol-2-ylidene Nucleus, Inorg. Chim. Acta 413 (2014) 221-230.
T. Ritter, M.W. Day, R.H. Grubbs, Rate acceleration in olefin metathesis through a fluorine-ruthenium interaction, J. Am. Chem. Soc. 128 (2006) 11768-11769.
A. Aktaş, S. Akkoç, Y. Gök, Palladium Catalyzed Mizoroki-Heck And Suzuki-Miyaura Reactions Using Napthalenomethyl-Substituted Imidazolidin-2-ulidene Ligands in Aqueous Media, J. Coord. Chem. 66 (2013) 2901-2909.
V. Resch, J. H. Schrittwieser, E. Siirola, W. Kroutil, Novel carbon-carbon bond formations for biocatalysis, Curr. Opin. Biotech. 22 (2011) 793-799.
R. E. Minto, B.J. Blacklock, Biosynthesis and function of polyacetylenes and allied natural products, Prog. Lipid. Res. 47 (2008) 233-306.
H.H. Kart, S. Özdemir Kart, M. Karakuş, M. Kurt, Ab initio/DFT Calculations of Butyl Ammonium Salt of O,O′-Dibornyl Dithiophosphate, Spectrochim Acta A, 129 (2014) 421–428.
N. Argaman, G. Makov, Density Functional Theory-An Introduction, Am. J. Phys. 68 (2000) 69-79.
S. Akkoç, Y. Gök, M. Akkurt, M. N. Tahir, Imidazole, Pyrimidine and Diazepine Containing Heteroaryl-Substituted Heterocyclic Salts as Efficient Ligand Precursors for Mizoroki-Heck Coupling Reaction: Synthesis, Structural Characterization and Catalytic Activities, J. Iran. Chem. Soc. 11 (2014) 1767-1774.
Stoe & Cie (2002). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.
G.M. Sheldrick, A short history of SHELX, Acta Cryst. A64 (2008) 112–122.
Spartan'10; Wavefunction, Inc.: Irvine, CA, 2011.
D. Young, Computational Chemistry, Wiley-Interscience, 2001. Appendix A. A.1.6 pg 330, SPARTAN.
İ. Ozdemir, N. Gurbuz, Y. Gok, B. Cetinkaya, N-functionalized azolin-2-ylidene-palladium-catalyzed heck reaction, Heteroatom Chemistry 2008, 19(1), 82-86.
L.J. Farrugia, WinGX and ORTEP for Windows: an update, J. Appl. Cryst. 45 (2012) 849–854.
H. Arslan, D. VanDerveer, I. Özdemir, N. Gürbüz, Y. Gök, B. Çetinkaya, 1,3-bis(2-thienylmethyl)-4,5-dihydroimidazolium trichlorido(6-p-cymene)ruthenate(II), Acta Cryst. E65 (2009) 165–166.
F.H. Allen, O. Kennard, D.G. Watson, L. Brammer, A.G. Orpen, R. Taylor, Tables of bond lengths determined by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds,
J. Chem. Soc. Perkin Trans. 2 (1987) 1–19.
J. Turk. Chem. Soc., Sect. A: Chem.