Theoretical Calculations on the Mechanisms of the GasPhase Elimination Kinetics of 2-Chloro-1-phenylethane, 3-Chloro-1-phenylpropane, 4-Chloro-1-phenylbutane, 5-Chloro-1-phenylpentane, and Their Corresponding

Chloroalkanes: The Effect of the Phenyl Ring

2 ALEXIS MALDONADO,1 JOSE R. MORA,1 SIMON J. SUBERO,2 MARCOS LORONO, TANIA CORDOVA,3 GABRIEL CHUCHANI1
1 2

Centro de Qu mica, Instituto Venezolano de Investigaciones Cient cas, Apartado 21827, CP 1020-A Caracas, Venezuela Departamento de Qu mica, Escuela de Ciencias, Universidad de Oriente Nucleo Sucre, Cumana, Sucre State, Venezuela 3 Department of Medicinal Chemistry, College of Pharmacy, University of Florida, Gainesville, FL 32610 Received 25 October 2010; revised 6 December 2010, 4 January 2011; accepted 7 January 2011 DOI 10.1002/kin.20548 Published online 22 April 2011 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: The kinetics and mechanisms of the dehydrochlorination of 2-chloro-1phenylethane, 3-chloro-1-phenylpropane, 4-chloro-1-phenylbutane, 5-chloro-1-phenylpentane, and their corresponding chloroalkanes were examined by means of electronic structure

Correspondence to: Jose R. Mora; e-mail: jrmora@ivic.gob.ve. Contract grant sponsor: Consejo de Desarrollo Cient co y Human stico. Contract grant number: PG-03-00-6499-2006. Supporting Information is available in the online issue at www.wileyonlinelibrary.com. c 2011 Wiley Periodicals, Inc.

THEORETICAL CALCULATIONS ON THE MECHANISMS OF THE GAS-PHASE ELIMINATION KINETICS calculation using density functional theory methods B3LYP/631G(d,p), B3LYP/631++G(d,p), MPW1PW91/631G(d,p), MPW1PW91/631++G(d,p), PBEPBE/631G(d,p), and PBEPBE/6 31++G(d,p). The potential energy surface was investigated for the minimum energy path. Calculated enthalpies and energies of activation are in good agreement with experimental values using the MPW1PW91 and B3LYP methods. The transition state of these reactions is a four-centered cyclic structure. The reported experimental results proposing neighboring group participation by the phenyl group was not supported by theoretical calculations. The rate-determining process in these reactions is the breaking of Cl C bond. The reactions are described as concerted moderately polar and nonsynchronous. C 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 292302, 2011

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INTRODUCTION
The relative sequence of neighboring phenyl group participation was reported in the rates of acetolysis and formolysis of unsubstituted and methoxy ringsubstituted -phenylalkyl p-bromobenzenesulfonates [1]. In these reactions, the anchimeric assistance of the phenyl group at the third position occurs readily, whereas at the fth and sixth positions, it is found to be rather weak. However, the participation of the phenyl ring at the fourth position was absent. Phenyl assistance was also described in the gas-phase elimination kinetics of unsubstituted and ring-substituted phenylethyl chlorides [2,3]. The aromatic ring caused a signicant increase in the rate of HCl elimination relative to ethyl chloride. This result suggested the formation of a very discrete phenonium ion in the transition state (TS) as depicted in Scheme 1. In Table I [4] we report the effect by a more remote phenyl ring in -phenylalkyl chlorides on the gas-phase elimination kinetics, and we compare it with that of the corresponding parent compounds. According to the result given in Table I, the aromatic nuclei at the third position was thought to favor anchimeric assistance for HCl elimination, whereas participation of the phenyl group at the fth position was considered rather weak. On the contrary, the participation of the phenyl group at the fourth and sixth positions appeared to be unimportant.

The results given in the previous work [4] suggested an interesting examination of the potential energy surface (PES) calculations at the density functional theory (DFT) level of the elimination kinetics of 2-chloro1-phenylethane, 3-chloro-1-phenylpropane, 4-chloro1-phenylbutane, 5-chloro-1-phenylpentane, and their corresponding chloroalkanes. In association with previous theoretical calculations of organic molecules in order to elucidate reaction mechanism in the gas phase [59], we have undertaken the estimation of the kinetic and thermodynamic parameters that may provide support or changes in the mechanism of the phenyl group participation in the dehydrochlorination of -phenylalkyl chlorides.

COMPUTATIONAL METHODS AND MODELS

Calculations of the PES for the gas-phase dehydrochlorination of 2-chloro-1-phenylethane, 3-chloro-1-phenylpropane, 4-chloro-1-phenylbutane, 5-chloro-1-phenylpentane, and their corresponding chloroalkanes were performed using DFT methods, B3LYP/631G(d,p), B3LYP/631G++(d,p), MPW91PW91/631G(d,p), MPW91PW91/6 31G++(d,p), PBEPBE/631G(d,p), and PBEPBE/6 31G++(d,p), implemented in Gaussian 03 [10]. Although DFT methods have been proven to provide good results in treating these systems, the higher level theories in which the electronic wave functions are considered as multistate determinants are still necessary to validate the accuracy of the DFT methods. We have chosen these methods based on previous successful studies in this type of reaction, providing reasonable results with low-computational cost compared with multistate determinant methods. The structures of reactant (R) and products (P) were optimized using the default parameters for convergence. TS structures were located using the quadratic synchronous transit protocol. Stationary

H
Scheme 1

Cl

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Table I Comparative Kinetic and Thermodynamic Parameters of the Gas-Phase Elimination of -Phenylalkyl Chlorides at 440 C Substrate CH3 CH2 Cl C6 H5 CH2 CH2 Cl CH3 CH2 CH2 Cl C6 H5 CH2 CH2 CH2 Cl CH3 CH2 CH2 CH2 Cl C6 H5 CH2 CH2 CH2 CH2 Cl CH3 CH2 CH2 CH2 CH2 Cl C6 H5 CH2 CH2 CH2 CH2 CH2 Cl
The parameters H= , S= , and

104 k1 (s1 ) Ea (kJ/mol) 1.35 7.73 0.10 4.47 3.36 0.16 5.37 8.27 0.39 5.44 6.51 0.12 241.8 4.2 220.9 4.6 229.2 5.4 238.4 3.5 230.7 3.1 220.5 5.8 244.0 6.2 231.2 4.9

Log A (s1 ) 13.84 0.20 13.07 0.35 13.44 0.28 13.99 0.26 13.63 0.24 13.07 0.43 14.61 0.46 13.75 0.36

H = (kJ/mol) 235.9 215.0 223.3 232.5 224.8 214.6 238.1 225.3

S = (J/molK) 4.5 10.2 3.1 7.4 0.5 10.2 19.3 2.8

G= (kJ/mol) 232.6 222.3 225.5 227.2 224.4 221.9 224.3 223.3

G= have been calculated and presented in this work.

points, minimum energy, and TSs were veried using frequency calculations. The TS structures were identied by means of normal-mode analysis by having a single imaginary frequency. Intrinsic reaction coordinate (IRC) calculations were carried out to conrm that the TS structures connected the R and P in the minimum energy path. Frequency calculations allowed obtaining zero-point vibrational energy (ZPVE), temperature corrections [E(T)], and absolute entropies [S(T)] assuming ideal gas behavior from the harmonic frequencies and moments of inertia by standard methods [11]. The average temperature and pressure values within the experimental range were used. Scaling factors for frequencies and zero-point energies were taken from the literature [12,13]. The rst-order rate coefcient k (T) was calculated using the transition state theory (TST) [14], assuming that the transmission coefcient is equal to 1 as expressed in the following equation: k (T ) = (kB T/h) exp( G# /RT) where G# is the Gibbs free energy change between the R and the TS, kB and h are the Boltzmann and Planck constants, respectively. G# was estimated by using the following equations: G# = H # T S# and, H # = V # + ZPVE + E (T) where V # is the potential energy barrier, and ZPVE and E (T) are the differences of ZPVE and temperature corrections between the TS and the R, respectively. Entropy values were estimated from vibrational analysis.

RESULTS AND DISCUSSION Kinetic and Thermodynamic Parameters

The study of the mechanism for dehydrochlorination of 2-chloro-1-phenylethane, 3-chloro-1-phenylpropane, 4-chloro-1-phenylbutane, 5-chloro-1-phenylpentane, and their corresponding chloroalkanes was carried out using DFT methods described above. Calculated parameters using DFT methods for the minimum energy pathway are reported in Table II. Calculations of these parameters show reasonable good agreement of calculated enthalpies of activation and energies of activation with the reported experimental values when using B3LYP and MPW1PW91 level of DFT Calculated entropies deviate from the experimental value due to the use of the harmonic approximation and the presence of low-frequency modes. The experimental entropy of activation -10 J/molK for 2-chloro-1-phenylethane and 4-chloro-1-phenylbutane implies the loss of degrees of freedom in the TS; conversely, in the case of 3-chloro-1-phenylpropane, 5-chloro-1-phenylpentane, and the corresponding saturated chloralkanes, the small increase in entropy suggests a looser TS conguration. The elimination reactions of 2-chloro-1-phenylethane and 4-chloro-1-phenylbutane have similar free energies of activation. For 3-chloro-1-phenylpropane, 5chloro-1-phenylpentane, and the corresponding saturated chloralkanes, the higher enthalpy of activation is partially compensated by more positive entropy of activation, resulting in higher free energy of activation and, consequently, smaller reaction rate coefcient compared with the other two substrates. We have selected the MPW1PW91/631++G(d,p) method for the geometries of the species involved in the reaction because we obtained enthalpies of activation closer to experimental values for all substrates in this study. These geometries were used in natural bond orbital (NBO) charges and bond order calculations described below.
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Table II Thermodynamic and Kinetic Parameters of the Gas-Phase Elimination of HCl from 2-Chloro-1-Phenylethane, 3-Chloro-1-Phenylpropane, 4-Chloro-1-Phenylbutane, 5-Chloro-1-Phenylpentane, and the Corresponding Saturated Chloralkanes at 440 C Method CH3 CH2 Cla Experimental MPW1PW91/631G(d,p) MPW1PW91/631++G(d,p) Experimental B3LYP/631G(d,p) B3LYP/631++G(d,p) MPW1PW91/631G(d,p) MPW1PW91/631++G(d,p) PBEPBE/631G(d,p) PBEPBE/631++G(d,p) Experimental B3LYP/631G(d,p) B3LYP/631++G(d,p) MPW1PW91/631G(d,p) MPW1PW91/631++G(d,p) PBEPBE/631G(d,p) PBEPBE/631++G(d,p) Experimental B3LYP/631G(d,p) B3LYP/631++G(d,p) MPW1PW91/631G(d,p) MPW1PW91/631++G(d,p) PBEPBE/631G(d,p) PBEPBE/631++G(d,p) Experimental B3LYP/631G(d,p) B3LYP/631++G(d,p) MPW1PW91/631G(d,p) MPW1PW91/631++G(d,p) PBEPBE/631G(d,p) PBEPBE/631++G(d,p) Experimental B3LYP/631G(d,p) B3LYP/631++G(d,p) MPW1PW91/631G(d,p) MPW1PW91/631++G(d,p) PBEPBE/631G(d,p) PBEPBE/631++G(d,p) Experimental B3LYP/631G(d,p) B3LYP/631++G(d,p) MPW1PW91/631G(d,p) MPW1PW91/631++G(d,p) PBEPBE/631G(d,p) PBEPBE/631++G(d,p) 104 k (s1 ) 1.31 1.75 4.72 7.76 87.17 219.64 9.83 21.31 1710.08 3602.01 4.47 73.05 221.40 9.88 24.54 1068.19 2484.25 3.29 37.68 116.71 4.31 48.26 502.73 1227.54 5.37 97.98 294.20 4.69 11.74 1462.82 3988.20 8.30 534.88 1843.22 297.34 155.70 5248.19 16377.61 5.44 95.58 304.94 13.17 33.48 1357.95 3306.96 Ea (kJ/mol) 241.8 243.8 237.9 220.9 219.2 213.7 230.7 226.2 201.2 197.2 229.2 224.3 217.3 236.1 230.3 208.8 203.3 238.4 224.0 217.7 235.4 222.0 208.4 203.6 230.7 223.3 216.3 240.3 234.4 207.9 201.7 220.5 215.0 207.2 217.6 220.5 201.1 194.9 244.0 223.0 215.9 234.6 228.7 207.6 202.0 Log A (s1 ) 13.84 14.10 14.10 13.07 13.99 13.99 13.89 13.90 13.97 14.00 13.44 14.29 14.26 14.29 14.26 14.32 14.29 13.98 13.98 14.02 13.88 13.95 13.97 14.00 13.63 14.35 14.31 14.27 14.24 14.40 14.37 13.07 14.48 14.44 14.41 14.34 14.45 14.49 14.61 14.31 14.29 14.30 14.28 14.34 14.32 H= (kJ/mol) 235.9 238.2 232.2 215.0 213.2 207.8 224.7 220.3 195.2 191.3 223.3 218.3 211.3 230.1 224.4 202.9 197.4 232.5 218.1 211.8 229.5 216.1 202.5 197.7 224.8 217.4 210.4 234.4 228.4 202.0 195.7 214.6 209.1 201.3 211.6 214.6 195.2 189.0 238.1 217.1 209.9 228.7 222.8 201.7 196.1 S= (J/molK) 4.5 10.0 9.9 10.2 7.4 7.4 5.4 5.5 6.9 7.6 3.1 13.11 12.48 13.01 12.56 13.70 13.02 7.4 7.2 7.8 5.3 6.5 6.9 7.6 0.5 14.24 13.49 12.77 12.08 15.13 14.68 10.2 16.7 16.0 15.4 14.1 16.1 17.0 19.3 13.53 13.18 13.36 12.87 14.04 13.58 G= (kJ/mol) 232.6 231.5 225.7 222.3 207.9 202.5 220.9 216.3 190.3 185.9 225.5 209.0 202.4 220.9 215.5 193.1 188.1 227.2 212.9 206.2 225.8 211.5 197.6 192.3 224.4 207.3 200.7 225.3 219.8 191.2 185.3 221.9 197.2 189.9 200.7 204.5 183.7 176.9 224.3 207.4 200.5 219.2 213.6 191.7 186.4
(Continued)

C6 H5 CH2 CH2 Cl

CH3 CH2 CH2 Cl

C6 H5 CH2 CH2 CH2 Cl

CH3 CH2 CH2 CH2 Cl

C6 H5 CH2 CH2 CH2 CH2 Cl

CH3 CH2 CH2 CH2 CH2 Cl

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Table II Continued Method C6 H5 CH2 CH2 CH2 CH2 CH2 Cl Experimental B3LYP/631G(d,p) B3LYP/631++G(d,p) MPW1PW91/631G(d,p) MPW1PW91/631++G(d,p) PBEPBE/631G(d,p) PBEPBE/631++G(d,p) 104 k (s1 ) 6.51 37.61 100.17 3.25 4.42 302.65 54812.10 Ea (kJ/mol) 231.2 223.4 216.2 235.1 229.2 208.1 208.4 Log A (s1 ) 13.75 13.94 13.84 13.74 13.43 13.73 16.00 H= (kJ/mol) 225.3 217.4 210.3 229.2 223.3 202.2 202.5 S= (J/molK) 2.8 6.33 4.48 2.47 3.28 2.28 45.90 G= (kJ/mol) 223.3 212.9 207.1 227.4 225.6 200.6 169.7

Theoretical calculation of the elimination kinetic of compound of reference ethyl chloride was reported in [9].

Figure 1 Optimized structures for reactant (R), transition state (TS), and product (P) in gas-phase HCl elimination of C6 H5 CH2 CH2 Cl obtained from MPW1PW91/631++G(d,p). [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

Figure 2 Optimized structures for reactant (R), transition state (TS), and product (P) in the gas-phase elimination of CH3 CH2 CH2 Cl at MPW1PW91/631++G(d,p). [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

TS AND MECHANISM
The optimized structures for reactants, TS, and P for the dehydrochlorination of 2-chloro-1-phenylethane, 3chloro-1-phenylpropane, 4-chloro-1-phenylbutane, 5chloro-1-phenylpentane, and the corresponding saturated chloralkanes from MPW1PW91/631G++(d,p) calculations are shown in Figs. 17, respectively. The TSs were veried by IRC calculations; the plots are given as Supporting Information Figs. 814. Geometrical parameters of the optimized R, TS, and P are summarized in Table III. Atom numbers in Scheme 2 are used in the discussion of the TS structural parameters, charges, and bond order analysis that follow.

The TS structure for the dehydrochlorination of 2-chloro-1-phenylethane, 3-chloro-1-phenylpropane, 4-chloro-1-phenylbutane, 5-chloro-1-phenylpentane, and the corresponding saturated chloralkanes is four-centered cyclic geometry composed of atoms Cl1 , C2 , C3 , and H4 . For 2-chloro-1-phenylethane, in the Cl1 C2 bond is elongated from about 1.80 A in the TS; this distance is slightly the R to 2.51 A larger in the TS for 3-chloro-1-phenylpropane, 4-chloro-1-phenylbutane, and 5-chloro-1-phenyl respectively). pentane (2.57, 2.56, and 2.55 A, Changes in C2 C3 bond are similar for the four in the substrates; this bond is shortened from 1.53 A in the TS, indicating the double bond R to 1.40 A
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Figure 3 Optimized structures for reactant (R), transition state (TS), and product (P) in gas-phase HCl elimination of C6 H5 CH2 CH2 CH2 Cl obtained from MPW1PW91/631++G(d,p). [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

Figure 4 Optimized structures for reactant (R), transition state (TS), and product (P) in gas-phase HCl elimination of CH3 CH2 CH2 CH2 Cl obtained from MPW1PW91/631++G(d,p). [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

Figure 5 Optimized structures for reactant (R), transition state (TS), and product (P) in gas-phase HCl elimination of C6 H5 CH2 CH2 CH2 CH2 Cl obtained from MPW1PW91/631++G(d,p). [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

Figure 6 Optimized structures for reactant (R), transition state (TS), and product (P) in gas-phase HCl elimination of CH3 CH2 CH2 CH2 CH2 Cl obtained from MPW1PW91/631++G(d,p). [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

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Figure 7 Optimized structures for reactant (R), transition state (TS), and product (P) in gas-phase HCl elimination of C6 H5 CH2 CH2 CH2 CH2 CH2 Cl obtained from MPW1PW91/631++G(d,p). [Color gure can be viewed in the online issue, which is available at wileyonlinelibrary.com.]

Scheme 2

formation. The C3 H4 is stretched in all substrates in the TS. The distance from 1.09 to 1.251.27 A H4 Cl1 is signicantly smaller in the TS for the in the reactants to four substrates; from about 2.9 A in the TS, as hydrogen H4 is transferred 1.881.89 A to for hydrogen chloride. Dihedral angles for 2-chloro-1-phenylethane, 4-chloro-1-phenylbutane, 5-chloro-1-phenylpentane, and corresponding saturated chloroalkanes show deviations from planarity in the TS conguration; conversely, in the case of 3-chloro-1-phenylpropane atoms, Cl1 , C2 , C3 , and H4 are in the same plane in the TS. The TS cyclic structure formed by atoms Cl1 , C2 , C3 , and H4 is out-of-plane with respect to the phenyl ring in all substrates. The imaginary frequency that characterizes the TS is mainly associated with the hydrogen H4 transfer from C3 to the chlorine Cl1 . IRC calculations were performed to verify the TS leading to the P and the R in the forward and reverse directions, respectively. Further examination of these elimination reactions to determine the nature of the TS was carried out by means of NBO calculations. NBO charges and bond indexes are discussed in the next sections.

NBO CHARGES
Natural bond orbital calculations have been used in the study of the changes occurring in a reaction.

Changes in electron density distribution in stationary points identied in the minimum energy pathway can be studied with NBO charges as shown in Table IV. Natural bond orbital charges for the four atoms directly involved in the reaction, Cl1 , C2 , C3 , and H4 , reveal small differences. Atom Cl1 in 4-chloro1-phenylbutane is more negative in the R compared with the other two substrates. However, for 3-chloro1-phenyl-1-phenylpropane, there is a larger increase in electron density at the Cl1 atom from the R to the TS (0.508) compared with 2-chloro-1-phenylethane (0.476), 4-chloro-1-phenylbutane (0.493), and 5chloro-1-phenylpentane (0.496). Changes in electron density at C2 show some differences as it becomes more positive; for 2-chloro-1-phenylethane, 3-chloro1-phenylpropane, and 4-chloro-1-phenylbutane, the change in charge is 0.239, 0.278, and 0.263, respectively. These results imply more charge separation at Cl1 C2 bond in the TS for 3-chloro1-phenylpropane. NBO charges show very small changes at C3 for all substrates; nonetheless, for 3-chloro-1-phenylpropane, C3 augments its electron density in the TS in greater extent (0.026) compared with 2-chloro-1-phenylethane (0.003) and 4-chloro-1-phenylbutane (0.013). At H4 , changes are similar for all substrates; H4 becomes more positive by 0.133, 0.131, and 0.125 for 2-chloro1-phenylethane, 3-chloro-1-phenylpropane, and 4chloro-1-phenylbutane, respectively.
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Table III Structural Parameters of Reactant (R), Transition state (TS), and Products (P) in HCl elimination from 2-Chloro-1-Phenylethane, 3-Chloro-1-Phenylpropane, 4-Chloro-1-Phenylbutane, 5-Chloro-1-Phenylpentane, and the Corresponding Saturated Chloralkanes Obtained from MPW1PW91/631++G(d,p) Calculations Interatomic Lengths (A) X R C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 Cl1 C2 1.799 1.799 1.799 1.800 1.803 1.799 1.799 2.518 2.552 2.570 2.564 2.555 2.554 2.553 5.998 3.217 10.746 3.993 3.733 3.993 3.992 C2 C3 1.523 1.516 1.516 1.516 1.519 1.516 1.516 1.399 1.395 1.395 1.396 1.395 1.395 1.395 1.335 1.322 1.330 1.318 1.331 1.318 1.318 C3 H4 1.094 1.094 1.094 1.095 1.094 1.095 1.095 1.268 1.262 1.248 1.254 1.256 1.260 1.261 8.130 3.570 12.597 3.131 3.568 3.131 3.131 H4 Cl1 2.921 2.918 2.914 2.921 2.855 2.920 2.918 1.876 1.866 1.894 1.890 1.884 1.875 1.873 1.280 1.285 1.280 1.308 1.288 1.308 1.308

TS

Dihedral angles (degrees) X C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 Cl1 C2 C3 H4 4.449 2.704 0.578 2.945 3.340 2.853 3.374 C2 C3 H4 Cl1 12.464 7.898 1.679 8.529 9.733 8.332 9.839 C3 H4 Cl1 C2 10.599 6.669 1.421 7.218 8.253 7.051 8.322 Imaginary frequency (cm1 ) C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 1301.15 1326.99 1231.97 1251.56 1268.57 1297.59 1300.96 H4 Cl1 C2 C3 4.610 2.829 0.594 3.041 3.464 2.975 3.521

Bond Order Analysis

Bond orders have been used to study the reaction progress along the minimum energy path [1517]. Wiberg bond indexes [18] were computed using the NBO program [19] implemented in Gaussian 03W. These indexes allow estimating bond orders from popInternational Journal of Chemical Kinetics DOI 10.1002/kin

ulation analysis. The reaction process is also described in using the synchronicity (Sy ) concept proposed by Moyano et al. [20] dened by the expression
n

Sy = 1
i =1

|Bi B av|/B av

(2n 2)

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Table IV NBO Charges of Reactant (R), Transition State (TS), and Products (P) in HCl Elimination from 2-Chloro-1-Phenylethane, 3-Chloro-1-Phenylpropane, 4-Chloro-1-Phenylbutane, 5-Chloro-1-Phenylpentane, and the Corresponding Saturated Chloralkanes Obtained from MPW1PW91/631++G(d,p) Calculations NBO Charges X R C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 Cl1 0.086 0.085 0.085 0.086 0.095 0.086 0.085 0.562 0.577 0.593 0.585 0.588 0.584 0.581 0.295 0.304 0.290 0.309 0.314 0.313 0.312 C2 0.446 0.455 0.456 0.450 0.448 0.449 0.449 0.207 0.191 0.178 0.183 0.185 0.187 0.187 0.429 0.451 0.462 0.487 0.455 0.488 0.487 C3 0.515 0.507 0.497 0.507 0.510 0.504 0.503 0.518 0.523 0.523 0.525 0.523 0.514 0.515 0.242 0.253 0.222 0.209 0.236 0.205 0.205 H4 0.266 0.257 0.257 0.255 0.261 0.255 0.256 0.399 0.387 0.388 0.388 0.386 0.385 0.385 0.295 0.296 0.290 0.297 0.305 0.301 0.300

TS C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 P C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2

where n is the number of bonds directly involved in the reaction. The synchronicity parameter had been used to explain whether a concerted reaction proceeds in a synchronic fashion where all events have the same progress along the reaction coordinate (Sy = 1) or whether the reaction is not synchronic (Sy = 0). The calculated bond index is Bi , and the relative variation of the bond index is obtained from Bi = BiTS BiR BiP BiR

where the superscripts R, TS, and P represent R, TS, and P, respectively. The average value is calculated from
n

phenylpentane, and the corresponding saturated chloralkanes, i.e., Cl1 C2 , C2 C3 , C3 H4 , and H4 Cl1 . Changes in other bonds are smaller and were not considered in the analysis. Examination of the calculated parameters given in Table V shows that the breaking of Cl1 C2 is the dominating process; however, there are small differences: for 3-chloro-1-phenylpropane and 5-chloro-1-phenylpentane about 68% progress in the TS and 67% for 2-chloro-1-phenylethane and 4chloro-1-phenylbutane. The breaking of C3 H4 bond shows intermediate progress, being slightly less advanced (50%) for 3-chloro-1-phenylpropane compared with the other three substrates: 54% for 2-chloro-1phenylethane, 52% for 4-chloro-1-phenylbutane, and 53% for 5-chloro-1-phenylpentane. The remaining reaction coordinates, i.e., the C2 C3 bond order change and H4 Cl1 bond formation are less advanced, with about 37% and 2526%, respectively, the later showing smaller progress for 3-chloro-1-phenylpropane. The above denition of the Sy parameter where the concerted synchronic process is characterized by Sy = 1 and concerted nonsynchronous reactions by Sy = 0, together with the calculated value for these reactions Sy = 0.79, demonstrates these reactions as concerted moderately polar and nonsynchronous processes. The changes observed in electron distribution and bond orders involving more charge separation in the TS for 3-chloro-1-phenylpropane explain the differences in activation energy. To further investigate possible phenyl group assistance, additional parameters are reported in Table VI. Atom C5 is the carbon at the phenyl ring linked to C3 . If the proposed participation is to be observed, then we expect that the distance C5 C2 diminishes in the TS, and also changes in charges at C5 and C5 C2 bond index. Calculated parameters illustrate that C5 is not likely to be involved in neighboring group participation; C5 C2 Wiberg bond indexes are negligible in the TS and a marginal change at C5 charge is observed. This observation, along with the TS geometry in which the four atoms involved in the changes in the TS form a pseudo-cycle that is out-of-plane with respect to the phenyl ring, thus preventing orbital overlap and effective electron delocalization, lead to disregard a possible participation by the phenyl group.

Bave = 1/n
i =1

Bi

CONCLUSIONS
The unimolecular gas-phase dehydrochlorination of 2-chloro-1-phenylethane, 3-chloro-1-phenylpropane, 4-chloro-1-phenylbutane, 5-chloro-1-phenylpentane, and the corresponding saturated chloralkane
International Journal of Chemical Kinetics DOI 10.1002/kin

Wiberg bonds indexes, Bi , were calculated for those bonds implicated in the dehydrochlorination reaction of 2-chloro-1-phenylethane, 3-chloro-1phenylpropane, 4-chloro-1-phenylbutane, 5-chloro-1-

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301

Table V Wiberg Bond Index of Reactant (R), Transition State (TS), and Products (P) in HCl Elimination from 2-Chloro-1-Phenylethane, 3-Chloro-1-Phenylpropane, 4-Chloro-1-Phenylbutane, 5-Chloro-1-Phenylpentane, and the Corresponding Saturated Chloralkanes Obtained from MPW1PW91/631++G(d,p) Calculations X BiR C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 C6 H5 CH3 C6 H5 CH2 CH3 CH2 C6 H5 CH2 CH2 CH3 CH2 CH2 C6 H5 CH2 CH2 CH2 Cl1 C2 0.9998 1.0033 1.0031 1.0027 0.9981 1.0028 1.0032 0.3283 0.3277 0.3185 0.3312 0.3235 0.3231 0.3246 0.0000 0.0107 0.0000 0.0038 0.0021 0.0037 0.0037 67.16 68.62 68.25 67.22 67.73 68.03 67.89 C2 C3 1.0081 1.0221 1.0208 1.0237 1.0217 1.0238 1.0235 1.3436 1.3821 1.3723 1.3759 1.3799 1.3832 1.3826 1.9033 1.9669 1.9757 1.9699 1.9767 1.9693 1.9691 37.48 38.10 36.81 37.22 37.51 38.01 37.98 C3 H4 0.8979 0.9019 0.9013 0.9015 0.9017 0.9014 0.9010 0.4126 0.4291 0.4463 0.4397 0.4348 0.4305 0.4300 0.0000 0.0087 0.0000 0.0060 0.0008 0.0060 0.0059 54.04 52.93 50.48 51.67 51.82 52.59 52.62 H4 Cl1 0.0022 0.0022 0.0021 0.0022 0.0032 0.0022 0.0022 0.2382 0.2494 0.2316 0.2333 0.2350 0.2418 0.2432 0.9156 0.8971 0.9186 0.8985 0.8929 0.8958 0.8962 25.84 27.62 25.09 25.78 26.05 26.81 26.96 Sy

BiTS

C6 H5 = 0.7908 CH3 = 0.8027 C6 H5 CH2 = 0.7900 CH3 CH2 = 0.7954 C6 H5 CH2 CH2 = 0.7961 CH3 CH2 CH2 = 0.7994 C6 H5 CH2 CH2 CH2 = 0.8002

BiP

%Ev

reactions has been studied by density functional methods to characterize the reaction path leading to the P observed. The TS is a four-centered cyclic structure that lies at an angle with respect to the phenyl ring. The reactions are described as concerted and moderately polar (Sy = 0.79), dominated by the breaking of the C Cl bond. Calculated enthalpy and energy of activation are in good agreement with experimental values at MPW1PW91/631++G(d,p) level of DFT. The changes in atom distances, electron distribution, and bond orders allow explaining the differences observed in energies of activation and reaction rate for 3-chloro-1-phenylpropane compared with 2-chloro-1-phenylethane, 4-chloro-1-phenylbutane, and 5-chloro-1-phenylpentane. For 3-chloro-1phenylpropane, the charge separation is greater in the TS, and consequently, the energy of activation is higher compared with the other two substrates.

The reported experimental results proposing neighboring group participation is not supported in this theoretical study. The optimized TS geometry does not allow orbital overlap for an effective electron delocalization from the phenyl group, the carbon linked to chlorine. This is demonstrated by NBO charges and bond orders.

SUPPORTING INFORMATION
Intrinsic Reaction Coordinates were obtained from the gas-phase elimination reaction of 2-chloro-1phenylethane, 3-chloro-1-phenylpropane, 4-chloro-1phenylbutane, and 5-chloro-1-phenylpentane. This material is available in the online issue at www.wileyonlinelibrary.com.

International Journal of Chemical Kinetics

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MALDONADO ET AL.

Table VI Distances, NBO Charges, and Wiberg in Bond Index at the Atoms that Could be Involved in Anchimeric Assistance in Reactant (R), Transition State (TS), and Products (P) in HCl Elimination from 2-Chloro-1-Phenylethane, 3-Chloro-1-Phenylpropane, 4-Chloro-1-Phenylbutane, and 5-Chloro-1-Phenylpentane Obtained from MPW1PW91/631++G(d,p) Calculations Distance (A) C5 -C2 2.487 3.088 3.281 6.378 2.536 2.975 4.459 6.283 2.515 2.954 3.790 6.110 Bond Index C5 -C2 0.0148 0.0016 0.0016 0.0003 0.0228 0.0024 0.0006 0.0002 0.0126 0.0019 0.0006 0.0005 NBO Charges C5 0.046 0.046 0.045 0.034 0.067 0.042 0.051 0.037 0.079 0.042 0.033 0.032

X R C6 H5 C6 H5 CH2 C6 H5 CH2 CH2 C6 H5 CH2 CH2 CH2 C6 H5 C6 H5 CH2 C6 H5 CH2 CH2 C6 H5 CH2 CH2 CH2 C6 H5 C6 H5 CH2 C6 H5 CH2 CH2 C6 H5 CH2 CH2 CH2

TS

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International Journal of Chemical Kinetics

DOI 10.1002/kin