Journal of Molecular Structure: THEOCHEM 803 (2007) 95–101

www.elsevier.com/locate/theochem

Theoretical study of CAH bond dissociation energies of HC(@X)R

{X = O, S, Se; R = H, CH3, Cl, NH2}
D. Kaur *, Rupinder Preet Kaur, Rajwinder Kaur
Department of Chemistry, Guru Nanak Dev University, Amritsar 143005, India

Received 12 June 2006; received in revised form 4 October 2006; accepted 4 October 2006
Available online 11 October 2006

Abstract

CAH bond dissociation for the molecule HC(@X)R {X = O, S, Se; R = H, CH3, Cl, NH2} have been studied at various theoretical
levels. Studies indicate that CAH BDE increases in the order of X as O < S < Se for R = H, CH3 and Cl. Results also indicate that CAH
BDE’s for substituted formaldehyde and its thio- and seleno-analogs have 7–16 kcal/mol BDE less than that of methane at G2MP2 the-
oretical level indicating magnificent stabilization of HC(@X) radical by C@X group. The radical stabilization energy relative to
HC(@X)H infer smaller variation in BDE due to substituent effect.
 2006 Elsevier B.V. All rights reserved.

Keywords: Bond dissociation energy; Ab initio methods; Radical stabilization energy; NBO analysis; Hyper conjugative interactions

1. Introduction co-enzyme B-12 mediated processes [8], whereas H-atom

abstraction reaction involving peptides radicals are associ-
The bond dissociation energy (BDE) is a fundamental ated with various physiological disorders [9,10] such as
factor influencing chemical reactivity. It is recognized as arteriosclerosis [11], diabetes, aging [10,12] and Alzheimer
a measure of bond strength and is widely utilized for the disease [13–16]. The biological conversion of oxygen into
estimation of heats of formation of organic compounds. water which involves hydrogen atom transfer sometimes
The identification of potential sites for free radical attack leads to formation of super oxide ions, peroxyl radicals
[1], the assessment of the effectiveness of antioxidants [2] and hydrogen peroxide that is called respiratory mistakes
and understanding chain transfer processes [3,4] are only [17]. Intramolecular hydrogen atom abstraction in radical
few examples out of numerous processes that require thor- cations and intramolecular proton transfer in the respective
ough information of bond dissociation energies. molecules have many features in common [18]. Aldehydes
Most of the organic and biochemical reactions involve are important reaction intermediates in photochemical air
abstraction of hydrogen atom that includes combustion, pollution which are also produced in hydrocarbon oxida-
polymerization, atmospheric and interstellar chemical tions [19]. Aldehydes consumption both in combustion
pathways. The oxidation of ribonucleosides and deoxyri- and in atmospheric chemistry involves abstraction of
bonucleosides by certain antibiotics, metal complexes and hydrogen atom [20,21]. Carbonyl free radicals [RAC()@O]
redox active metalloenzymes has been suggested to occur are short lived intermediates in the atmospheric degrada-
through hydrogen abstraction [5–7]. H-atom abstraction tion of volatile organic compounds. Formation of acyl rad-
by the adenosyl radical is the key activation step in icals occur mainly by hydrogen abstraction from aldehydes
and to small extent by halogen extraction from acyl halides
*
Corresponding author. Tel.: +91 183 2258802 09; fax: +91 183
is important for organic synthesis involving acyl radicals
2256619. [22]. There are two types of reactions involving acyl radi-
E-mail address: damanjit32@yahoo.co.in (D. Kaur). cals. First, RACOAX can be transformed into RACOAY

0166-1280/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.theochem.2006.10.002
96 D. Kaur et al. / Journal of Molecular Structure: THEOCHEM 803 (2007) 95–101

through homolytic substitution in which the acyl radical is where Ee is electronic energy, ZPE is zero point vibrational
the key intermediate. Second, acyl radical can add to dou- energy [39], Htrans is translational enthalpy of molecule,
ble or triple bonds, forming acyl products in a direct way. Hrot is rotational enthalpy of molecule, Hvib is vibrational
This reaction helps in intramolecular cyclization [23–26]. enthalpy [40,41] of molecule and RT (PV work term) is
The homolytic bond dissociation energy of the COAH conversion factor from energy to enthalpy.
bond affects considerably the mechanism and kinetics of The thermal contribution to enthalpy is particularly sen-
the reactions involving acyl radicals. The effect of substitu- sitive to low frequency vibrations. Hence, two scale factors
ents on the stability of free radical is also important in are used; one for the ZPE and another one for the vibra-
understanding the nature of reactions involving radicals tional contribution to enthalpy. By following the compre-
as reactants, products or intermediates [27]. The stability hensive paper of Scott et al., ZPE energies are scaled by
of substituted acyl radicals is reflected by the CAH bond 0.9135 at HF/6-31+G* and these scaled ZPE values are
dissociation energy of the corresponding substituted car- used at MP2/6-31+G* theoretical level and by 0.9806 at
bonyl compound [28]. Due to difficulty in dealing with B3LYP levels [42]. Vibrational frequencies for calculating
the acyl radicals, only bond dissociation energy of few alde- vibrational enthalpy is scaled by 0.8945 at HF/6-31+G*
hydes has been determined so far. According to Yong Feng and these scaled values are used at MP2/6-31+G* theoret-
et al., composite methods like G3, CBS-4M and CBSAQ ical level and by 0.9899 at B3LYP levels.
all give satisfactory CAH BDE’s within calculation error The electronic energy of atomic hydrogen atom in DFT
of 1 kcal/mol [29]. They also concluded that method and calculations is basis set dependent as can be observed from
basis set effects on geometry optimization are small Jursic’s data (0.50027 for 6-31G, 0.50216 for 6-311G
whereas on BDE’s are large. basis set and 0.50226 hartree for 6-311++G basis set.
The importance of acyl radicals demands knowledge Pople et al., suggested high-level correction for bound
about the CAH bond dissociation energies and stability unpaired electron and corrected the electronic energy of
of radicals formed from carbonyl compounds. For this hydrogen atom to 0.50000 hartree in G2 method [43].
purpose the present study is devoted to the determination DiLabio et al., suggested that for hydrogen atom being
of CAH BDE’s and substituent effect on BDEs and radical unique one electron system, a similar correction should
stabilization energies of radicals of the RC(@X)H mole- be applied in DFT calculations for the evaluation of
cules (X = O, S, Se and R = H, CH3, Cl, NH2). BDE by fixing electronic energy of hydrogen to 0.50000
hartree [38]. This has been found to decrease the deviation
2. Computational details of calculated bond dissociation energies from the experi-
mental data. The electronic energy of hydrogen atom is
All the calculations reported in the present study were fixed as 0.50000 hartree in present studies.
carried out using Gaussian 98 program suite [30]. Full The vibrational contribution to enthalpy requires a care-
geometry optimizations were performed on each species ful treatment since low frequency vibrations can make a
without any symmetry constraint at each particular basis significant contribution. Following SR rules all scaled tor-
set. Each optimized structure was characterized by fre- sional modes below 260 cm1 are replaced by classical rota-
quency calculations to be a minimum without any imagi- tional limit 1/2RT [42]. Since the H-atom has no rotational
nary vibrational frequency. The various levels at which and vibrational contribution the expression for enthalpy
optimizations were done are B3LYP/6-31+G*, B3LYP/6- for the H-atom becomes
311++G(d, p), ROB3LYP/6-311++G(d, p), MP2/6- H 298 ¼ Ee þ H trans þ RT
31+G*. The calculations using composite methods
G2MP2 [31], CBSAQ and CBSAM [32] have been per-
formed to improve accuracy of relative energies. Calcula- 3. Results and discussion
tions were also performed using restricted open (RO)
shell formalism at DFT and ab initio methods. Full geometry optimizations for the molecules
BDE is calculated as the enthalpy change of the follow- HAC(@X)R [X = O, S, Se; R = H, CH3, Cl, NH2] have
ing reaction in the gas phase at 298 K and 1 atm pressure. been performed at the B3LYP/6-31+G*, B3LYP/6-
311++G(d, p), ROB3LYP/6-311++G(d, p), MP2/6-
A–BðgÞ ! AðgÞ þ BðgÞ 31+G*. The calculations using composite methods
The bond dissociation energy is defined as the sum of heat G2MP2 [31], CBSAQ and CBS-4M [32] have also been per-
of formation (Hf,298) of the products (radicals) minus formed to improve accuracy of relative energies. The bond
those of reactants (parent molecule) [28,33–35]. distances CAH, CAX and bond angles RACAX in the
molecules along with CAX bond distance and RACAX
BDE ¼ DH 298 ¼ H f ðRC XÞ þ H f ðH Þ  H f ðRCXHÞ bond angle in radicals at ROB3LYP/6-311++G(d, p) theo-
The BDE has been calculated by using the following retical level for comparative understanding are given in
equation [36–38] Table 1. These geometrical parameters are important as
they reflect the strength of bond to be dissociated and vari-
DH 298 ¼ DEe þ DZPE þ DH trans þ DH rot þ DH vib þ RT ations in bonding interactions due to the presence of substi-
 D. Kaur et al. / Journal of Molecular Structure: THEOCHEM 803 (2007) 95–101 97

Table 1
Important geometrical parameters for the molecules HC(@X)R; X = O, S, Se and R = H, CH3, Cl, NH2 at B3LYP/6-311++G(d,p) theoretical level
No. Molecule CAH CAX RACAX
Molecule Molecule Radical Molecule Radical
1 HC(@O)H 1.108 1.202 1.173 122.0 124.8
2 HC(@S)H 1.090 1.615 1.568 122.1 131.9
3 HC(@Se)H 1.087 1.755 1.707 121.8 131.0
4 H(@O)CH3 1.112 1.206 1.180 124.9 129.1
5 H(@S)CH3 1.093 1.624 1.576 126.5 138.6
6 H(@Se)CH3 1.090 1.767 1.717 126.7 139.1
7 HC(@O)Cl 1.096 1.179 1.156 123.4 129.1
8 HC(@S)Cl 1.086 1.604 1.576 126.0 134.9
9 HC(@Se)Cl 1.085 1.750 1.723 126.4 135.2
10 HC(@O)NH2 1.106 1.212 1.202 124.9 129.6
11 HC(@S)NH2 1.092 1.645 1.603 126.1 136.3
12 HC(@Se)NH2 1.089 1.794 1.751 126.2 139.1
Bond distances are in Å and bond angles in degrees.

X- X X+

C C C
H R+ H R H R-
III I II

Scheme 1.

tuent and on radical formation. The CAH bond distances

decrease in the order of X as O > S > Se. The ACH3 substi-
tuent increases the CAH bond distance of formaldehyde by
0.004 Å whereas the ACl substituent decreases the bond
distance by 0.012 Å. The CAO bond distance undergoes
comparatively larger variation. The variations in the bond
distances and bond angles can be explained using reso-
nance model as shown in Scheme 1.
The electron donor substituents favor structure III while
the electron withdrawing substituents increases the contri- Fig. 1. Relative trends in variation of C@X bond distance in HC(@X)R;
bution of structure II resulting in increase and decrease X = O, S, Se and R = H, CH3, Cl, NH2.
in CAX bond distances in the two cases, respectively.
The CAX bond distance is decreased considerably in radi-
cals relative to the parent molecule. As can be seen from basis set on computation of CAH BDEs has been explored
Table 1 and Fig. 1, the variation is larger in X = S or Se by full optimization using 6-31+G* and 6-311++G(d,p)
in comparison to X = O. The increase in R1ACAX basis sets at the B3LYP theoretical level and the results
(R1 = the substituent atom attached to carbonyl carbon) are given in Table 2. As can be seen from the table, the
angle in radicals also substantiates increasing CAX interac- BDE values do not show significant variation with change
tions in the radical. in basis set. The small basis set effects in DFT method
result from the fact that electron correlation is handled
through a functional. Our earlier results on BDEs suggest-
4. Bond dissociation energies ed that inclusion of RO formalism in density functional
method decreases the deviation from experimental values,
The computed results for the gas phase CAH BDEs in the BDEs at ROB3LYP/6-311++G(d, p) are also evaluated
HAC(@X)R molecules are reported in Table 2. Experimen- [35]. The composite methods are well known to provide
tal values of BDEs wherever available are also included in results with the high accuracy. However, the applicability
Table 2. The theoretical evaluation of BDEs for these three of these methods is limited to small molecules containing
molecules at ROB3LYP/6-311++G(d, p), G2MP2 and less than eight atoms. The DFT methods on the other hand
CBS-Q levels show less than 2 kcal/mol deviation from allow considerably large molecules to compute with only
the experimental results. MP2/6-31+G* method underesti- limited loss of accuracy. The CAH BDEs at ROB3LYP/
mates the CAH BDEs. Even the inclusion of RO formal- 6-311++G(d, p) theoretical level for H2C(@O), H2C(@S)
ism fails to improve the results. The influence of size of and HC(@O)CH3 molecules are showing deviations of only
98 D. Kaur et al. / Journal of Molecular Structure: THEOCHEM 803 (2007) 95–101

Table 2
CAH BDE’s (in kcal/mol) for the molecules HC(@X)R {X = O, S, Se and R = H, CH3, Cl, NH2} at different theoretical levels
No. Molecule B3LYP/ B3LYP/ ROB3LYP/ MP2/ ROMP2/ G2MP2 CBS-Q CBS-4M Expa
6-31+Ga 6-311++G(d,p) 6-311+G(d,p) 6-31+Ga 6-31+Ga
1 HC(@O)H 87.17 87.61 88.49 76.83 75.93 89.38 88.53 89.23 88.04 ± 0.16
2 HC(@S)H 91.87 92.52 93.33 88.94 83.01 95.48 92.99 93.81 94.0 ± 1.2
3 HC(@Se)H 93.06 94.52 95.38 95.75 84.58 98.53 – –
4 H(@O)CH3 87.49 88.32 89.06 78.30 77.44 90.27 89.35 89.78 89.24
5 H(@S)CH3 89.99 91.04 91.84 85.99 81.79 94.21 92.10 91.59
6 H(@Se)CH3 89.24 98.52 93.59 89.82 82.51 98.16 – 97.03
7 HC(@O)Cl 89.98 91.19 92.01 80.85 79.52 92.16 90.99 101.31
8 HC(@S)Cl 92.23 93.85 94.18 90.24 84.21 96.29 93.53 92.97
9 HC(@Se)Cl 91.28 93.67 – 94.69 83.98 98.05 – 103.22
10 HC(@O)NH2 91.97 92.11 93.47 83.08 82.27 95.24 94.27 94.52
11 HC(@S)NH2 90.68 91.46 92.38 82.54 81.42 93.63 92.44 92.00
12 HC(@Se)NH2 89.15 92.03 92.87 82.32 81.11 94.31 – 93.12
a
Experimental values of CAH bond dissociation energies Refs. [44–46].

0.33, 0.70 and 0.34 kcal/mol from the experimental values, radicals which in turn decide the BDE. The E(2) values
while the deviation is comparatively larger in BDEs associated with different electron delocalizations are
obtained at G2MP2 theoretical level. Relatively more pre- reported in Table 3. Density matrix for an open shell mol-
cise values are evaluated at the CBS-Q level for H2C(@S) ecule factors into two equivalent spin density matrices for a
and HC(@O)CH3 molecules. and b spin. The distinct spin densities suggest that no single
The CAH BDEs increase in the order of X as O < S < Se set of spatial orbital is optimal for describing both spin sys-
for R = H, CH3 and Cl at ROB3LYP/6-311++G(d, p), tems. The occupancies and energies of these orbitals of dif-
G2MP2 and CBSAQ theoretical levels as reflected by the ferent spin densities indicate that radical center is
results in the Table 2 and trends depicted in Fig. 2. With characterized by the presence of carbon non bonding orbi-
R = NH2, no such trend is observed. The CAH BDE is tal (lone pair) nC, which is occupied in a spin system. In
increased in case of R = NH2 and X = O while it is addition, there is one more non bonding orbitals occupied
decreased in case of R = NH2 and X = S and Se relative by the a spin system present on X atom and one electron of
to the value in respective formaldehyde. The BDE values
of HC(@X)H molecules are nearly 7–16 kcal/mol lower
than the CAH BDE for methane (105.78 kcal/mol at Table 3
G2MP2 theoretical level) which clearly suggest that The second order energies E(2) (in kcal/mol) in HC(@X)R {X = O, S, Se
HC(@X) group stabilizes the radical. Henry et al., suggest- and R = H, CH3, Cl, NH2] obtained by using NBO analysis at MP2/6-
ed that the stabilization arises from the interaction of rad- 31+G* theoretical level
ical 2p orbital with p and p* orbitals of the C@O bond [47]. R Species Delocalizationa X=O X=S X = Se
The NBO analysis of the molecules and their respective H Molecule nx fi r*CAH 24.33 13.56 10.91
radicals has been carried out to understand the role of elec- nX fi r*CAH 24.19 13.42 10.77
tron delocalization on the stability of molecules and their Radical nX fi r*CAH (a) 14.05 10.33 9.02
CH3 Molecule nx fi r*CAC 21.56 12.29 10.42
nX fi r*CAH 25.74 13.49 10.70
Radical nX fi r*CAC (a) 12.28 10.96 10.20
Cl Molecule nx fi r*CACl 50.10 28.65 23.35
nX fi r*CAH 22.87 11.50 8.18
nCl fi r*CAX 29.42 24.26 37.19
Radical nX fi r*CACl (a) 36.55 19.11 11.21
nCl fi r*CAX (a) – 13.45 –
nCl fi r*CAX (b) 12.42 20.38 16.58
nCl fi r*CAX (b) 13.32 24.03 0.64
nCl fi r*CAX (b) 13.40 7.14 0.57
NH2 Molecule nx fi r*CAN 30.16 18.07 15.13
nX fi r*CAH 26.04 12.90 9.55
nN fi r*CAX 88.27 110.75 120.54
Radical nX fi r*CAN (a) 15.18 12.00 11.52
nN fi r*CAX (b) 42.44 62.85 69.80
nN fi n*C (a) 61.05 – –
nX fi n*C (a) 143.97 – –
nN fi n*C (b) – 65.42 68.77
nX fi n*C (b) – 105.90 90.08
Fig. 2. Relative trends in bond dissociation energies of HC(@X)R; X = O,
a
S, Se and R = H, CH3, Cl, NH2. The spin of electrons in radicals is reported in parentheses.
 D. Kaur et al. / Journal of Molecular Structure: THEOCHEM 803 (2007) 95–101 99

b spin is occupying pCAX orbital. The energies of these BDE for X = O and R = CH3, Cl results from the higher
orbitals, two non bonded orbitals, one each on C and X stabilization of the substituted formaldehyde relative to
and one pCAX orbital are recorded along with their occu- the respective radical. The substituents effect of CH3, Cl
pancies in Table 4. As the energies of these three orbitals on the CAH BDE of thio and seleno formaldehydes are
lie in close range to one another and these orbitals do much smaller but decrease the BDE. Liao et al., have sug-
not possess any occupancy in the equivalent spatial orbital gested that since the polarity of the C@Se bond is reverse of
of opposite spin, the bonding interaction between these that in C@O bond, this tends to expand the valence orbitals
may arise from the three electron two center system. This on carbon and contract the valence orbitals on selenium
three electron two center stabilization is responsible for which in turn leads to better overlap between the two
decrease in CAH BDE of HC(@X)R molecules relative [48]. In accordance with this the electron releasing substitu-
to that in methane. ent tend to increase negative polarity of carbonyl carbon
The presence of ANH2 substituent decreases CAH thereby decrease size discrepancy between the valence orbi-
BDEs in HC(@X)NH2 with X = S and Se. With the pres- tals which becomes more important in radicals due to three
ence of substituents ACH3, ANH2 and Cl on formalde- electron two center bond. This is also supported by DCAX
hyde, CAH BDEs are increased while a slight decrease in (Fig. 1) which is larger in substituted thio and seleno form-
values is seen with similar substituents on thio and seleno aldehydes in comparison to formaldehydes. The NBO
formaldehydes. The E(2) values responsible for the stabil- analysis suggests decrease in nN fi r*CAX in radical rela-
ization of molecule and radical in HC(@X)NH2 where tive to that of the molecule that predicts that the BDE
X = O, S, Se and R = H, CH3, Cl; decrease in radical rel- should increase in NH2 substituted NH2C(@X)H mole-
ative to the values in the molecule. Increase in CAH cules. The additional stabilization of radical in these species
may result from interaction of the lone pair present on
Table 4 nitrogen with the radical center. The highly electronegative
Energies and Occupancies of some a and b spin NBOs that are important oxygen with short bond distance does not allow the lone
for three electron two center interactions pair on nitrogen to interact with the radical center resulting
Radical Orbital Occupancies Energies in increase of CAH BDE.
a b a b
5. Radical stabilization energies
HC(@O) pCAO – 0.999 – 0.67130
nC 0.997 – 0.60650 –
nO 0.971 – 0.55967 – The radical stabilization energy (RSE) is a measure of
HC(@S) pCAS 0.992 0.998 – 0.42657 effect of substituent on the stability of radical relative to
nC 0.979 – 0.54791 – its effect on the parent molecule. Coote et al., reported that
nS – – 0.44087 –
the effect of alkyl substituent (R = ACH3, ACH2CH3,
HC(@Se) pCASe – 0.996 – 0.39545
nC 0.995 – 0.55923 – AC(CH3)2H, AC(CH3)3 on RAX (X = F, OH, OCH3,
nSe 0.983 – 0.43775 – CH3, H) BDEs varies according to the nature of X [49].
CH3(@O) pCAO 0.970 0.998 – 0.55360 Different trends for RSE of ACH3, ACH2CH3,
nC 0.973 – 0.49386 – AC(CH3)2H, AC(CH3)3 are obtained depending on the
nO – – 0.54643 –
nature of X. Increasing electronegativity of X, increases
CH3(@S) pCAS – 0.981 – 0.60325
nC 0.970 – 0.48842 – the importance of dipolar form of resonance structure
nS 0.980 – 0.48647 – thereby increasing the BDE. Since radical stabilization
CH3(@Se) pCASe – 0.964 – 0.68482 energy is a relative energy, its value is important in under-
nC 0.969 – 0.48683 – standing the effect of substituent on the reactivity of mole-
nSe 0.983 – 0.52129 –
cules. The radical stabilization energies {RSE =
ClC(@O) pCAO 0.994 0.999 – 0.78265
nC 0.926 – 0.68153 – BDERef  BDE[RC(@X)H]; ref = CH4 and HC(@X)H} are
nO – – 0.55597 – listed in Table 5. The trends in RSE for the three series
ClC(@S) pCAS – 0.993 – 0.53326 are shown in Fig. 3. Henry et al., reported radical stabiliza-
nC 0.990 – 0.60692 – tion energies of substituted methyl radicals to be 4.8, 6.1
nS 0.954 – 0.45062 –
and 13.2 kcal/mol for the substituents R = ACH3, ANH2
ClC(@Se) pCASe – 0.989 – 0.50396
nC 0.991 – 0.59829 – and Cl at ROB3LYP/6-311+G(3d,p)// ROB3LYP/6-
nSe 0.962 – 0.46956 – 31G(d) level [47]. The CHO group stabilizes the methyl
NH2C(@O) pCAO 0.973 0.995 – 0.59396 radical by 9.95 kcal/mol at the same theoretical level. Our
nC 0.805 – 0.54842 – results suggest that RSE of 16.39 kcal/mol at G2MP2
nO – – 0.37537 –
due to the presence of carbonyl group in formaldehyde
NH2C(@S) nS – 0.809 – 0.27582
nC 0.967 – 0.52237 – which is much higher than the value obtained by Henry
nS 0.974 – 0.42527 – et al. for HC(@O)CH3 molecule.
NH2C(@Se) nSe 0.819 – 0.26266 The RSEs for thio and selenoformaldehyde are 10.29 and
nC 0.966 – 0.52154 – 7.24 kcal/mol with reference to methane at G2MP2 level
nSe 0.976 – 0.43652 –
which are much smaller in comparison to the value for form-
100 D. Kaur et al. / Journal of Molecular Structure: THEOCHEM 803 (2007) 95–101

Table 5
RSE (in kcal/mol) for the molecules HC(@X)R {X = O, S, Se and R = H, CH3, Cl, NH2] at ROB3LYP/6-311++G(d, p) and G2MP2 theoretical levels
No. Molecule Radical Stabilization energies (RSE) with respect to
Methane (CH4) HC(@X)H
ROB3LYP/6-311++G(d, p) G2MP2 ROB3LYP/6-311++G(d, p) G2MP2
1 HC(@O)H 14.63 16.39 0.0 0.0
2 HC(@S)H 9.79 10.29 0.0 0.0
3 HC(@Se)H 7.74 7.24 0.0 0.0
4 H(@O)CH3 14.06 15.5 0.57 0.89
5 H(@S)CH3 11.28 11.56 1.49 1.27
6 H(@Se)CH3 9.53 7.61 1.79 0.37
7 HC(@O)Cl 11.11 13.61 3.52 2.78
8 HC(@S)Cl 8.94 9.48 0.85 0.81
9 HC(@Se)Cl 8.56 7.72 1.19 0.48
10 HC(@O)NH2 9.65 10.53 4.98 5.86
11 HC(@S)NH2 10.74 12.14 0.95 1.85
12 HC(@Se)NH2 10.25 11.46 2.51 4.22

present but one of these (nO fi n*C(2)) does not stabilize

the radical center (both of same spin density). The difference
in substituent effect on RSE relative to HC(@X)H where
X = O, S, Se can be realized as arising out of difference in
polarity of CAX bond which in turn decreases energy differ-
ence between HOMO and LUMO and allows for better
interaction with the substituent in molecule and radical.

6. Conclusion

In this study, we have reported the CAH BDE for

HC(@X)R (X = O, S, Se and R = H, CH3, Cl, NH2)
molecules obtained at B3LYP/6-31+G*, B3LYP/
6-311++G(d, p), ROB3LYP/6-311++G(d,p), MP2/
6-31+G*, G2MP2, CBS-Q and CBS-4M theoretical levels.
The results at ROB3LYP/6-311++G(d, p) level for
Fig. 3. The relative trends in radical stabilization energies (RSE) in the HC(@O)H, HC(@S)H and CH3C(@O)H molecules deviate
molecule HC(@X)R; X = O, S, Se and R = H, CH3, Cl, NH2. only by 0.33, 0.70 and 0.34 kcal/mol from the experimental
results. Comparison of the CAH BDEs of HC(@O)H,
HC(@S)H and HC(@Se)H with that of methane molecule
aldehyde. As discussed in the previous section, RSE is the suggested magnificent stabilization of the radical by the
result of formation of three electron two center bond as indi- carbonyl group, that has been explained on the basis of
cated by the NBO analysis. The bond is stronger in radical three electron two center bond between C and X. The RSEs
with X = O because of smaller distance between the two cen- of molecules [HC(@X)H] decreases in the order of X as
ters in comparison to the radicals with X = S or Se. The pres- O > S > Se. The reason for decrease in RSE is the increas-
ence of CH3 substituent along with the C@X bond, decreases ing size of chalcogen which is responsible for weaker three
RSE in case of X = O while increase in RSE results in X = S electron two center bond. The radical stabilization energies
and Se. This variation can be understood in terms of obser- of CH3, Cl and NH2 substituted formaldehydes relative to
vation made by Liao et al., that reversal in polarity of CAX HC(@X)H infer smaller variation in BDE due to the sub-
bond helps in strengthening CAX bond. The behavior of stituent in addition to the carbonyl group. The concept
NH2 substituent along with X = S or Se on CAH BDE of polarity difference in CAX bond from X = O, S, Se
appears to be anomalous. RSE is decreased for NH2C(@O) has been utilized to explain the effect of CH3 and Cl substi-
radical while it is increased for NH2C(@S) and NH2C(@Se) tuent on the CAH BDEs of the molecules. The nitrogen of
radicals relative to their respective C(@X)H. The lone pairs NH2 substituent which has been reported to be highly delo-
present on nitrogen and X interact with radical center calized in amides in the order of X as O < S < Se, but RSEs
through nX fi n*C(1) and nN fi n*C(1) interactions as sug- indicate that C(@S)NH2 and C(@Se)NH2 are the radicals
gested by NBO analysis (Table 3, n* represents Lewis unoc- that are stabilized by the interaction of radical center with
cupied orbital) that stabilize the radical in the order of X as nitrogen lone pair. The similar interactions are absent in

S > Se. In case of X = O, the similar delocalizations are C(@O)NH2 radical.
 D. Kaur et al. / Journal of Molecular Structure: THEOCHEM 803 (2007) 95–101 101

Acknowledgement [28] D.F. McMillen, D.M. Golden, Annu. Rev. Phys. Chem. 33 (1982)
493.
[29] Y. Feng, H. Huang, L. Liu, Q.X. Guo, Phys. Chem. Chem. Phys. 5
The authors are thankful to Council of Scientific and (2003) 685–690.
Industrial Research (CSIR), New Delhi for the financial [30] M.J. Frisch, G.W. Trucks, H.B. Schiegel, G.E. Scuseria, M.A. Robb,
assistance in the present research work. J.R. Cheeseman, V.G. Zakrzewski, J.A. Montgomery, R.E. Strat-
mann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N.
Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R.
References Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski,
G.A. Peterson, P.Y. Ayala, Q. Cui, K. Morokuma, D.K. Malick,
[1] E.I. Izgorodina, M.L. Coote, L. Radom, J. Phys. Chem. A 109 (2005) A.D. Rubuck, K. Raghavchari, J.B. Foresman, J. Cioslowski, J.V.
7558–7566. Oritz, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi,
[2] G.R. Buettner, Arch. Biochem. Biophys. 300 (1993) 535. R. Gomperts, R.L. Martin, D.L. Fox, T. Keith, M.A. Al-Laham,
[3] M. Mandalo, A.M. Grana, R.A. Mosquera, Chem. Phys. Lett. 400 C.Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P.M.W.
(2004) 169. Gill, B.G. Jhonson, W. Chen, M.W. Wong, J.L. Andres, M.H.
[4] E.T. Densiov, Polym. Degrad. Stab. 49 (1995) 71. Gordon, E.S. Replogle, J.A. Pople, Gaussian 98, Revision-A.11.2.
[5] C.J. Burrows, J.G. Muller, Chem. Rev. 98 (1998) 1109. Gaussian Inc., Pittsburgh, PA, 1998.
[6] H. Chen, P. Yang, Prog. Chem. 14 (2002) 239. [31] L.A. Curtiss, K. Raghavachari, J.A. Pople, J. Chem. Phys. 98 (1993)
[7] O.D. Schaerer, Angew. Chem. Int. Ed. 42 (2003) 2946. 1293.
[8] M.L. Coote, J. Phys. Chem. A 108 (2004) 3865–3872. [32] J.W. Ochterski, G.A. Petersson, J.A. Montgomery Jr., J. Am. Chem.
[9] E.R. Stadtman, B.S. Berlett, Chem. Res. Toxicol. 10 (1997) 485–494. Soc. 117 (1995) 11299.
[10] K.B. Beckman, B.N. Ames, Physiol. Rev. 78 (1998) 547–581. [33] P. Burk, Illmar A. Koppel, Alar Rummel, A. Trummal, J. Phys.
[11] S. Fu, M.J. Davies, R. Stocker, R.T. Dean, Biochem. J. 333 (1998) Chem. A 104 (2000) 1602.
519–525. [34] Asit K. Chandra, Pham Cam Nam, M.T. Nguyen, J. Phys. Chem. A
[12] S. Linton, M.J. Davies, R.T. Dean, Expt. Gerontol. 36 (2001) 1503– 107 (2003) 9182.
1518. [35] D. Kaur, R.P. Kaur, J. Mol. Struc. (Theochem.) 757 (2005)
[13] R.T. Dean, S. Fu, R. Stocker, M.J. Davies, Biochem. J. 324 (1997) 1–18. 53.
[14] P. Brunelle, A. Rauk, J. Alzheimer’s Dis. 4 (2002) 283–289. [36] G.A. DiLabio, D.A. Pratt, A.D. LoFaro, J.S. Wright, J. Phys. Chem.
[15] A. Rauk, Can. Chem. News 53 (2001) 20–21. A 103 (1999) 16502.
[16] A. Rauk, D.A. Armstrong, D.P. Fairhe, J. Am. Chem. Soc. 122 [37] Asit K. Chandra, T. Uchimaru, Int. J. Mol. Sci. 3 (2002) 407.
(2000) 9761–9767. [38] G.A. DiLabio, A.D. LoFaro, J.S. Wright, J. Phys. Chem. A 103
[17] B. Halliwell, J.M.C. Gutteridge, Free Radicals in Biology and (1999) 1653.
Medicine, Claredon Press, Oxford, UK, 1985. [39] D.A. Pratt, J.S. Wright, K.U. Ingold, J. Am. Chem. Soc. 121 (1999)
[18] K.M. Strik, L.K.M. Kiminkinen, H.I. Kenttamaa, Chem. Rev. 92 4877.
(1992) 1649–1665. [40] P. Sinha, S.E. Boesch, C. Gu, R.A. Wheeler, A.G. Wilson, J. Phys.
[19] M.T. Rayez, J.C. Rayez, T. Berces, G. Landray, J. Phys. Chem. 97 Chem. A 108 (2004) 9213.
(1993) 5570–5576. [41] D.A. McQurrie, Statistical Mechanics, Harper and Row, New York,
[20] M. Hallquist, I. Wangberg, E. Ljunstrom, Environ. Sci. Technol. 31 1976.
(1997) 3166. [42] A.P. Scott, L. Radom, J. Phys. Chem. A 100 (1996) 16502.
[21] A. Alvarado, J. Arey, R. Atkinson, J. Atmos. Chem. 31 (1998) 281. [43] J.A. Pople, M.H. Gordon, D.J. Fox, K. Raghavchari, L.A. Curtiss, J.
[22] B. Viskolcz, T. Berces, Phys. Chem. Chem. Phys. 2 (2000) 5430–5436. Chem. Phys. 10 (1989) 5622.
[23] J. Quirante, X. Vila, C. Escolano, J. Bonjoch, J. Org. Chem. 67 (2002) [44] R. Walsh, S.W. Benson, J. Am. Chem. Soc. 88 (1966) 4570.
2323. [45] R. Becerra, I.W. Carpenter, R. Walsh, J. Phys. Chem. A 101 (1997)
[24] K. Yamada, H. Fujihara, Y. Tamamoto, Y. Miwa, T. Taga, K. 4185.
Tomioka, Org. Lett. 4 (2002) 3509. [46] J. Berkowitz, G.B. Ellison, D. Gutman, J. Phys. Chem. 98 (1994)
[25] A.J. McCarroll, J.C. Walton, Angew Chem. Int. Ed. Engl. 40 (2001) 2744.
2225. [47] D.J. Henry, C.J. Parkinson, P.M. Mayer, L. Radom, J. Phys. Chem.
[26] M.L. Bennasar, T. Roca, R. Griera, M. Bassa, J. Bosch, J. Org. A 105 (2001) 6750.
Chem. 67 (2002) 6268. [48] H.L. Liao, M.D. Su, S.Y. Chu, Chem. Phys. 261 (2000) 275–
[27] A.R. Cherkasov, M. Jonsson, V.I. Galkin, R.A. Cherkasov, Russ. 287.
Chem. Rev. 70 (2001) 1. [49] M.L. Coote, A. Pross, L. Radom, Org. Lett. 5 (2003) 4689.