(This is a sample cover image for this issue. The actual cover is not yet available at this time.) This article appeared in a journal published by Elsevier. The attached copy is furnished to the author for internal non-commercial research and education use, including for instruction at the authors institution and sharing with colleagues. Other uses, including reproduction and distribution, or selling or licensing copies, or posting to personal, institutional or third party websites are prohibited. In most cases authors are permitted to post their version of the article (e.g. in Word or Tex form) to their personal website or institutional repository. Authors requiring further information regarding Elsevier’s archiving and manuscript policies are encouraged to visit: http://www.elsevier.com/copyright Author's personal copy Journal of Molecular Structure 1036 (2013) 151–160 Contents lists available at SciVerse ScienceDirect Journal of Molecular Structure journal homepage: www.elsevier.com/locate/molstruc Structure, vibrational assignment, and NMR spectroscopy of 1,2-bis (dichloroacetyl) cyclopentadiene Sayyed Faramarz Tayyari a,⇑, Somayeh Laleh b, Mansoureh Zahedi-Tabrizi c, Mohammad Vakili b a Chemistry Department, Shahrood Branch, Islamic Azad University, Shahrood, Iran Chemistry Department, Ferdowsi University of Mashhad, Mashhad 91775-1436, Iran c Chemistry Department, Alzahra University, Tehran, Iran b h i g h l i g h t s " bis(dichloroacetyl)cyclopentadiene forms strong intramolecular hydrogen bond. " The potential function for proton movement is a low barrier double minimum. " The OH stretching vibration is observed at about 1700 cm 1 . " The observed NMR chemical shifts are in agreement with the theoretical values. a r t i c l e i n f o Article history: Received 7 July 2012 Received in revised form 25 September 2012 Accepted 25 September 2012 Available online 2 October 2012 Keywords: 1,2-Bis (dichloroacetyl) cyclopentadiene Intramolecular hydrogen bond Very strong hydrogen bond Density functional Theory NMR Vibrational assignment a b s t r a c t Molecular structure, intramolecular hydrogen bond (IHB), 1H and 13C chemical shifts, and vibrational assignment of newly prepared 1,2-bis (dichloroacetyl) cyclopentadiene (DCACP), have been investigated by means of density functional theory (DFT) calculations. In addition, the geometry of the most stable conformer was also optimized at the MP2/6-31G level. By calculations at the B3LYP level, using 6311++G basis set, the IR band frequencies of the most stable conformer and its deuterated analogue and the 13C and 1H chemical shifts were clearly assigned. In addition, the anharmonic vibrational wavenumbers in solution were also calculated at the B3LYP/6-31G level. All theoretical calculations and experimental spectroscopy data are consistent with a very strong intramolecular hydrogen bond in this f-diketone. According to the theoretical calculations, the enolated proton in DCACP slightly deviates from half way between the two oxygen atoms, Cs symmetry, which suggests existence of a low barrier double minimum potential for this system. Ó 2012 Elsevier B.V. All rights reserved. 1. Introduction It has been proposed that the short and strong hydrogen bonds with low-barrier (67 kcal/mol) play important role in enzymatic processes [1,2]. The information on intramolecular hydrogen bonding in particular is very useful to understand various molecular properties. The intramolecular hydrogen bonding may be responsible for the molecular geometries as well as the stability of a certain predominant conformation. Among many intramolecularly hydrogen bonded systems, the conjugated dicarbonyl compounds have been widely investigated not only by theoretical approaches but also by experimental methods [3–13]. Conjugated dicarbonyl compounds, such as b-dicarbonyls and 1,2-diacyl-cyclopentadienes, are capable to form very strong intra⇑ Corresponding author. Tel.: +98 511 8780216. E-mail address: [email protected] (S.F. Tayyari). 0022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.molstruc.2012.09.069 molecular hydrogen bond. The strength of hydrogen bond in these systems increases by p-electron conjugation with the chelated rings [14]. In spite of extensive works on structure and properties of hydrogen bonds in the enol form of b-dicarbonyl compounds, only a few reports considering the hydrogen bonding in 1,2diacyl-cyclopentadienes are appeared in the literatures. These compounds solely exist in the enol form, Fig. 1, characterized by a seven-membered ring [15–19], and their proton chemical shifts are consistent with a very strong hydrogen bond [17,20,21]. These compounds are classified by Gilli and Bertolasi [22] as fdiketone enols. The simplest member of this class of compounds is 6-hydroxy-1-formylfulvene (HFF), which has been the subject of a number of practical [16–20] and theoretical [13] investigations. The microwave spectrum of HFF [16] is consistent either a C2v or a Cs with an O O distance near to 2.5 Å. An investigation on IR spectrum of HFF [18], which only considers a few bands, supports the presence of rapidly interconverting Cs forms, while the C2v nu- Author's personal copy 152 S.F. Tayyari et al. / Journal of Molecular Structure 1036 (2013) 151–160 2.2. Instrumentation Fig. 1. The enol form of DCACP and its atom numbering system. clear symmetry is supported by the NMR data [21]. On the other hand, Perrin and Ohta [23,24] by using the NMR method of isotopic perturbation of equilibrium indicated existing of an asymmetric structure for HFF. Solid state X-ray and neutron diffraction data [17] indicate a slightly asymmetric and nearly linear hydrogen bond with an O O distance of 2.513 and 2.550 Å, respectively, which the latter is consistent with the calculated results (2.556 Å) at the MP2/6-31G level by Millefiori and Alparone [13]. Deuteron quadrupole coupling constant studies suggests a low barrier double minimum potential for HFF and its 1,6-diphenyl derivative [25]. Except for HFF, the X-ray crystallography of two other members of this class of compounds has been reported, which exhibit short, strong, and nearly linear hydrogen bonds with a length at about 2.44 Å [15]. The aim of the present paper is to predict the structure, nature of the intramolecular hydrogen bond of DCACP by means of density functional theory (DFT). The calculated NMR chemical shifts and FT-IR spectrum will be compared with the corresponding experimental values. 2. Experimental 2.1. Preparation DCACP was prepared by modified procedures of Linn and Sharkey [26] as follows: phenyl-lithium was prepared from 21 ml (0.2 mol) bromobenzene and 2.8 g (0.4 mol) lithium in dry ether under an atmosphere of argon. To this solution, 13.2 g (0.2 mol) freshly distilled cyclopentadiene in 30 ml dry diethyl ether was added dropwise. To the resulting well-stirred suspension of the lithium cyclopentadiene there was added, dropwise over a course of 30 min at 0 °C, 19.2 g (0.2 mol) dichloroacetyl chloride in 30 ml dry diethyl ether. There was an immediate formation of a bright yellow color, which gradually darkened. Stirring was continued for an additional 30 min then the reaction mixture was hydrolyzed with dilute aqueous acetic acid. The bright red ether layer was separated and the aqueous layer extracted twice with 10 ml ether. The combined organic solution was washed with water and dried over anhydrous sodium sulfate. The solvent was removed by evaporation to leave a dark yellow solid. Recrystallization from cyclohexane gave 14.4 g (25%) yellow needles, m.p. 141.5–142.5 °C. Deuterated DCACP (D-DCACP) was prepared by adding 3 ml D2O to a solution of 1 g DCACP in 5 ml CCl4. The mixture was left overnight, at room temperature in a dry box. Then the organic layer was separated and dried over Na2SO4 and vacuumed off to remove the solvent and water. This method was repeated three times. The NMR experiments were performed on dilute CDCl3 and [2H6]-acetone solutions at 300 K. The NMR spectra were obtained on a FT-NMR, Brucker DRX 500 AVANCE spectrometer equipped with a z-gradient accessory and an inverse (or direct detection) 5 mm diameter probehead working at 500.13 MHz for 1H and 125.76 MHz for 13C. The chemical shifts were referenced to the signal of TMS. The Mid-IR spectra of DCACP and D-DCACP were recorded as KBr disk and CCl4 solution in the range of 4000–500 cm1 with resolution of 2 cm1 by averaging the results of 20 scans on a Bomem MB-154 Fourier Transform Spectrophotometer. The Far-IR spectra in the region 600–100 cm1 were obtained using a Thermo Nicolet NEXUS 870 FT-IR spectrometer equipped with a DTGS/polyethylene detector and a solid substrate beam splitter. The spectrum was collected with a resolution of 2 cm1 by signal averaging the results of 64 scans. 3. Method of analysis The Gaussian 09 [27] program was used for all quantum mechanical computations. The full geometry optimizations for all possible chelated and the corresponding open structures were performed at the B3LYP level [28,29] using 6-31G, 6-311G, and 6311++G basis sets. In addition, the geometry of the most stable conformer was also optimized at the MP2/6-31G⁄⁄ level. For the chelated conformers, the optimization and vibrational frequency calculations were also performed at the B3LYP level, using 6311++G basis set. The frequencies for infrared fundamentals of the vibrational modes of the most stable conformer and its deuterated analog were also calculated by anharmonic method at the B3LYP/6-31G level, and we show below that these predictions agree more satisfactorily with the measured frequencies. The assignment of the calculated wavenumbers is aided by the animation option of the GaussView 5 [30] graphical interface for Gaussian programs, which gives a visual representation of the shape of the vibrational modes. To obtain the geometry of DCACP conformers, the ACHCl2 groups rotation minima were calculated separately, at the B3LYP/ 6-31G level, for each of two groups, by assuming that the molecular geometry can relax during rotation (i.e. for each value of torsion angle the molecular geometry was fully optimized). The potential scans for the internal rotation of both CHCl2 groups, about C12AC6 and C11AC8 bonds (see Fig. 1), were obtained by allowing the H17C12C6O7 and H16C11C8O9 dihedral angles to vary from 0° to 180° by steps of 15°. By this method, four stable chelated conformers were obtained which are shown in Fig. 2. These stable conformers were further fully optimized in the gas phase and in solution at the B3LYP level using 6-31G, 6311G, and 6-311++G basis sets. To calculate the hydrogen bond strength of the chelated conformers, the OAH bond of the chelated conformers, A-I to A-IV, were rotated about CAO bond by 180° and then the resulted structures were fully optimized to obtain the final open structures, B-I to B-IV. The absolute shieldings for all stable chelated conformers of DCACP and tetramethylsilane (TMS) have been obtained using the gauge-including atomic orbital (GIAO) method [31–35] at the B3LYP/6-311++G level. The predicted 13C and 1H chemical shifts are derived from equation d = ro r, where d is the chemical shift, r is the absolute shielding, and r0 is the absolute shielding of TMS. Acetone was selected for studying the relative stability of conformers in solution following the SCRF-PCM method [36], according to which the solute is embedded in the dielectric medium Author's personal copy 153 S.F. Tayyari et al. / Journal of Molecular Structure 1036 (2013) 151–160 A-I (0.00) A-II (0.90) A-III (1.40) A-IV (1.33) B-I (22.79) B-II (16.60) B-III (24.32) B-IV (18.38) Fig. 2. The stable possible cis-enol: (A) conformers of DCACP and their corresponding open structures. (B) The relative energies are given in parentheses (in kcal/mol). surrounded by a cavity shaped in the form of the solute [37,38]. The van der Waals radii suggested by Bondi [39] were adopted for atoms. Specific solute–solvent effects are not taken into account at this level of calculation and the obtained solvation energies correspond to the electrostatic contributions, which, however, play a dominant role in tautomerization reactions [40]. 4. Results and discussions 4.1. Molecular geometry By rotation of CHCl2 groups around C6AC12 and C8AC11 bonds, four stable chelated conformers were obtained, which are fully optimized at the B3LYP level using 6-31G, 6-311G, and 6311++G basis sets. The relative energies in the gas phase and in solutions of chloroform and acetone, dipole moments, and the hydrogen bond strengths (EHB), the energy difference between the chelated and corresponding open conformer (B structure in Fig. 2) are collected in Table 1, whilst the geometrical parameters for all stable conformers in the gas phase and in solution are compared in Table 2. In the last column of Table 2 the geometrical parameters of B-IV are also listed. The conformation of CHCl2 groups with respect to the plane of molecule (Fig. 2) has great influence on the geometry of the chelated ring. The O O distance varies from 2.447 Å in the conformation A-III to 2.493 Å in the conformation A-I (at the B3LYP/6311++G level). As the calculations at the MP2/6-31G and B3LYP (using different basis sets) levels predict, A-I is the most stable conformation in the gas phase. However, the calculated relative energies obtained at different level of theory for A-I to A-IV conformers are slightly different. The calculated relative energies for other conformers obtained at various levels of theory are only 0.90–1.40 kcal/mol higher than that of A-I conformation. Of course, such a little difference in energy is not enough to determine the stability of a conformer. The optimization calculation in the solvent media, using PCM method, without considering special solvent– solute interactions, indicates that in solution A-IV is the most stable conformation. The stability increasing of A-IV, compared to that of other conformers, is due to its considerably high value of dipole moment. In the CH3CN solution, calculated at the B3LYP/6311++G level, the energies of A-I, A-II, and A-III conformers are 1.18–3.6 kcal/mol higher than that of A-IV conformer. By going from the gas phase to acetone solution, the geometry of A-IV shows the highest changes among all conformers. In solution, the O O Table 1 Relative energies (kcal/mol) and dipole moments for DCACP conformers obtained at the B3LYP level using various basis sets and different media.a. Basis sets 6-31G e 6-311G e 6-311++Ge MP2/631Ge 6-311G b 6-311G c 6-311++Gb 6-311++Gc 6-311++Gd l d(Debye) l e (Debye) A-I 0.00(17.97) 0.00(16.48) 0.00(16.60) 0.00(15.09) A-II 0.65(23.93) 1.01(20.88) 0.90(21.89) 0.85(20.39) A-III 1.24(25.11) 1.37(20.97) 1.40(22.92) 1.31(19.93) A-IV 0.97(18.56) 0.73(16.31) 1.33(17.05) 0.64(15.32) C2v 1.46 1.47 1.63 1.93 0.54 1.16 0.42 1.05(15.56) 1.18(20.54) 4.4 3.0 2.53 3.58 2.30 3.44(19.94) 3.60(11.20) 1.4 1.2 1.70 2.13 1.58 2.14 2.21(15.80) 4.7 3.2 0.00 0.00 0.00 0.00(15.20) 0.00(13.88) 7.4 5.0 0.81 0.80 0.80 7.6 5.0 a Figures in parentheses are corresponding EHB (in kcal/mol); l, dipole moment (calculated with the 6-311++G** basis set). b Calculated in chloroform. c In acetone. d In CH3CN. e In the gas phase. distance and CAO and C@O bond lengths increase by 0.004, 0.008, and 0.006 Å, respectively, while, the C1AC6 and C2AC8 bond lengths decrease by 0.005 and 0.007 Å, respectively. The OAH bond lengths in all chelated conformers are considerably long, 1.027–1.057 Å, but in the open structures its value is about 0.970 Å. The calculated O O distance in the chelated frameworks of DCACP is in good agreement with those observed for two other members of this class of compounds, 2,3-diacetyl-5-nitrocyclopentadiene (NO2-DACP), 2.446(2) Å, and 2,3-dibenzoyl-5-nitrocyclopentadiene (NO2-DBCP) 2.433(2) Å [15]. On the other hand, the calculated O O distance in the chelated DCACP is considerably shorter than those obtained for malonaldehyde (2.587 Å [8]), hexafluoro-acetylacetone (2.592 Å [9]), and acetylacetone, AA, (2.544 Å [11]), all calculated at the B3LYP/6-311++G level. These results indicate formation of much stronger hydrogen bond in this molecule compared with those in the enol form of b-diketones, which is consistent with the NMR results. Comparing the geometrical parameters of chelated and open conformations reveals that the cyclopentadiene ring participates in the p-electron conjugation of the chelated ring. The C1AC2 bond distance, 1.487 Å, and its very small change by going from open to the chelated structure, 0.007 Å (see Table 2), indicates that this Author's personal copy 154 S.F. Tayyari et al. / Journal of Molecular Structure 1036 (2013) 151–160 Table 2 Selected bond distances (Å) and bond angles (°) of calculated stable chelated DCACP at the B3LYP/6-311++G level. A-I Bond distances C1AC2 C1AC5 C2AC3 C4AC5 C3AC4 C1AC6 C2AC8 C6AO7 C8AO9 C6AC12 C8AC11 OAH H O O O C4AH14 C5AH15 C3AH13 C12AH17 C12ACl18 C11ACl20 C11AH16 Bond angles OAH O C2C1C5 C1C2C3 C2C3C4 C3C4C5 C2C1C6 C1C2C8 C1C6O7 C2C8O9 C6O7H10 C1C5H15 C5C4H14 C2C3H13 U1 U2 a A-II A-III A-IV B-IV G S G S G S G S S 1.479 1.437 1.396 1.379 1.416 1.386 1.428 1.298 1.246 1.513 1.539 1.027 1.477 2.493 1.080 1.079 1.080 1.080 1.800 1.801 1.084 1.481 1.438 1.399 1.379 1.416 1.383 1.425 1.303 1.249 1.511 1.539 1.028 1.472 2.492 1.080 1.079 1.079 1.079 1.804 1.803 1.083 1.481 1.434 1.398 1.380 1.415 1.382 1.423 1.305 1.250 1.523 1.538 1.037 1.449 2.478 1.079 1.079 1.080 1.084 1.800 1.801 1.084 1.482 1.434 1.399 1.381 1.414 1.382 1.422 1.306 1.252 1.523 1.538 1.036 1.477 2.481 1.080 1.079 1.079 1.083 1.802 1.803 1.083 1.479 1.430 1.402 1.383 1.412 1.387 1.425 1.298 1.247 1.524 1.532 1.057 1.397 2.447 1.078 1.080 1.080 1.084 1.799 1.797 1.081 1.481 1.431 1.404 1.384 1.412 1.385 1.421 1.301 1.251 1.523 1.532 1.048 1.419 2.461 1.080 1.079 1.080 1.083 1.801 1.801 1.080 1.477 1.434 1.400 1.381 1.414 1.390 1.431 1.292 1.241 1.514 1.534 1.039 1.442 2.472 1.080 1.080 1.080 1.080 1.798 1.796 1.080 1.480 1.435 1.401 1.381 1.413 1.385 1.424 1.300 1.247 1.512 1.533 1.036 1.451 2.476 1.080 1.080 1.080 1.079 1.801 1.801 1.080 1.487 1.456 1.388 1.365 1.429 1.371 1.456 1.325 1.217 1.510 1.556 0.969 – 2.689 1.080 1.079 1.079 1.079 1.805 1.808 1.078 169.7 105.9 106.6 109.7 108.6 129.0 127.3 126.0 124.6 110.8 126.1 125.5 126.0 179.8 0.0 170.4 105.9 106.4 109.8 108.7 129.1 127.4 125.8 124.6 110.5 126.1 126 125.7 180.0 0.0 170.4 106.1 106.4 109.7 108.8 129.0 127.3 125.6 124.6 110.7 125.3 125.5 125.9 0.0 0.0 171 106 106.3 109.7 108.7 129.0 127.5 125.4 124.6 110.6 125.5 125.9 125.8 0.0 0.0 171.2 106.3 106.2 109.7 108.7 128.4 127.1 125.4 124.6 110.9 125.3 126.3 125.9 0.0 180.0 171.6 106.2 106.2 109.7 108.7 128.6 127.4 125.3 124.8 110.7 125.5 125.9 126.4 0.0 179.9 170.2 106.0 106.4 109.8 108.6 128.6 127.1 125.9 124.6 111.0 126.2 126.3 126.0 174.5 172.8 170.7 106.0 106.3 109.8 108.6 128.7 127.3 125.7 124.8 110.6 126.1 126.0 126.9 179.8 179.9 – 105.8 106.6 110.6 108.4 131.7 129.8 122.8 126.5 111.7 126.2 126.3 126.6 179.8 179.1 U1 and U2 are O7C6C12H17 and O9C8C11H16 dihedral angels, respectively; G and S stand for calculations in the gas phase and in acetone solution, respectively. bond slightly participates in the conjugated p-electron system. However, elongation of C@C bonds and shortening of CAC bonds of the cyclopentadiene ring by about 0.013–0.021 Å (compare the last two columns of Table 2), upon formation of intramolecular hydrogen bond, strongly supports participation of cyclopentadiene ring in the p-electron delocalization of the chelated ring. Changing from open conformers to the chelated structures causes a large lengthening of C@O and C1@C6 (0.03 and 0.014 Å, respectively) and shortening of CAO and C2AC8 bond distances (0.025 and 0.032 Å, respectively). These results suggest establishing of high degree of p-electron delocalization in the chelated ring upon formation of intramolecular hydrogen bond, which in turn assists the increasing of the hydrogen bond strength. These results interpret the formation of very strong hydrogen bond in 1,2-diacyl cyclopentadiene systems and support the resonance-assisted hydrogen-bonding hypothesis (RAHB) of Gilli et al. [14] for this system. As it is shown in Table 2, the OO distance of stable conformers lays in the 2.49–2.45 Å range, and the hydrogen bond system is nearly linear, with an O–HO angle of about 170–171°. These results suggest formation of a very strong hydrogen bond in DCACP conformers, which is supported with an EHB in the 16.6–22.9 and 15.2–19.9 kcal/mol range in the gas phase and in acetone solution (calculated at the B3LYP/6-311++G level), respectively. As it is shown in Table 1, the corresponding values calculated at the MP2/6-31G level is slightly different from those obtained at the B3LYP/6-311++G level. The EHB’s of conformers A-II and AIII are considerably higher than that of conformers A-I and A-IV. This difference caused by three factors: (1) difference in hydrogen bond strength in the chelated conformers. (2) Hydrogen bonding formation between OH and the two Cl atoms of the CHCl2 groups in the open structures of A-I and A-IV, which reduces the energy of the trans-enol forms. (3) Repulsion between enolated and CHCl2 group’s H atoms in the open structures of B-II and B-III, which cause an increase in their energies. By considering these factors, therefore, it may conclude that 16.6 and 15.2 kcal/mol is the lower limit for the hydrogen bond strength in DCACP in the gas phase and solution, respectively. According to the calculated results (Table 2), the C6AC12 and C8AC11 bond lengths in A-IV are 1.512 and 1.533 Å, respectively, which are considerably longer than that calculated for CACH3 bond lengths in AA, 1.497 and 1.513 Å [11]. The Electrostatic effects can rationalize this lengthening of the CAC bonds qualitatively if we assume that the small but negative net charge on the CH3 carbon becomes positive upon chlorination. In this picture, the attractive interaction (CdAC+d) in CACH3 becomes repulsive (C+dAC+d) if chlorination occurs on terminal carbon atoms. This simple electrostatic mode has been proposed to explain the abnormally high value of CACF3 bond lengths, 1.521 and 1.543 Å, in HFAA [9]. The most important geometrical parameters for the A-IV conformer related to the intramolecular hydrogen bond, calculated in the gas phase and in solution, are listed in Table 3. As it is shown Author's personal copy 155 S.F. Tayyari et al. / Journal of Molecular Structure 1036 (2013) 151–160 Table 3 The most important geometrical parameters for the A-IV conformer. A Gas B C Table 4 1 H chemical shifts (ppm) of some 1,2-diacylcyclopentadienes. D Sol. Gas Sol. Gas Sol. Gas Sol. Bond distance (Å) C1AC6 1.390 C2AC8 1.431 C6AO7 1.292 C8AO9 1.241 OAH 1.039 H O 1.442 O O 2.472 1.385 1.424 1.300 1.247 1.036 1.451 2.476 1.389 1.431 1.291 1.240 1.039 1.441 2.471 1.385 1.425 1.297 1.245 1.037 1.447 2.476 1.394 1.429 1.292 1.249 1.054 1.405 2.452 1.389 1.424 1.298 1.254 1.051 1.414 2.459 1.387 1.435 1.304 1.249 1.024 1.482 2.499 1.386 1.432 1.308 1.251 1.025 1.479 2.497 Bond angle (°) OAH O 170.2 170.7 170.3 170.9 171.2 171.8 171.0 171.5 a A, B, C stand for 6-311++G, 6-311G, and 6-31G basis sets, respectively; D, calculated at the MP2/6-31G level; sol, acetone solution. in Table 3, the calculated OO distance for the most stable conformer of DCACP varies from 2.452 to 2.503 Å. However, it has been shown that calculation at the B3LYP/6-31G overestimates the hydrogen bond strength and gives considerably shorter OO distance compared to that obtained at the B3LYP/6-311++G level [41–43], therefore it may be concluded that the hydrogen bond distance in A-IV conformer is in the 2.472–2.503 Å range. All calculations, except calculations at the MP2/6-31G level, indicate that the OO distance in solution is slightly longer than in the gas phase. As it is also shown in Table 3, the length of polar bands, CAO and C@O, in solution increases, whilst the CAC and C@C bond lengths are slightly decreased compared to those in the gas phase. By increasing the OO distance the OAH bond length decreases. The relative energies of C2v structure of A-IV (putting the H atom in the midway between two O atoms) are also listed in Table 1. As it is shown in Table 1, the relative energy of the C2v structure is less than 2 kcal/mol in the gas phase and less than 1 kcal/ mol in solution, which supports existence of a very strong hydrogen bond in DCACP with low barrier potential to proton tunneling in the system. Solvent dOH dH (13,15) dH (14) dH (R) Ref. HFF DACP DACP DBCP CDCl3 CCl4 CDCl3 CCl4 16.1 18.0 18.15 18.45 7.17 7.2 7.32 7.15 6.37 6.25 6.39 6.35 [20] [21] [20] [21] DBCP CDCl3 18.43 7.24 6.46 D-t-BuCP DTCP Bis(pNO2)BCP NO2DACP DCACP DCACP DCACP CCl4 CDCl3 CDCl3 19.2 18.29 18.23 7.48 7.83 7.25 6.25 6.55 6.6 8.57 2.5 2.53 7.9–7.25 (m) 7.76– 7.81(m) 1.47 7.2,7.66,7.68 7.96, 8.39 CDCl3 CDCl3 CD3CN d6Acetone 19.35 17.34 17.40 17.41 7.86 7.57 7.83 8.02 – 6.57 6.72 6.68 2.6 6.78 7.33 7.59 [20] T.W T.W T.W Gas Gas Gas Gas Acetone Acetone Acetone Acetone 17.03 16.91 18.75 19.05 16.74 16.87 18.11 17.78 8.57 7.87 7.91 7.58 8.13 8.37 8.18 8.01 6.70 6.71 6.70 6.67 6.94 6.91 6.95 6.92 6.29 6.58 6.64 6.99 6.78 6.44 7.22 7.26 Calculatedb A-I A-II A-III A-IV A-I A-II A-III A-IV [20] [21] [20] [20] a HFF, hydroxyl formylfulvene; DACP, 1,2-diacetylcyclopentadiene; DBCP, dibenzoylcyclopentadiene; D-t-BuCP, bis(t-butanoyl)cyclopentadiene; T.W, this work; DTCP, 1,2-dithenoylcyclopentadiene. b Calculated at the B3LYP/6-311++G** level. Table 5 Calculated and observed HFFb DCACP DCACP Calculatedc A-I A-II A-III A-IV A-I A-II A-III A-IV 4.2. Analysis of NMR spectra The observed and calculated 1H and 13C NMR chemical shifts for DCACP are listed in Tables 4 and 5, respectively. In Table 4, the 1H chemical shifts of DCACP are compared with those of several 1,2diacyl-cyclopentadiene compounds. According to Tables 4 and 5, good agreements exist between the calculated and observed results. The full 1H spectrum could be assigned on the basis of signal integrations and splitting patterns. The full 13C spectrum of DCACP was assigned by comparing with the corresponding spectrum of HFF [23] and calculated results. The data in Table 4 indicates that the hydrogen bond in DCACP is stronger than that in HFF but slightly is weaker than that in 1,2diacetyl-cyclopentadiene, DACP. The weakening of the hydrogen bond upon substitution of H atoms of the methyl groups by chlorine atoms could be attributed to the electron withdrawing character of Cl atoms. Para-substitution of phenyl groups in DBCP by NO2, bis (p-NO2B) CP, shifts the 1H signal of the hydrogen bonded proton from 18.43 ppm to 18.23 ppm (see Table 4), which supports weakening of the hydrogen bond by an electron-withdrawing group in R position. On the other hand, substitution of the 4-position of cyclopentadiene ring of DACP by NO2 group (NO2DACP) considerably shifts the 1H signal downfield (ca. 1.2 ppm), i.e. increasing the strength of the bond. These effects could be explained as follows: In the p-NO2 substituted DBCP, the nitro group acts as a withdrawing group, which reduces the electron density on the carbonyl Compound a b c 13 C chemical shifts for some 1,2-diacylcyclopentadienes.a Solvent C6,8 C1,2 C3,5 C4 R CDCl3 CDCl3 Acetone-d6 176.0 176.88 177.33 126.5 120.92 121.44 141.2 140.27 142.62 125.2 125.82 126.72 – 66.27 67.09 Gas Gas Gas Gas Acetone Acetone Acetone Acetone 184.45 183.11 184.74 183.02 185.96 188.16 187.76 185.19 123.73 123.97 125.07 125.57 127.71 127.43 128.31 129.02 146.80 144.58 143.90 142.53 151.40 151.33 150.78 151.7 128.08 128.12 127.58 126.77 133.55 132.87 133.30 133.37 88.80 86.59 85.68 83.24 90.97 92.47 90.12 88.36 Rf 70.28 68.54 67.79 65.80 78.77 79.68 78.10 76.71 R, CHCl2-carbon; Rf, corrected according to Ref. [47]. Data from Ref. [23]. Calculated at the B3LYP/6-311++G** level. group of the chelated ring, therefore, decreases the hydrogen bond strength. The similar behaviors have been observed for the enol form of b-diketones when the terminal group substituted by electron withdrawing groups [9,41]. On the other hand, in the case of substitution of NO2 in the 4-position of the CP ring in DACP, the nitro group enhances the p-electron delocalization by resonating with the CP and chelated rings. This behavior is very similar when the hydrogen atom of 3-position of AA is replaced by NO2 group (the proton chemical shifts of enolated proton of AA and NO2-AA are 15.4 [44] and 16.86 ppm [45], respectively). Substitution of t-butyl for the CH3 groups in DACP shifts the signal of OH proton 1.2 ppm downfield, i.e. considerably increases the hydrogen bond strength. It is interesting that the similar behavior is observed for b-diketone system. The chemical shifts of AA [44] and 1,3-di (t-butyl) propane-1, 3-dione [46] are Author's personal copy 156 S.F. Tayyari et al. / Journal of Molecular Structure 1036 (2013) 151–160 observed at 15.4 and 16.3 ppm, respectively, which causes a downfield shift of 0.9 ppm upon substitution of both CH3 groups by t-butyl. This effect could be attributed to the pushing of both oxygen atoms together by the bulky group, which results in a stronger hydrogen bond. As it is indicated in Table 4, the results of experimental proton chemical shifts are in good agreement with the corresponding calculated results for A-IV conformer. Table 5 reveals that the predicted 13C chemical shifts obtained at the B3LYP level, except for CHCl2 groups’ carbon, are in agreement with the experimental results. A large deviation is observed for the chemical shift of the chlorinated carbons, which is 21.27 ppm for the most stable conformer in solution, A-IV. A similar behavior for double chlorinated carbon atoms has been reported by Koivisto et al. [47]. These authors found a deviation of 14.2–18.7 ppm for CHCl2 groups in polychlorinated dihydro- Table 6 Theoretical and experimental vibrational frequencies of DCACP(A-IV).a Theoretical Experimental F1 IIR F2 AR Fan F3 3120 3111 3102 3094 3090 2306 1611 1579 1526 1499 1433 1394 1380 1294 1282 1278 1258 1225 1222 1201 1122 1082 1070 998 938 942 885 839 794 781 775 757 751 709 698 676 629 585 561 534 496 377 367 318 311 234 232 218 187 177 166 145 101 77 34 29 11 2 2 4 1 1 1712 968 806 61 83 266 194 208 73 40 239 290 36 30 0 33 173 106 24 19 1 2 5 37 7 220 14 5 69 506 0 343 2 11 4 7 3 10 1 1 0 2 7 0 1 0 0 1 0 0 0 0 3116 3105 3095 3085 3074 2318 1628 1601 1529 1499 1438 1397 1379 1311 1284 1278 1257 1227 1224 1198 1121 1110 1072 998 941 927 867 842 796 782 775 760 748 720 711 692 646 590 568 534 495 376 369 318 311 233 231 217 184 180 166 144 101 77 35 27 11 242 53 58 23 19 84 76 107 20 7 58 22 82 235 27 15 21 4 6 1 94 1 4 62 13 0 5 28 28 7 10 10 7 41 30 13 2 1 0 22 1 5 17 8 7 0 1 0 0 1 3 4 2 4 4 2 2 3134 3117 3109 3138 3081 1538 1617 1583 1511 1385 1440 1405 1334 1220 1256 1312 1257 1229 1259 1197 1113 2022 1066 998 939 927 880 837 788 774 771 748 757 710 687 675 622 588 572 522 507 384 342 321 306 235 229 212 186 185 169 148 93 70 17 6 NC 3116 3105 3097 3084 3079 2142 1604 1588 1518 1488 1427 1389 1370 1288 1273 1260 1244 1201 1198 1188 1110 1073 1061 987 927 922 867 824 785 766 761 747 742 700 687 667 619 578 554 528 490 374 369 314 308 232 229 215 187 176 165 143 100 75 33 27 16 IRCCl4 3092(1) 3039(1) 2925 (2) 2852(1) 1718(14) 1626(32) 1603(100) 1492(13) 1461(12) 1440(21) 1426(36) 1408(33) 1315(3) 1261(44) 1261 1253(26) 1228(5) 1203(8) 1171(1) 1099(2) 1074(11) 1049(14) 1028(6) 948(2) 918(1) 841(3) 725(3) 700(2) 657(20) 657 564(4) 512(7) Assignments IRSolid 3124(5) 3102(13) 3037(20) 2925 (2) 2853(1) 1696(15) 1613(100) 1568(43) 1497(43) 1484(18) 1449(28) 1419(30) 1401(24) 1312(5) 1265(80) 1265 1261(83) 1246(9) 1202(35) 1167(3) 1106(6) 1088(20) 1043(23) 1003(5) 944(3) 928(2) 884(1) 840(17) 795(97) 788(25) 761(22) 751(29) 731(39) 708(21) 657(97) 657 590(6) 561(17) 537(6) 500(10) 237(10) 1 2 3 mCH(R) mCH(R) mOH dOH,mC@C dOH,mC@O 4, msCAC@O, mCAO 5, dOH 6, mCAC, mCAO 7,dCAH(R), mCAC,mCAO 8,msC@C 9, mCAC, dCH(R) 10, dCH(R) 11, dCH(R) 11, dCH(R) cCH(R) cCH(R) dCH(R), 12 13 cOH 15 15.mCAR 16 17 18 19 dR-C@O, nOHO, dR-C@O, 21 20 22 dR-C@O, dR-C@O 23 msCCl2 24, msCCl2 25 maCCl2, cOH 26 maCCl2 27 dCACAR, dC@CAO, 21 dC5C1C6, dC1C2C3 dC1C2C7, dC2C1C6 mOHO dC@O, CCl2sci mOHO, CCl2 sci. 28, cC@O, cCAO 29 xCCl2 cCAO, cC@O, 28 dCACAR qR 27, cC@O, cCAO qR pCAR sR pCP sCP a F1 and F2, stand for scaled (by 0.9609 and 0.9859 for higher and lower than 1700 cm1) wavenumbers calculated at the B3LYP/6-311++G** in acetone solution and gas phase, respectively; Fan, and F3, stand for anharmonic and scaled (by 0.9539 and 0.9705 for higher and lower than 1700 cm1) wavenumbers, calculated at the B3LYP/631G** level in acetone solution, respectively; NC, not converged; R, CHCl2 group; m, stretching, d, in-plane bending; q, in-plane rocking; p, out-of-plane bending mode; x, wagging; sci, scissoring; CP, cyclopentadiene frame; m,O-H. . .O, hydrogen bond stretching. Author's personal copy 157 S.F. Tayyari et al. / Journal of Molecular Structure 1036 (2013) 151–160 camphenes calculated at the B3LYP/6-311G level. Koivisto et al. [47] suggested the following equation for correction of calculated 13 C chemical shift of double chlorinated carbons: dobs ¼ 0:791dcalc þ 6:817 with a standard deviation of 2.314 ppm. This correction for the 13C chemical shift of CHCl2 groups of DCACP is given in Table 5, which indicates good agreement with the experimental value. 4.3. Analysis of the IR spectra The calculated scaled harmonic and anharmonic vibrational frequencies and their assignments for the most stable conformer of DCACP and its corresponding deuterated analogous in solution along with the observed infrared frequencies are listed in Tables 6 and 7, respectively. As it is shown in these tables, calculated wavenumbers obtained for solution and gas phase, except for a few cases, are almost the same. According to Tables 6 and 7, the calculated anharmonic and scaled harmonic wave numbers, except for OH stretching and out-of-plane bending modes, are very Table 7 Theoretical and experimental vibrational frequencies of D-DCACP(A-IV).a Theoretical a Experimental F1 F2 IIR AR Fan F3 IRSolid 3120 3111 3102 3094 3090 1752 1592 1526 1507 1431 1407 1387 1292 1283 1279 1260 1225 1221 1205 1162 1109 1069 972 941 937 885 839 791 791 780 773 754 749 708 697 677 625 584 561 523 494 376 359 317 308 234 232 217 186 178 166 145 100 77 33 28 10 3116 3105 3095 3085 3074 1770 1619 1533 1512 1439 1410 1384 1308 1285 1279 1258 1227 1225 1202 1162 1106 1071 972 940 926 866 842 810 793 781 775 758 748 719 709 692 641 590 567 523 494 375 361 318 307 232 230 216 183 180 165 143 100 77 35 27 11 2 3 2 2 3 713 726 36 65 86 7 173 39 46 44 80 25 18 9 61 4 53 25 7 0 2 3 57 22 58 127 18 1 72 217 1 132 0 4 1 3 3 5 0 0 0 1 4 0 0 0 0 0 0 0 0 0 242 53 58 23 19 8 69 62 44 79 48 52 249 22 31 20 4 6 1 38 44 4 61 15 0 5 27 1 28 7 10 13 7 42 27 13 2 1 0 19 2 4 16 10 6 0 1 0 0 1 3 4 2 4 4 2 2 3134 3117 3109 3139 3082 1322 1588 1516 1221 1437 1413 1284 1245 1147 1307 1257 1229 1261 1194 1178 1104 1061 977 938 927 879 836 824 781 774 773 744 754 707 687 674 621 587 572 513 507 384 339 321 301 235 230 211 186 186 168 146 95 70 19 4 NC 3116 3104 3097 3084 3079 1685 1592 1519 1472 1427 1403 1368 1281 1266 1264 1246 1201 1198 1190 1157 1099 1060 962 927 922 867 823 784 783 765 760 744 740 699 686 667 615 577 554 517 489 372 361 313 305 232 228 214 185 175 164 143 99 75 33 27 16 3124(5) 3102(13) 3037(20) 2965 2925 ? 1604(100) 1513(22) 1475(26) 1440(40) 1418(28) 1393(80) 1315(26) 1268(74) 1257(47) 1248(28) 1201(36) 1230(11) 1201 1157(29) See footnotes of Table 6; m, O-D. . .O, hydrogen bond stretching. 1070(30) 972(11) 948(3) 928(4) 838(33) 756(50) 794(82) 785(50) 785 742(56) 729 (60) 719 (97) 645(89) 559(31) 499(10) 236 (12) Assignments 1 2 3 mCH(R) mCH(R) mOD, mC@CAO, mC@O mC@O, mC@C, mOD 4, mC@C, mC@O, mOD 5, mC@O, mC@C, mOD 6, mCAC, mCAO 7,dCAH(R), mCAC,mCAO 8,msC@C 9, mCAC, dCH(R) 10, dCH(R) 11, dCH(R) 11, dCH(R) cCH(R) cCH(R) 12, dCH(R), dOD dOD, 13 13, dOD 14 dOD, 15, mCAR 17 16 18 19 cOD dRAC@O, 1 20 22 dRAC@O, dRAC@O 23 msCCl2 24, msCCl2 25 maCCl2, cOD 26,.maCCl2 27 21, dCACAR, nOD O dC5C1C6, dC1C2C3 dC1C2C7, dC2C1C6 mOD O dC@O,CCl2sci mOD O, CCl2 sci. 28, cC@O, cCAO 29 xCCl2 cCAO, cC@O, 28 dCACAR qR 28, cC@O, cCAO qR pCAR sR pCP sCP Author's personal copy 158 S.F. Tayyari et al. / Journal of Molecular Structure 1036 (2013) 151–160 close to each other. The deconvoluted IR spectrum of DCACP in the 1900–1000 cm1 region is given in the Fig. 3. Comparison between IR spectra of DCACP and its deuterated analogue is given in Fig. 4. The assignments of the experimental frequencies are based on the observed band frequencies and intensity changes in the infrared spectra of the deuterated species and confirmed by establishing one to one correlation between observed and theoretically calculated frequencies. The calculated frequencies are slightly higher than the experimental values. Two factors may be effective for the discrepancies between the observed and calculated spectra of these compounds. The first is caused by the environment. DFT calculations have been done at the gas phase and the experimental frequencies are obtained from solid state. The second reason for this discrepancy is the fact that the experimental values are anharmonic frequencies while the computed data are harmonic frequencies. The overestimation of the computed wavenumbers is quite systematic and can be corrected by applying appropriate scaling factors or scaling equations [48,12,49]. In Tables 6 and 7 the calculated harmonic frequencies are scaled by different scaling factors for the regions above and below 1700 cm1, recommended by Tayyari et al. [48]. However, to show the effect of solvent and anharmonicity, the vibrational frequencies were also obtained in solution (acetone) at the B3LYP/6-311++G level, and calculating the anharmonic wavenumbers at the B3LYP/6-31G level in solution. The notations for cyclopentadienyl group vibrations are according to the illustrations in Fig. 5. 4.3.1. CH stretching modes We assigned three bands at above 3000 cm1 to the CH stretching vibrations of CP ring. These bands occur at 3124, 3102, and 3037 cm1 2.0 1.5 1.0 0.5 0.0 1800 1600 1400 1200 1000 Fig. 3. The deconvoluted IR spectrum of DCACP in the solid state. 2.5 2.0 1.5 1.0 0.5 0.0 1600 1200 800 Fig. 4. Comparing the IR spectra of DCACP and D-DCACP in the 1800–500 cm1 region. in the solid phase. Two relatively weak bands at 2925 and 2853 cm1 are assigned to the CH stretching modes of the CHCl2 groups. 4.3.2. OH stretching mode The most interesting fundamental in IR spectrum of the titled compound is the OH stretching vibration, mOH. According to the harmonic approximation calculations, obtained at the B3LYP/6311++G level in the solution and in the gas phase, we expect to observe this band as a very strong band at about 2300 cm1, for the most stable conformer (A-IV). By using the 6-31G basis set the corresponding wavenumber obtained at about 2140 cm1. However, the observed IR spectrum does not exhibit any broad band in this region. As it is shown in Table 6, by considering the anharmonicity, calculations at the B3LYP/6-31G level predict the OH stretching to be occurred at about 1500 cm1. This result shows that this vibration should be highly anharmonic. With such a huge anharmonicity calculating the exact wavenumbers is almost impossible, because the shape of the potential function is very sensitive to the level of calculation and used basis set. However, it is well known that strong intramolecular hydrogen bonding leads to large anharmonic effects, resulting in a shift of mOH towards lower wavenumbers and possibly enhanced coupling with other modes. The recent theoretical analysis by Szczepaniak et al. [50] demonstrates how anharmonic effects associated with strong intramolecular hydrogen bonding may lead to a drastic shift of mOH towards lower wavenumbers and redistribution of the associated IR intensity over several other modes. As it is shown in Fig. 4, a weak and broad band is observed at about 1700 cm1, which disappears in the deuterated analogous. This band is attributed to the OH stretching mode. Deconvolution of the IR spectrum of DCACP (in the solid state) in the 1800–1000 cm1 range, Fig. 3, shows a weak and broad band at about 1700 cm1. 4.3.3. 1700–1300 cm1 region The deconvoluted IR spectrum of DCACP in the solid phase shows two bands at 1613 and 1568 cm1 which involve C@C and C@O stretching motions, which the latter is strongly coupled to the OH in-plane bending vibration. In the IR spectrum in solution these bands show a blue shift and occur at 1626 cm1 and 1603 cm1, respectively. The phase sensitivity of these two vibrational modes is well predicted by the calculated results (see Table 6). Upon deuteration the former was observed at 1604 cm1 and assigned to the C1@C6, which in the light and deuterated compounds it is coupled to the OH in-plane bending and OD stretching vibrations, respectively. The 1568 cm1 band is disappeared in the deuterated compound and a new band appears at 1157 cm1. The corresponding band in deuterated AA is observed at 1079 cm1 [51], which supports much stronger hydrogen bond in DCACP than that in AA. The strong IR band at 1419 cm1 is assigned to the symmetric C2AC8 and C6AO7 stretching mode, which is strongly coupled to the cyclopentadiene (CP) ring’s CAH in-plane bending movements. The weak band at about 1312 cm1 is attributed to the CAC stretching of the terminal groups, which is coupled to the CAH bending of the CP ring. 4.3.4. Below 1300 cm1 In the solid phase, the strong IR band observed at 1261 cm1 is assigned to the coupled CH in-plane-bending vibrations of the CP ring and terminal groups. The two IR bands at 1228 and 1203 cm1 in solution are assigned to the CH in-plane and out-of-plane bending modes of the CHCl2 groups, respectively. The relatively broad band observed at 1088 cm1 in the solid state IR spectrum is assigned to the OH out-of-plane bending vibration. The corresponding band in AA was observed at 940 cm1 [51], Author's personal copy S.F. Tayyari et al. / Journal of Molecular Structure 1036 (2013) 151–160 159 Fig. 5. The notations for cyclopentadienyl group vibrations. which also indicates much stronger hydrogen bond in DCACP than in AA. The corresponding band in the IR spectrum of b-diketones appears in the 850–970 cm1 range [8,9,11], which is also in agreement with much stronger intramolecular hydrogen bond in DCACP than that in the enol forms of b-diketones. The corresponding band in the deuterated analogue was observed as a relatively broad band at 756 cm1. The strong bands at 708, 657, and 590 cm1 are caused by CACl stretching vibrations and the 237 cm1 band is related to the CCl2 wagging mode. 5. Conclusions A conformation analysis at DFT-B3LYP level using 6-31G, 6311G, and 6-311++G basis sets was preformed for DCACP. Four stable conformers with little energy difference were obtained, which their relative stabilities seem to be solvent dependent. From comparison of observed and calculated NMR chemical shifts by GIAO method, it is concluded that the H atoms of CHCl2 are engaged in an intermolecular hydrogen bond with the solvent molecules. Author's personal copy 160 S.F. Tayyari et al. / Journal of Molecular Structure 1036 (2013) 151–160 The optimized geometrical parameters of all stable chelated conformers indicate presence of a very strong intramolecular hydrogen bond in all chelated stable conformers with a hydrogen bond strength more than 16.6 kcal/mol. The strength of the bond is confirmed with a large proton chemical shift of about 17.4 ppm, which is almost solvent independent. By comparing of the relative energies of the most stable conformer and the C2v structure of DCACP a low barrier double minimum potential energy is concluded for the intramolecular hydrogen bond system in DCACP. The OAH stretching, in-plane and out-of-plane bending and OO stretching modes also indicate that the hydrogen bond strength in DCACP is much stronger than that in the enol form of b-diketones. References [1] W.W. Cleland, P.A. Frey, J.A. Gerlt, J. Biol. Chem. 273 (1998) 25529. [2] T.K. Harris, Q. Zhao, A.S. Mildvan, J. Mol. Struct. 552 (2000) 97. [3] S.F. Tayyari, M. Zahedi Tabrizi, F. Tayyari, F. Milani-Nejad, J. Mol. Struct. (Theochem) 637 (2003) 171. [4] M. Zahedi Tabrizi, S.F. Tayyari, F. Tayyari, M. Behforouz, Spectrochim. Acta A 60 (2004) 111. [5] V. Bertolasi, P. Gilli, V.F. Ferretti, G. Gilli, J. Am. Chem. Soc. 113 (1991) 4917. [6] Y.H. Mariam, R.N. Musin, J. Mol. Struct. (Theochem) 549 (2001) 123. [7] G. Buemi, F. Zuccarello, J. Mol. Struct. (Theochem) 581 (2002) 71. [8] A. Nowroozi, S.F. Tayyari, H. Rahemi, Spectrochim. Acta Part A 59 (2003) 1757. [9] S.F. Tayyari, F. Milani-Nejad, H. Rahemi, Spectrochim. Acta Part A 58 (2002) 1669. [10] S.F. Tayyari, M. Zahedi-Tabrizi, H. Azizi-Toopkanloo, S.S. Hepperle, Y.A. Wang, Chem. Phys. 368 (2010) 62. [11] S.F. Tayyari, H. Reissi, F. Milani-Nejad, I.S. Butler, Vibrat. Spectrosc. 26 (2001) 187. [12] J. Spanget-Larsen, Chem. Phys. 240 (1999) 51. [13] S. Millefiori, A. Alparone, J. Chem. Soc. Faraday Trans. 90 (1994) 2873. [14] G. Gilli, F. Bellucci, V. Ferretti, V. Bertolasi, J. Am. Chem. Soc. 111 (1989) 1023. [15] G. Fergusen, W.C. Marsh, R.J. Restivo, D. Lloyd, J. Chem. Soc. Perkin Trans. 2 (1975) 998. [16] H.M. Pickett, J. Am. Chem. Soc. 95 (1973) 1770. [17] H. Fuess, H.J. Lindner, Chem. Ber. 108 (1975) 3096. [18] K. Hafner, H.E. Kramer, H. Musso, G. Ploss, G. Schulz, Chem. Ber. 97 (1964) 2066. [19] R.S. Brown, A. Tse, T. Nakashima, R.C. Haddon, J. Am. Chem. Soc. 101 (1979) 3157. [20] M. Rajabi, M. Sc. Thesis, University of Ferdowsi, Mashhad, Iran, 1994. [21] D. Lloyd, N.W. Preston, J. Chem. Soc. C (1969) 2464. [22] G. Gilli, V. Bertolasi, in: Z. Rappoport (Ed.), The Chemistry of Enols, John Wiley and Sons, NY, 1990. [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] [42] [43] [44] [45] [46] [47] [48] [49] [50] [51] C.L. Perrin, B.K. Ohta, Bioorg. Chem. 30 (2002) 3. C.L. Perrin, B.K. Ohta, J. Mol. Struct. 644 (2003) 1. L.M. Jackman, J.C. Trewella, R.C. Haddon, J. Am. Chem. Soc. 102 (1980) 2519. W.J. Linn, W.H. Sharkey, J. Am. Chem. Soc. 79 (1957) 4970. Gaussian 09, Revision A.02, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian, Inc., Wallingford CT, 2009. A.D. Becke, J. Chem. Phys. 98 (1993) 5648. C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785. GaussView 5.0.8, Gaussian Inc., Garnegie Office, Park, Pittsburgh, PA 15106, USA. F. London, J. Phys. Radium, Paris 8 (1937) 397. R. McWeeny, Phys. Rev. 126 (1962) 1028. R. Ditchfield, Mol. Phys. 27 (1974) 789. J.L. Dodds, R. McWeeny, A.J. Sadlej, Mol. Phys. 41 (1980) 1419. K. Wolinski, J.F. Hilton, P. Pulay, J. Am. Chem. Soc. 112 (1990) 8251. J. Tomasi, M. Persico, Chem. Rev. 94 (1994) 2027. J.L. Pascual-Ahuir, E. Silla, J. Tomasi, R. Bonaccorsi, J. Comp. Chem. 8 (1987) 778. B. Mennucci, J. Tomasi, J. Chem. Phys. 106 (1997) 5151. A. Bondi, J. Phys. Chem. 68 (1964) 441. V. Barone, C. Adamo, J. Phys. Chem. 99 (1995) 15062. M. Zahedi-Tabrizi, F. Tayyari, Z. Moosavi-Tekyeh, A. Jalali, S.F. Tayyari, Spectrochim. Acta Part A 65 (2006) 387. S.F. Tayyari, A.R. Nekoei, M. Vakili, M. Hassanpour, Y.A. Wang, J. Theor. Comp. Chem. 5 (2006) 647. S.F. Tayyari, H. Rahemi, A.R. Nekoei, M. Zahedi-Tabrizi, Y.A. Wang, Spectrochim. Acta Part A 66 (2007) 394. R.L. Lintvedt, H.F. Holtzclaw Jr., J. Am. Chem. Soc. 88 (1966) 2713. S.F. Tayyari, Z. Moosavi-Tekyeh, M. Soltanpour, A. Brenji, R.E. Sammelson, J. Mol. Struct. 892 (2008) 32. C.D. Nonhebel, Tetrahedron 24 (1968) 1869. J.J. Koivisto, E.T. Kolehmainen, V.A. Nikiforov, M.J. Nissinen, K.A. Tuppurainen, M. Perakyla, S. Miltsov, V.S. Karavan, Arkivoc III (2001) 95. S.F. Tayyari, T. Bakhshi, S.J. Mahdizadeh, S. Mehrani, R.E. Sammelson, J. Mol. Struct. 938 (2009) 76. P. Pulay, X. Zhou, G. Fogarasi, in: R. Fausto (Ed.), Recent Experimental and Computational Advances in Molecular Spectroscopy, Kluver Academic, Netherlands, 1993, pp. 88–111. K. Szczepaniak, W.B. Person, D. Hadzˇi, J. Phys. Chem. A 109 (2005) 6710. S.F. Tayyari, F. Milani-Nejad, Spectrochim. Acta Part A 56 (2000) 2679.
© Copyright 2024