Abstract
In the present work, a detailed investigation of synergistic effects between the intramolecular hydrogen bond (IMHB) and π-electron delocalization (π-ED) of 3-hydroxy prop-2-en thial (HPT) and its halogenated derivatives was performed. For this purpose, at first, the π-ED in the enol form of the benchmark systems by various aromaticity indices such as λ, λ́, HOMA, NICS, PDI, ATI, and FLUπ were evaluated. On the other hand, the strength of IMHB by various descriptors such as energetical, geometrical, spectral, topological, and molecular orbital parameters was also estimated. For better understanding the nature of the synergistic phenomenon, we examined and compared the linear relationships between the π-ED indices with the HB descriptors. Our results show that the geometrical indicators have the best linear relationships with all of the mentioned HB parameters. Also, according to their absolute linear correlation coefficients, the following order is concluded:
λ > λ > HOMA > FLUπ > ATI > NICS (1) > PDI > NICS (0)Finally, the synergistic effect between the π-ED and IMHB from the position and nature point of views is discussed. These results clearly show that the synergistic effect of R1 derivatives is negative, while the corresponding effects of R2 and R3 ones are positive. Moreover, the synergetic effects also depend on the nature of substitutions especially their electronegativity values (F > Br > Cl).
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References
Jeffrey GA, Saenger W (2012) Hydrogen bonding in biological structures. Springer Science & Business Media.
Jeffrey GA (1997) An introduction to hydrogen bonding. Oxford University Press, New York
Desiraju GR, Steiner T (2001) The weak hydrogen bond in structural chemistry and biology. Oxford University Press, Oxford, MS
Grabowski SJ (2006) Hydrogen bonding – new insights. Springer, Berlin
Gilli G, Gilli P (2009) The nature of hydrogen bond. Oxford University Press, New York
Sobczyk L, Grabowski SJ, Krygowski TM (2005) Interrelation between H-bond and Pi-electron delocalization. Chem Rev 105(10):3513–3560
Grabowski SJ (2006) Theoretical studies of strong hydrogen bonds. Annual Reports Section“ C”(Physical Chemistry) 102:131-165.
Maharramov AM, Mahmudov KT, Kopylovich MN, Silva MFCGDA, Pombeiro AJL (2016) Non-covalent interactions in the synthesis and design of new compounds. Wiley Online Library.
Etter MC (1990) Encoding and decoding hydrogen-bond patterns of organic compounds. Acc Chem Res 23(4):120–126
Steiner T (2002) The hydrogen bond in the solid state. Angew Chem Int Ed 41:48–76
Desiraju GR (2007) Kristall-Engineering: eine holistische Darstellung. Angew Chem 119:8492–8508
Scheiner S (1997) Hydrogen bonding. a theoretical perspective. Oxford University Press, New York.
Gilli P, Gilli G (2010) Hydrogen bond models and theories: the dual hydrogen bond model and its consequences. J Mol Struct 972(1-3):2–10
Mahmudov KT, Pombeiro AJ (2016) Resonance-assisted hydrogen bonding as a driving force in synthesis and a synthon in the design of materials. Chem Eur J 22(46):16356–16398
Gilli P, Bertolasi V, Pretto L, Lyčka A, Gilli G (2002) The nature of solid-state N− H⊙⊙⊙ O/O− H⊙⊙⊙ N tautomeric competition in resonant systems. Intramolecular proton transfer in low-barrier hydrogen bonds formed by the⊙⊙⊙ OC− CN− NH⊙⊙⊙⇄⊙⊙⊙ HO− CC− NN⊙⊙⊙ Ketohydrazone− Azoenol System. A variable-temperature x-ray crystallographic and DFT computational study. J Am Chem Soc 124(45):13554–13567
Gilli P, Bertolasi V, Pretto L, Ferretti V, Gilli G (2004) Covalent versus electrostatic nature of the strong hydrogen bond: discrimination among single, double, and asymmetric single-well hydrogen bonds by variable-temperature X-ray crystallographic methods in β-diketone enol RAHB systems. J Am Chem Soc 126(12):3845–3855
Gilli P, Bertolasi V, Ferretti V, Gilli G (2000) Evidence for intramolecular N− H⊙⊙⊙ O resonance-assisted hydrogen bonding in β-enaminones and related heterodienes. A combined crystal-structural, IR and NMR spectroscopic, and quantum-mechanical investigation. J Am Chem Soc 122(42):10405–10417
Cleland W, Kreevoy MM (1994) Low-barrier hydrogen bonds and enzymic catalysis. Science 264(5167):1887–1890
Cleland WW, Frey PA, Gerlt JA (1998) The low barrier hydrogen bond in enzymatic catalysis. J Biol Chem 273(40):25529–25532
Nowroozi A, Roohi H, Hajiabadi H, Raissi H, Khalilinia E, Najafi Birgan M (2011) OH⋯ S intramolecular hydrogen bond in thiomalonaldehyde derivatives; a quantum chemical study. Comput Theor Chem 963(2-3):517–524
Raissi H, Nowroozi A, Mohammdi R, Hakimic M (2006) Intramolecular hydrogen bond, molecular structure and vibrational assignment of tetra-acetylethane: a density functional study. Spectrochim Acta A Mol Biomol Spectrosc 65(3-4):605–615
Raissi H, Nowroozi A, Roozbeh M, Farzada F (2006) Molecular structure and vibrational assignment of (trifluoroacetyl) acetone: a density functional study. J Mol Struct 787(1-3):148–162
Nowroozi A, Mohammadzadeh Jahani P, Asli N, Hajiabadi H, Dahmardeh S, Raissi H (2012) Evaluation of the origin of conformational and tautomeric preferences in N-formylformamide–a quantum chemical study. Int J Quantum Chem 112(2):489–497
Nowroozi A, Raissi H, Hajiabadi H, Mohammadzadeh Jahani P (2011) Reinvestigation of intramolecular hydrogen bond in malonaldehyde derivatives: an ab initio, AIM and NBO study. Int J Quantum Chem 111(12):3040–3047
Hargis JC, Evangelista FA, Ingels JB, Schaefer HF (2008) Schaefer Short intramolecular hydrogen bonds: derivatives of malonaldehyde with symmetrical substituents. J Am Chem Soc 130(51):17471–17478
Sanz P, Mó O, Yáñez M, Elguero J (2007) Non-resonance-assisted hydrogen bonding in hydroxymethylene and aminomethylene cyclobutanones and cyclobutenones and their nitrogen counterparts. ChemPhysChem 8(13):1950–1958
Sanz P, Mó O, Yáñez M, Elguero J (2008) Bonding in tropolone, 2-aminotropone, and aminotroponimine: no evidence of resonance-assisted hydrogen-bond effects. Chem Eur J 2008; 14(14):4225-4232.
Alkorta I, Elguero J, Mó O, Yáñez M, Del Bene JE (2004) Do coupling constants and chemical shifts provide evidence for the existence of resonance-assisted hydrogen bonds? Mol Phys 102(23-24):2563–2574
Góra RE, Maj M, Grabowski SJ (2013) Resonance-assisted hydrogen bonds revisited. Resonance stabilization vs. charge delocalization. Phys Chem Chem Phys 15(7):2514–2522
Rozas I, Alkorta I, Elguero J (2001) Intramolecular hydrogen bonds in o rtho-substituted hydroxybenzenes and in 8-susbtituted 1-hydroxynaphthalenes: can a methyl group be an acceptor of hydrogen bonds? J Phys Chem A 105(45):10462–10467
Nowroozi A, Roohi H, Sadeghi MS, Sheibaninia M (2011) The competition between the intramolecular hydrogen bond and π-electron delocalization in trifluoroacetylacetone—a theoretical study. Int J Quantum Chem 111(3):578–585
Nadim ES, Raissi H, Yoosefian M, Farzad F, Nowroozi A (2010) Ab initio and DFT computational studies on molecular conformations and intramolecular hydrogen bonding in 3-mercapto-but-2-enethial. J Sulfur Chem 31(4):275–285
Chen C, Shyu SF (2000) Conformers and intramolecular hydrogen bonding of the oxalic acid monomer and its anions. Int J Quantum Chem 76(4):541–551
Haddon R (1980) Symmetrical hydrogen bonding: molecular orbital theory of the. Pi-electron component. J Am Chem Soc 102(6):1807–1811
Higgins J, Zhou X, Liu R, Huang TTS (1997) Theoretical study of thermal decomposition mechanism of oxalic acid. J Phys Chem A 101(14):2702–2708
Giricheva NI, Girichev GV, Lapshina SB, Kuzmina NI (2000) Molecular structure of dipivaloylmethane and the intramolecular hydrogen bond problem. J Struct Chem 41(1):48–54
Bernardi F, Csizmadia IG, Mangini A (1985) Organic sulfur chemistry. Elsevier Science Pub, Co
Block E (2013) Reactions of organosulfur compounds: organic chemistry: a series of monographs. Academic press
Patai S, Rappoport Z (1986) The chemistry of organic selenium and tellurium compounds. John Wiley & Sons
McReynolds MD, Dougherty JM, Hanson PR (2004) Synthesis of phosphorus and sulfur heterocycles via ring-closing olefin metathesis. Chem Rev 104(5):2239–2258
Duus F (1979) Enol-enethiol tautomerism of β-thioxoketones. Phosphorus Sulfur Rel Elem 6(1-2):83–83
Berg U, Sandström J, Carlsen L, Duus F (1983) β-Thioxoketones. Part 9. A dynamic 1H nuclear magnetic resonance spectroscopic study of thioacetylacetone and related β-thioxoketones. Direct observation of the enol and enethiol tautomeric constituents and their interconversion. J Chem Soc Perkin Trans 2(9):1321–1325
Carlsen L, Duus F (1980) β-Thioxoketones. Part 6. Electronic absorption spectra of aromatic β-thioxoketones. A study of enol–enethiol tautomerism. J Chem Soc Perkin Trans 2(12):1768–1773
Nørskov-Lauritsen L, Carlsen L, Duus F (1983) Definitive evidence for the existence of the hydrogen-bonding enol form of non-aromatic β-thioxoketones. X-Ray crystal structure of 1-(1-methylcyclopropyl)-3-thioxobutan-1-one. J Chem Soc Chem Commun 9:496–498
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, Vreven Jr T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2003) Gaussian 03 revision C 02 (or D 01). Gaussian Inc, Pittsburgh
Biegler KF, Schonbohm J, Bayles D (2001) AIM2000: a program to analyze and visualize atoms in molecules. J Comput Chem 22:545–559
Glendening ED, Reed AE, Carpenter JE, Weinhold F (1992) NBO, Version 3.1 University of Wisconsin, Madison.
Hameka HF (1958) On the nuclear magnetic shielding in the hydrogen molecule. J Mol Phys 1:203–215
Gilli G, Bellucci F, Ferretti V, Bertolasi V (1989) Evidence for resonance-assisted hydrogen bonding from crystal-structure correlation on the enol form of the bdiketone fragment. J Am Chem Soc 111:1023–1028
Nakhaei E, Nowroozi A (2016) On the performance of resonance assisted hydrogen bond theory in malonaldehyde derivatives. Comput Theor Chem 1096:27–32
Krygowski TM, Cyranski MK (1996) Separation of the energetic and geometric contributions to the aromaticity of p-electron carbocyclics. Tetrahedron 52:1713–1722
Schleyer PVR, Maerker C, Dransfeld A, Jiao H, Hommes NJR (1996) Nucleusindependent chemical shifts: a simple and efficient aromaticity probe. J Am Chem Soc 118:6317–6318
Poater J, Feradera X, Duran M, Sola M (2003) The delocalization index as an electronic aromaticity criterion: application to a series of planar polycyclic aromatic hydrocarbons. Chem Eur J 9:400–406
Bultinck P, Ponec R, Van Damme S (2005) Multicenter bond indices as a new measure of aromaticity in polycyclic aromatic hydrocarbons. J Phys Org Chem 18:706–718
Matito E, Salvador P, Sola M (2006) Aromaticity measures from fuzzy-atom bond orders (FBO). The aromatic fluctuation and the para-delocalization (PDI) indexes. J Phys Chem A 110:5108–5113
Matsushita† O, Derkacheva VM, Muranaka A, Shimizu S, Uchiyama M, Luk’yanets EA, Kobayashi N (2012) Rectangular-shaped expanded phthalocyanines with two central metal atoms. J Am Chem Soc 134(7):3411-3418.
Gilli G, Bellucci F, Ferretti V, Bertolasi V (1989) Evidence for resonance-assisted hydrogen bonding from crystal-structure correlations on the enol form of the. Beta -diketone fragment. J Am Chem Soc 111(3):1023–1028
Nowroozi A, Raissi H, Farzad F (2005) The presentation of an approach for estimating the intramolecular hydrogen bond strength in conformational study of β-Aminoacrolein. J Mol Struct THEOCHEM 730(1-3):161–169
Buemi G, Zuccarello F (2004) DFT study of the intramolecular hydrogen bonds in the amino and nitro-derivatives of malonaldehyde. Chem Phys 306(1-3):115–129
Jabłoński M, Kaczmarek A, Sadlej AJ (2006) Estimates of the energy of intramolecular hydrogen bonds. J Phys Chem A 110(37):10890–10898
Schuster P, Zundel G (1976) The hydrogen bond structure and spectroscopy. North-Holland, Amsterdam
Nowroozi A, Hajiabadi H, Akbari F (2014) H···O and OH···S intramolecular interactions in simple resonance-assisted hydrogen bond systems: a comparative study of various models Struct. Chem 25:251–258
Jesus AL, Redinha J (2011) Charge-assisted intramolecular hydrogen bonds in disubstituted cyclohexane derivatives. J Phys Chem A 115(48):14069–14077
Nowroozi A, Raissi H, Hajiabai H, Mohammadzadeh P (2011) Reinvestigation of intramolecular hydrogen bond in malonaldehyde derivatives: an ab initio, AIM and NBO study. Int J Quantum Chem 111:3040
Nowroozi A, Roohi H, Hajiabadi H, Raissi H, Khalilinia E, Najafi M (2011) A comparative study of two-ring resonance-assisted hydrogen bond systems. Comput Theor Chem 963:517
Richard F, Bader R (1990) Atoms in molecules: a quantum theory. Oxford University Press
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Nowroozi, A., Housaindokht, M.R. & Nakhaei, E. A detail investigation of synergistic effects between the intramolecular hydrogen bond and π-electron delocalization in 3-hydroxy prop-2-en thial and its derivatives. Struct Chem 32, 709–718 (2021). https://doi.org/10.1007/s11224-020-01649-y
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DOI: https://doi.org/10.1007/s11224-020-01649-y