Canadian Journal of

Chemistry

Revue canadienne de

chimie

Volume 93

An NRC Research
Press Journal

2015

Une revue de
NRC Research
Press

www.nrcresearchpress.com

279

ARTICLE
Substituent effect on NH bond dissociation enthalpies of
carbamates: a theoretical study

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

Rupinder preet Kaur, Damanjit Kaur, and Ritika Sharma

Abstract: The present investigation deals with the study of the NH bond dissociation enthalpies (BDEs) of the Y-substituted
(NH2-C(=X)Y-R) and N-substituted ((R)(H)NC(=X)YH) carbamates (X, Y = O, S, Se; R = H, CH3, F, Cl, NH2), which have been evaluated
using ab initio and density functional methods. The variations in NH BDEs of these Y-substituted and N-substituted carbamates
as the effect of substituent have been understood in terms of molecule stabilization energy (ME) and radical stabilization energy
(RE), which have been calculated using the isodesmic reactions. The natural bond orbital analysis indicated that the electrodelocalization of the lone pairs of heteroatoms in the molecules and radicals affect the ME and RE values depending upon the type
and site of substitution (whether N- or Y-). The variations in NH BDEs depend upon the combined effect of molecule stabilization
and radical stabilization by the various substituents.
Key words: carbamates, substituent effect, molecule stabilization energy, radical stabilization energy, natural bond orbital,
electron delocalization.
Rsum : La prsente tude sintresse aux enthalpies de dissociation des liaisons (EDL) NH de carbamates Y-substitus
(NH2-C(=X)Y-R) et N-substitus ((R)(H)NC(=X)YH) (X, Y = O, S, Se; R = H, CH3, F, Cl, NH2), lesquels ont t valus a` laide de mthodes
ab initio et de la fonctionnelle de la densit. Les variations des EDL NH de ces carbamates, consquences de leffet de substituant,
ont t apprhendes du point de vue de lnergie de stabilisation molculaire (ESM) et de lnergie de stabilisation radicalaire
(ESR) qui ont t calcules a` partir des ractions isodesmiques. Lanalyse des orbitales naturelles de liaison a montr que la
dlocalisation lectronique des paires isoles dhtroatomes dans les molcules et les radicaux affectait les valeurs de lESM et
de lESR, en fonction du type et du site de substitution (N- ou Y-). Les variations des EDL NH dpendent des effets combins des
stabilisations molculaire et radicalaire par divers substituants. [Traduit par la Rdaction]
Mots-cls : carbamates, effet de substituant, nergie de stabilisation molculaire, nergie de stabilisation radicalaire, orbitale
naturelle de liaison, dlocalisation lectronique.

Introduction
In reactions involving radical intermediates, no quantity is
more important than the homolytic bond dissociation energy
(BDE).1 Thermodynamics of reactions involving the free radical is
governed by enthalpy change accompanying the formation of
the free radical, i.e., BDE.2 The BDEs act as database for reecting
the intrinsic or instantaneous strength of the bond as well as the
stability of the radicals obtained after cleavage. These are one of
the important properties of molecules for considering their decomposition and chemical reactivities and for estimating their
heat of formation.3 The accurate prediction of BDEs has numerous applications, including the identication of sites for potential
free radical attack in peptides, the assessment of the effectiveness
of antioxidants, and the study of chain-transfer processes (such as
long-chain branching) in free radical polymerization.47 Most of
the organic and biochemical reactions involve abstraction of the
hydrogen atom that includes combustion, polymerization, atmospheric, and interstellar chemical pathways. The oxidation of ribonucleosides and deoxyribonucleosides by certain antibiotics,
metal complexes, and redox active metalloenzymes has been suggested to occur through hydrogen abstraction.810 Hydrogen atom
abstraction by the adenosyl radical is the key activation step in
coenzyme B-12 mediated processes,11 whereas hydrogen atom abstraction reactions involving peptide radicals are associated with

various physiological disorders12,13 such as arteriosclerosis,14 diabetes, aging,15,16 and Alzheimers disease.1719
The NH bond is a key functional group in organic and biological chemistry. The class of compounds containing NH bonds has
attracted a large number of researchers due to their presence in
pharmaceutical agents,2024 building blocks of biomolecules,
synthetic commercial products and toxic substances, and2527
antioxidants and as22,2830 complexing agents,31 herbicides, and
surfactants.22,30,32 Nitrogen-centered radicals are of synthetic importance33 where they have been used in a number of cyclization
processes34 and homolytic amination reactions of aromatic molecules. The NH bond cleavage is also reported in the proton
transfer enzymatic reactions catalyzed by acetylcholinestrase. Nitrogen derivatives of amides, lactams, carbamates, and imides
have been shown to be effective initiators for the metal-catalyzed
living radical polymerization of methacrylates.35
Determination of NH BDEs of carbamates is important from
biological, synthetic, medicinal as well as industrial perspective, as they exhibit complex chemical and biological activities as synthetic intermediates, protecting groups, chelating
agents, and free radical scavengers and being constituents of
insecticides, pesticides, fungicides, antiviral, antifungal, antibacterial, antiparasitic, antiproliferative, antidermatophytic,
antitumor agents, chemotherapeutic drugs, antioxidants, and
industrial chemicals.3643

Received 18 July 2014. Accepted 3 October 2014.

R. Kaur and R. Sharma. Guru Nanak Dev University College, Verka, Distt, Amritsar 143001, India.
D. Kaur. Department of Chemistry, Guru Nanak Dev University, Amritsar 143005, India.
Corresponding author: Rupinder preet Kaur (e-mail: rupinderpreet@gmail.com).
Can. J. Chem. 93: 279288 (2015) dx.doi.org/10.1139/cjc-2014-0326

Published at www.nrcresearchpress.com/cjc on 20 October 2014.

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

280

Can. J. Chem. Vol. 93, 2015

The strength of a bond is sensitive to the number of atoms/

groups attached to the atom involved in bond dissociation. A
substituent inuences the bond strength of a molecule in a quantitative sense. The strength of the NH bond is sensitive to the
number of atoms attached to the nitrogen.44,45 Substituents present on the radical because of their steric or electronic nature
inuence both the kinetic and thermodynamic stability of the
radical.46 Substituents through their steric effects can play a
signicant role in the kinetic stabilization, whereas lowering
of energy of the ground state plays an important role in the thermodynamic stabilization of the radical. It is therefore the intrinsic
property that is principally inuenced by the ability of the substituents to delocalize the unpaired electron.47 This can reduce
the reactivity by reducing the spin densities on radical center. The
measure of stability of nitrogen-centered radicals is provided by
the NH homolytic BDE.
The effect of the substituent on the intrinsic structure, reactivity, and energetics of carbamates has been analyzed by studying
the BDE in NH2C(=X)Y-R and (R)(H)NC(=X)YH (X, Y = O, S, Se; R = H,
F, Cl, CH3, NH2) molecules.

Scheme 1. (a) Different possible conformations for Y substitution.

(b) Different possible conformations for nitrogen substitution. Here,
i indicates the orientation of Y-R with respect to the C=X group
and j indicates the orientation of R-N with respect to the C=X
group. The dihedral angles for syn (S) and anti (A) conformation are
0.0 and 180.0, respectively.

R5

The BDE at 298 K was calculated by using the thermochemical

scheme supplied by Gaussian as in the following equation:
BDE298(R1R2) = [f H298(R1) + f H298(R2)] f H298(R1R2), in which
R1R2 is the neutral molecule and R1 and R2 are the corresponding radicals.49 By following the comprehensive paper of Merrick
et al., zero-point energies are scaled by a factor of 0.9153 at HF/631+G*, and these scaled zero-point vibration energy values are
used for applying corrections to energies evaluated at the MP2/631+G* theoretical level and by 0.9806 at the B3LYP levels.50 Vibrational frequencies for calculating vibrational enthalpy are scaled
by 0.8945 at HF/6-31+G*, and these scaled values are used for the
MP2/6-31+G* theoretical level and by 0.9989 for the B3LYP level.51
The electronic energy of atomic hydrogen atom in DFT calculations is basis set dependent, as can be observed from Jursic
and Martins data (0.50027 hartree for the 6-31G basis set,
0.50216 hartree for the 6-311G basis set, and 0.50226 hartree for
the 6-311++G basis set).52 Pople et al. suggested a high-level correction for bound unpaired electrons and corrected the electronic
energy of the hydrogen atom to 0.50000 hartree in the G2 method.53
DiLabio and Pratt suggested that for the hydrogen atom being a
unique one-electron system, a similar correction should be applied in DFT calculations for the evaluation of BDE by xing the
electronic energy of hydrogen to 0.50000 hartree.54 This has
been found to decrease the deviation of calculated BDEs from
experimental data. The electronic energy of the hydrogen atom is
xed as 0.50000 hartree in the present studies.

H7
N

H6

Syn (Si)

An (Ai)

1 (a)

X1
5H

A-B g A g B g

C2
Y3

Computational details
All of the calculations reported in the present study were carried out using the Gaussian 98 program suite.48 Full geometry
optimizations were performed on each species without any
symmetry constraint at the B3LYP/6-31+G* and MP2/6-31+G*
theoretical levels. Each optimized structure was characterized by
frequency calculations to be a minimum without any imaginary
vibrational frequency. The geometries optimized at the B3LYP/631+G* level have been used to calculate single point energies at the
6-31+G* and 6-311++G** basis sets using restricted open-shell formalism. The CBS-Q composite level has also been used to calculate
the BDEs. The calculations have been performed using the Gaussian 09 program suite.
BDE is calculated as the enthalpy change of the following reaction in the gas phase at 298 K and 1 atm of pressure:

X1

C2
Y3

H
AiSj

SiSj

C
Y

H6

R7
N4

SiAj

H
N

AiAj

1 (b)

Results
Geometries of Y-substituted and N-substituted carbamates
The different conformations for Y-substituted (NH2-C(=X)Y-R)
and N-substituted ((R)(H)NC(=X)YH) carbamates (X, Y = O, S, Se; R =
H, CH3, F, Cl, NH2) have been optimized at the B3LYP/6-31+G* and
MP2/6-31+G* theoretical levels. Scheme 1a depicts the two energy
minima corresponding to syn (Si) and anti (Ai) orientations of
NH2C(=X)Y-R that differ in relative position of R (YR bond) with
respect to the C=X group. Scheme 1b depicts four energy minima, SiSj, AiSj, SiAj, and AiAj, corresponding to orientations of
(R)(H)NC(=X)YH that depict the relative position of NR and YH
bonds with respect to C=X bond. In our earlier reports,55 we observed the syn orientation to be more stable than anti in the case
of carbamic acid and its higher chalcogenide (sulfur, selenium)
analogs in the absence of any substituent. The higher stability of
syn orientation has been assigned to stronger conjugative interactions involving the lone pair of electrons on N, X, and Y and the
C=X bond. The substituents can alter the relative stability of syn
and anti conformers through inductive effect, variation in the
conjugative interactions, and in addition the steric interactions.
With the presence of substituents uorine, chlorine, and NH2 at Y,
the anti orientation is more stable than syn (with the exception of
chlorine (X = S, Y = O) and NH2 (X = S, Y = O)) but with R = CH3, the
syn conformation is relatively more stable for all X, Y = O, S, Se, as
can be seen from Table 1. Of the four optimized orientations for
each nitrogen-substituted molecule, the orientation SiAj is the
most stable when R = F, Cl, NH2 but with R = CH3 (X, Y = O, X = S,
Y = O, S, Se) the SiSj and with R = CH3 (X, Y = Se) the AiAj orientations are the most stable one.
Published by NRC Research Press

Kaur et al.

281

Table 1. The most stable conformation of the Y-substituted NH2C(=X)Y-R and nitrogen-substituted
(R)(H)NC(=X)YH (X, Y = O, S, Se; R = H, CH3, F, Cl, NH2) molecules under study at the MP2/6-31+G*
theoretical level.

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

Molecule

Molecule

R at Y position

Most stable
conformation

O
O
O
S
S
S
Se
Se
Se
O
O
O
S
S
S
Se
Se
Se
O
O
O
S
S
S
Se
Se
Se
O
O
O
S
S
S
Se
Se
O
O
O
S
S
S
Se
Se
Se

O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
O
S
Se
O
S
Se
O
S
Se

Si
Si
Si
Si
Si
Si
Si
Si
Si
Ai
Ai
Ai
Ai
Ai
Ai
Ai
Ai
Ai
Ai
Ai
Ai
Si
Si
Ai
Ai
Ai
Ai
Si
Si
Si
Si
Si
Si
Si
Si
Si
Ai
Ai
Ai
Ai
Ai
Ai
Ai
Ai

Cl

CH3

NH2

R at N position

Most stable
conformation

O
O
O
S
S
S
Se
Se
Se
O
O
O
S
S
S
Se
Se
Se
O
O
O
S
S
S
Se
Se
Se
O
O
O
S
S
S
Se
Se
O
O
O
S
S
S
Se
Se
Se

O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
O
S
Se
O
S
Se
O
S
Se

Si
Si
Si
Si
Si
Si
Si
Si
Si
SiAj
SiAj
SiAj
SiAj
SiAj
SiAj
SiAj
SiAj
AiAj
SiAj
SiAj
SiSj
SiAj
SiAj
SiAj
SiAj
SiAj
SiAj
SiSj
SiAj
SiAj
SiSj
SiSj
SiSj
SiAj
AiSj
SiAj
SiAj
SiAj
SiAj
SiAj
SiAj
SiAj
SiSj
AiAj

Cl

CH3

NH2

Note: i indicates the orientation of Y-R with respect to the C=X group and j indicates the orientation of R-N
with respect to the C=X group.

NH BDEs of H2NC(=X)Y-R (X, Y = O, S, Se) and

(R)(H)NC(=X)YH (X, Y = O, S, Se) molecules
The radicals corresponding to the most stable conformations of
(R)(H)NC(=X)YH and H2NC(=X)Y-R (X, Y = O, S, Se; R = H, F, Cl, CH3,
NH2) molecules have also been optimized at the B3LYP/6-31+G*
and MP2/6-31+G* theoretical levels. The NH BDEs of these
molecules have been evaluated using the ROB3LYP/6-31+G*//
B3LYP/6-31+G* (L1), ROB3LYP/6-311++G(d,p)//B3LYP/6-31+G* (L2),
UMP2/6-311++G(d,p)//MP2/631+G* (L3), and CBS-Q (L4) theoretical
levels and are reported in Tables 2 and 3. The BDEs obtained using
DFT method ROB3LYP/6-311++G(d,p)//B3LYP/6-31+G* are higher
than the values obtained with the MP2/6-311++G(d,p)//MP2/631+G* method. The NH BDE of H2N-C(=O)OH (113.42 kcal/mol at
the L2 theoretical level) is higher than that of NH3 (107.3 kcal/mol
at the L2 theoretical level) but for H2N-C(=X)OH (X = S, Se), the NH

BDE is 4.16 and 11.40 kcal/mol, respectively, lower than that of

NH3. The comparison of BDEs for NH2C(=X)-OH (X = O, S, Se) molecules at the L2 theoretical level with those in the respective
amides shows that the NH BDE for X = O is lower (by 1.08 kcal/
mol), while the BDEs with X = S, Se are higher (1.58 and 3.23 kcal/
mol, respectively) relative to the corresponding NH BDEs of
amides at the L2 theoretical level.56 The NH BDE in carbamic acid
and its thio- and seleno- analogs decreases in the order of X as
O > S > Se for each Y = O, S, Se and in the order of Y as O > S > Se
for each X = O, S, Se. The variation in NH BDE is higher in the case
of charge in chalcogen at position X than in the case of change at
position Y. The trends in NH BDEs in the order of X and Y remain
unchanged with the presence of substituents at nitrogen and Y.
The data in Table 2 reect the decrease in NH BDEs of nitrogensubstituted carbamates with the presence of substituents uorine,
Published by NRC Research Press

282

Can. J. Chem. Vol. 93, 2015

Table 2. NH bond dissociation enthalpies (kcal/mol) for (R)(H)NC(=X)YH (X, Y = O, S, Se; R = H, F, Cl,
CH3, NH2) at the ROB3LYP/6-31+G*//B3LYP/6-31+G* (L1), ROB3LYP/6-311++G(d,p)//B3LYP/6-31+G* (L2), and
UMP2/6-311++G(d,p)// MP2/6-31+G(d,p) (L3) theoretical levels.
L1

L3

Y=O

Y=S

Y = Se

Y=O

Y=S

Y = Se

Y=O

Y=S

Y = Se

O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se

109.46
98.79
94.67
91.67
81.76
81.92
94.48
87.79
82.20
104.39
97.54
93.56
78.17
76.36
76.56

107.20
94.80
90.16
89.92
88.82
75.58
94.04
85.06
79.96
100.94
94.33
88.68
75.85
72.74
72.38

106.94
92.94
87.32
89.36
80.69
74.05
89.50
82.88
76.92
98.68
94.60
85.58
76.36
72.31
70.43

113.42
103.14
95.90
103.60
84.97
78.16
97.51
90.47
83.60
107.05
100.13
92.44
80.62
78.61
78.54

113.36
97.22
90.17
92.99
91.52
75.99
94.03
87.58
80.73
103.93
96.40
88.65
78.36
74.87
74.23

111.79
92.77
86.13
92.14
82.69
75.78
93.04
83.59
77.50
103.17
97.15
85.22
79.81
74.24
72.49

112.08
98.38
92.07
94.14
84.90
75.07
98.16
91.72
77.60
106.86
104.30
79.71
79.71
78.04
78.49

111.22
94.67
84.04
94.84
83.75
73.99
97.06
86.03
75.60
103.71
91.90
82.31
78.55
77.80
83.49

110.58
92.39
83.75
94.16
79.81
77.32
97.60
79.96
76.27
103.22
94.07
84.14
80.04

Cl

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

L2

CH3
NH2

81.02

Table 3. NH bond dissociation enthalpies (kcal/mol) for Y-substituted carbamates H2NC(=X)Y-R (X,
Y = O, S, Se; R = H, F, Cl, CH3, NH2) at the ROB3LYP/6-31+G*//B3LYP/6-31+G* (L1), ROB3LYP/6-311++G(d,p)//
B3LYP/6-31+G* (L2), and UMP2/6-311++G(d,p)// MP2/6-31+G(d,p) (L3) theoretical levels.
L1

L2

L3

Y=O

Y=S

Y = Se

Y=O

Y=S

Y = Se

Y=O

Y=S

Y = Se

O
S
Se
O
S
Se
O
S
Se
O
S
Se
O
S
Se

109.46
98.79
94.67
114.07
103.49
99.32
108.51
96.55
91.64
109.60
95.54
86.82
109.73
95.61
89.38

107.20
94.80
90.16
109.40
108.32
94.09
108.61
99.01
94.09
106.92
96.24
89.03
111.49
95.50
92.20

106.94
92.94
87.32
112.92
96.64
91.91

113.42
103.14
95.90
127.37
106.45
101.49
111.39
99.08
95.17
112.24
97.69
92.47
112.27
97.60
89.37

113.36
97.22
90.17
115.59
103.70
94.59
111.41
101.46
94.09
109.86
97.82
88.81
114.30
95.63
91.95

111.79
92.77
86.13
116.62
97.20
101.49

112.08
98.38
92.07
127.18
97.48
107.04
107.26
92.01
82.14
115.93
92.41
88.48
112.24
92.17
82.81

111.22
94.67
84.04
115.58
100.47
124.90
110.87
100.21
90.34
109.80
93.26
87.82
112.60
94.95
85.26

110.58
92.39
83.75
134.30
109.77
95.14

Cl

CH3
NH2

97.13
92.46
105.75
93.29
87.97
95.31
91.79

Fig. 1. Trends in NH bond dissociation enthalpies (BDE) of

(R)(H)NC(=X)YH (X = O, S, Se; Y = O, S, Se; R = H, CH3, NH2, Cl, F) at
the ROB3LYP/6-311++G(d,p)//B3LYP/6-31+G* theoretical level.

97.72
91.75
108.35
92.37
87.98
95.75
90.82

97.62
118.88
101.97
97.53
88.45
121.06
91.66

Fig. 2. Trends in NH bond dissociation enthalpies (BDE) of

H2NC(=X)Y-R (X = O, S, Se; Y = O, S, Se; R = H, F, Cl, CH3, NH2) at the
ROB3LYP/6-311++G(d,p)//B3LYP/6-31+G* theoretical level.

Published by NRC Research Press

Kaur et al.

283

Table 4. Molecule stabilization effect (ME) (kcal/mol), radical stabilization effect (RE) (kcal/mol), and total stabilization
effect (RSE) (kcal/mol) for nitrogen-substituted carbamic acid (R)(H)NC(=X)YH (X, Y = O, S, Se; R = F, Cl, CH3, NH2) at the
ROB3LYP/6-31+G*//B3LYP/6-31+G* theoretical level.
BDE

Y=S

Y = Se

Y=O

Y=S

Y = Se

ME

RE

TSE

ME

RE

TSE

ME

RE

TSE

O
S
Se
O
S
Se
O
S
Se
O
S
Se

17.79
17.03
12.75
14.98
11.00
12.47
5.07
1.25
1.11
31.29
22.43
18.11

17.28
6.79
14.58
13.16
9.74
10.20
6.26
0.47
1.48
31.35
22.06
17.78

17.58
12.25
13.27
17.44
10.06
10.40
8.26
1.66
1.74
30.58
20.63
16.89

11.16
13.72
9.92
0.98
8.46
5.67
0.02
0.88
9.51
0.81
0.59
2.88

7.10
6.70
2.83
5.17
2.54
6.97
5.10
2.13
4.34
30.49
23.79
20.99

18.26
17.02
12.75
14.97
10.99
12.64
5.08
1.25
5.16
31.30
23.20
18.11

8.97
6.49
5.70
8.59
6.68
4.68
0.84
0.88
2.14
0.38
1.37
3.45

8.36
0.11
8.88
4.67
3.07
5.51
5.47
1.36
3.65
31.48
24.28
19.26

17.32
6.38
14.58
13.26
9.75
10.19
6.31
0.48
1.51
31.10
22.91
16.02

7.04
4.71
4.35
6.00
4.95
2.40
0.06
1.92
3.62
3.09
2.79
4.64

10.54
7.53
8.92
11.18
5.49
8.00
8.34
0.27
5.60
33.31
25.54
21.53

17.58
12.24
13.27
17.18
10.44
10.40
8.28
1.65
1.98
30.21
22.75
16.89

Cl

CH3

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

Y=O

NH2

te: BDE = BDEH2NC(=X)YH BDE(R)(H)NC(=X)YH.

Table 5. Molecule stabilization effect (ME) (kcal/mol), radical stabilization effect (RE) (kcal/mol), and total stabilization
effect (TSE) (kcal/mol) for H2N-C(=X)YR (X, Y = O, S, Se; R = H, F, Cl, CH3, NH2) molecules at the ROB3LYP/6-31+G*//B3LYP/
6-31+G* theoretical level.
BDE

Y=O

Y=S

Y = Se

Y=O

Y=S

Y = Se

ME

RE

TSE

ME

RE

TSE

ME

RE

TSE

O
S
Se
O
S
Se
O
S
Se
O
S
Se

4.61
5.70
4.65
0.95
2.24
3.03
0.14
3.25
7.85
0.27
3.18
5.29

2.20
13.52
3.93
1.41
4.21
3.93
0.28
1.44
1.13
4.29
0.70
2.04

5.98
3.70
4.59

4.19
5.14
1.19
0.35
0.65

2.37
4.47

1.44
4.50
9.48
5.36
2.02
3.39
2.00
1.50
2.72
1.11
1.62
1.01

5.79
0.21
4.84
4.41
0.20
6.24
2.84
4.98
9.01
1.37
1.55
6.30

4.35
4.71
4.64
0.95
2.22
2.85
0.84
3.48
7.83
0.26
3.17
5.29

6.88
12.09
13.56
4.03
8.84
10.82
3.32
4.08
5.20
6.74
9.38
10.32

4.72
1.42
9.62
4.24
4.64
7.64
3.66
2.66
6.32
2.49
8.68
8.29

2.16
13.51
3.94
1.36
4.20
3.18
0.34
1.42
1.12
4.25
0.70
2.03

6.61
10.53
14.26

8.12
12.37
2.36
2.36
3.79

0.62
6.83
9.67

3.93
7.22
3.23
2.01
3.15

5.99
3.70
4.59

4.19
5.15
1.20
0.35
0.64

7.59
10.88

5.22
6.42

2.37
3.46

Cl

CH3
NH2

te: BDE = BDENH2C(=X)YH BDENH2C(=X)YR.

Fig. 3. Trends in molecular stabilization energies (ME) of

(R)(H)NC(=X)YH (X = O, S, Se; Y = O, S, Se; R = H, CH3, NH2, Cl, F) at
the ROB3LYP/6-31+G*//B3LYP/6-31+G* theoretical level.

Fig. 4. Trends in molecular stabilization energies (ME) of

H2NC(=X)Y-R (X = O, S, Se; Y = O, S, Se; R = H, CH3, NH2, Cl, F) at the
ROB3LYP/6-31+G*//B3LYP/6-31+G* theoretical level.

chlorine, CH3, and NH2 at nitrogen relative to H2NC(=X)YH (X,

Y = O, S, Se). The largest decrease in NH BDE with substitution at
nitrogen is indicated in the case of R=NH2. As can be observed
from the table, the variation in NH BDE as the result of substitution is higher with change in X from oxygen to sulfur or selenium.
The variations in NH BDEs with the presence of substituents at
position Y are relatively smaller in comparison with the variations with substituents at nitrogen (see Tables 2 and 3). There is

an increase in NH BDE with the presence of highly electronegative substituent uorine at Y but the increase in BDE with the
substituents NH2 and Cl is reected only for molecules with X,
Y = S, Se in H2NC(=X)YR molecules (Table 3). The decrease in
NH BDE results in H2NC(=X)YR (R = Cl, NH2 with X = O, S, Se
and with Y = O) molecules. There is negligible to small variation
in NH BDEs in H2NC(=X)YCH3 (X, Y = O, S, Se) relative to
H2NC(=X)YH.
Published by NRC Research Press

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

284

Can. J. Chem. Vol. 93, 2015

The substituents at position Y in the molecules are at position

to the NH bond; therefore, their effect on NH BDE is expected to
be small. However, the signicant variation in NH BDE due to the
presence of the highly electronegative uorine substituent at the
Y position suggests the importance of substituents at the position also. As can be seen from the Table 2, the NH BDEs in
(R)(H)NC(=X)YH (X = O; Y = O, S, Se) decrease in the order
H > CH3 > Cl > F > NH2, while with (X = S; Y = O, S, Se), these
decrease in the order H > CH3 > Cl > F > NH2 and for (X = Se; Y = O,
S, Se) decrease follows the order H > CH3 > Cl > F > NH2. In Figs. 1
and 2, plots indicating the trends in NH BDEs with substitution
of (R)(H)NC(=X)YH and NH2C(=X)YR (X = O, S, Se; Y = O, S, Se)
molecules by uorine, chlorine, CH3, and NH2 substituents are
depicted. These plots reect that the substituent effect is more
pronounced in nitrogen-substituted relative to the Y-substituted
molecules and the substituent effect is not operative through
inductive effect only. In contrast with NH2C(=X)YR molecules, the
trend with respect to various substituents does not differ much in
the case of (R)(H)NC(=X)YH molecules for all of the possibilities of
X = O, S, Se; Y = O, S, Se. The variation in NH BDE as the result of
substitution is evaluated as
BDE BDENH2C(X)YH BDENH2C(X)YR or (R)(H)NC(X)YH

Fig. 5. Trends in relative stabilization energies (RE) of

(R)(H)NC(=X)YH (X = O, S, Se; Y = O, S, Se; R = H, CH3, NH2, Cl, F) at
the ROB3LYP/6-31+G*//B3LYP/6-31+G* theoretical level.

Fig. 6. Trends in relative stabilization energies (RE) of H2NC(=X)Y-R

(X = O, S, Se; Y = O, S, Se; R = H, CH3, NH2, Cl, F) at the ROB3LYP/631+G*//B3LYP/6-31+G* theoretical level.

The values for BDE for (R)(H)NC(=X)YH and H2NC(=X)YR (X = O, S,

Se; Y = O, S, Se) molecules are given in Tables 4 and 5, respectively.
The data in Tables 4 and 5 show that the highest BDE in
(R)(H)NC(=X)Y (X = O, S, Se; Y = O, S, Se) is reected by R = NH2,
while in the case of H2NC(=X)YR (X = O, S, Se; Y = O, S, Se), the
variation is largest for R = F.
Substituent effect on the stability of the molecule and
radical
Since the variation in BDE is the result of the effect of the
substituent on the relative stability of the molecule and the radical, to understand the role of substitution on the stability of the
two species, the molecule stabilization energy (ME) and radical
stabilization energy (RE) have been evaluated. The ME and RE for
(R)(H)NC(=X)YH are evaluated as the enthalpy changes associated
with the isodesmic reactions 1 and 2, respectively:

(1)

(2)

The ME and RE values for (R)(H)NC(=X)YH (X, Y = O, S, Se; R = H, F,

Cl, CH3, NH2) are reported in Table 4 at the ROB3LYP/6-31+G*//
B3LYP/6-31+G* theoretical level. Positive ME values, as dened
here, denote greater stability of the molecule relative to H2NC(=X)YH
and contribute to an increase in BDE. Positive RE values indicate greater stability of the radical relative to the unsubstituted
reference radical species NH.C(=X)YH and contribute to a decrease in BDE. The stabilization of molecules and their respective radicals can be rationalized in terms of electronic and
steric factors. The electronic factors result from the change in
electron delocalization, change in ionic and covalent character
of bonds, and additional noncovalent interactions like the hydrogen bond if any.
Table 4 lists the ME and RE values for (R)(H)NC(=X)YH (X, Y = O,
S, Se; R = H, F, Cl and NH2) molecules and their respective radicals.

ME values for (R)(H)NC(=X)YH molecules with R = F, Cl are negative, suggesting destabilization of the molecules with substitution, while with R = CH3, NH2; X, Y = O, S, Se, positive ME values
(with two exceptions) reect stabilization of the molecule by such
substitutions. The range of ME values in (R)(H)NC(=X)YH molecules when X = O, S, Se and Y = O is from 13.72 to 9.51 kcal/mol.
The ME values range from 8.97 to 3.45 kcal/mol when X = O, S, Se
and Y = S and from 7.04 to 4.64 kcal/mol when X = O, S, Se and Y =
Se. The strongest destabilization effect is reected by substitution
of uorine at the nitrogen in (R)(H)NC(=X)YH molecules.
The positive RE values for the radicals (R)NC(=X)YH (X, Y = O, S,
Se; R = F, Cl, CH3, NH2) indicate a stabilizing effect of the substituent on the stability of the radical and it tends to lower the BDE.
The magnitude of the RE value is higher than |ME| in nearly 70% of
the radicals under study. The largest RE values are evaluated for
R = NH2 for all X and Y. The RE values of (R)NC(=X)YH radicals
when X = O, S, Se and Y = O range from 2.13 to 30.39 kcal/mol. The
RE values range from 0.11 to 31.48 kcal/mol when X = O, S, Se and
Y = S and from 0.27 to 33.31 kcal/mol when X = O, S, Se and Y = Se.
The ME and RE in H2NC(=X)Y-R molecules are evaluated employing the following isodesmic reactions:

(3)

Published by NRC Research Press

Kaur et al.

285

Table 6. Important lone pair occupancies on different atoms in (R)(H)NC(=X)YH and H2NC(=X)YR (X = O, S, Se; Y = O, (S), [Se]; R = F, Cl, CH3, NH2)
molecules at the MP2/6-31+G* theoretical level.
(R)(H)NC(=O)YH

(R)(H)NC(=S)YH

H2NC(=S)YR

(R)(H)NC(=Se)YH

H2NC(=Se)YR

(O)

(Y)

(N)

(O)

(Y)

(N)

(S)

(Y)

(N)

(S)

(Y)

(N)

(Se)

(Y)

(N)

(Se)

(Y)

(N)

1.87
(1.87)
[1.87]
1.87
(1.87)
[1.87]
1.87
(1.87)
[1.86]
1.88
(1.87)
[1.87]
1.87
(1.87)
[1.86]

1.90
(1.91)
[1.93]
1.87
(1.87)
[1.89]
1.88
(1.89)
[1.92]
1.90
(1.91)
[1.92]
1.90
(1.91)
[1.91]

1.83
(1.82)
[1.80]
1.90
(1.90)
[1.90]
1.87
(1.86)
[1.85]
1.79
(1.77)
[1.77]
1.79
(1.78)
[1.80]

1.87
(1.87)
[1.87]
1.84
(1.86)
[1.86]
1.85
(1.86)
[1.86]
1.87
(1.88)
[1.87]
1.87
(1.88)

1.90
(1.91)
[1.93]
1.92
(1.90)
[1.91]
1.92
(1.91)
[1.92]
1.87
(1.88)
[1.91]
1.89
(1.90)

1.83
(1.82)
[1.80]
1.79
(1.78)
[1.78]
1.81
(1.79)
[1.78]
1.84
(1.83)
[1.81]
1.83
(1.79)

1.88
(1.89)
[1.88]
1.87
(1.88)
[1.88]
1.87
(1.88)
[1.87]
1.88
(1.89)
[1.88]
1.88
(1.88)
[1.88]

1.88
(1.88)
[1.90]
1.85
(1.83)
[1.85]
1.86
(1.85)
[1.87]
1.88
(1.89)
[1.90]
1.88
(1.87)
[1.89]

1.76
(1.85)
[1.75]
1.87
(1.87)
[1.87]
1.81
(1.82)
[1.77]
1.72
(1.71)
[1.71]
1.73
(1.73)
[1.73]

1.88
(1.89)
[1.88]
1.82
(1.85)
[1.85]
1.86
(1.85)
[1.84]
1.89
(1.89)
[1.88]
1.88
(1.88)
[1.88]

1.88
(1.88)
[1.90]
1.90
(1.86)
[1.87]
1.90
(1.88)
[1.89]
1.85
(1.85)
[1.87]
1.89
(1.87)
[1.89]

1.76
(1.85)
[1.75]
1.73
(1.73)
[1.72]
1.78
(1.73)
[1.75]
1.78
(1.78)
[1.75]
1.75
(1.73)
[1.72]

1.90
(1.91)
[1.90]
1.88
(1.90)
[1.89]
1.89
(1.89)
[1.89]
1.90
(1.91)
[1.90]
1.90
(1.91)
[1.90]

1.88
(1.87)
[1.88]
1.84
(1.82)
[1.83]
1.86
(1.85)
[1.86]
1.87
(1.86)
[1.89]
1.88
(1.88)
[1.87]

1.81
(1.74)
[1.74]
1.86
(1.86)
[1.86]
1.76
(1.75)
[1.78]
1.71
(1.69)
[1.69]
1.72
(1.71)
[1.71]

1.90
(1.91)
[1.90]
1.88
(1.85)
[1.84]
1.86
(1.85)
[1.84]
1.90
(1.90)
[1.90]
1.89
(1.90)
[1.89]

1.88
(1.87)
[1.88]
1.91
(1.84)
[1.85]
1.89
(1.86)
[1.87]
1.85
(1.84)
[1.86]
1.88
(1.86)
[1.88]

1.81
(1.74)
[1.74]
1.75
(1.71)
[1.70]
1.73
(1.71)
[1.70]
1.75
(1.74)
[1.74]
1.73
(1.71)
[1.70]

Cl

CH3

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

H2NC(=O)YR

NH2

Table 7. Lone pair occupancies on X and N of (R)NC(=X)YH (X, Y = O, (S), [Se]; R = H, F, Cl, CH3, NH2)
radicals at the MP2/6-31+G* theoretical level.
(R)NC(=O)YH

(R)NC(=S)YH

(R)NC(=Se)YH

1(N)

1(N)

1(N)

2(N)

2(S)

2(Se)

0.99
(0.99)
[0.99]
0.99
(0.99)
[0.99]
0.97
(0.97)
[0.97]
0.98
(0.98)
[0.98]
0.96
(0.96)
[0.95]
0.99
(0.99)
[0.98]

0.99
(0.99)
[0.99]
0.98
(0.99)
[0.99]
0.95
(0.95)
[0.95]
0.97
(0.97)
[0.97]
0.97
(0.97)
[0.97]
0.99
(0.99)
[0.98]

0.95
(0.97)
[0.95]
0.95
(0.95)
[0.95]
0.94
(0.94)
[0.94]
0.89
(0.88)
[0.88]
0.96
(0.96)
[0.96]
0.94
(0.94)
[0.92]

0.98
(0.98)
[0.98]
0.98
(0.98)
[0.98]
0.96
(0.96)
[0.95]
0.97
(0.97)
[0.96]
0.96
(0.97)
[0.97]
0.98
(0.98)
[0.98]

0.98
(0.98)
[0.98]
0.98
(0.97)
[0.98]
0.96
(0.96)
[0.95]
0.97
(0.97)
[0.96]
0.97
(0.97)
[0.97]
0.98
(0.97)
[0.98]

0.98
(0.98)
[0.98]
0.98
(0.98)
[0.97]
0.95
(0.95)
[0.93]
0.97
(0.97)
[0.97]
0.97
(0.97)
[0.97]
0.98
(0.98)

0.98
(0.98)
[0.98]
0.97
(0.98)
[0.97]
0.95
(0.95)
[0.94]
0.97
(0.97)
[0.96]
0.97
(0.97)
[0.96]
0.98
(0.98)

0.96
(0.96)
[0.96]
0.95
(0.96)
[0.96]
0.89
(0.92)
[0.92]
0.89
(0.92)
[0.92]
0.91
(0.90)
[0.90]
0.96
(0.96)

0.95
(0.95)
[0.95]
0.96
(0.95)
[0.94]
0.96
(0.95)
[0.97]
0.84
(0.82)
[0.93]
0.91
(0.90)
[0.89]
0.93
(0.89)
[0.95]

Cl

CH3
NH2
NO2
OH

(4)

The ME and RE values for the H2N-C(=X)YR molecules are recorded

in Table 5. As can be seen from the table, the ME values are
positive for X = S, Se and Y = O, S, Se in H2N-C(=X)YR molecules
with R = F, Cl, CH3, NH2 with two exceptions, while negative ME
values result in the case of X = O and Y = O with all four substituents. The molecular stabilization resulting from these substituents present at Y in H2N-C(=X)YR with X = S, Se and Y = O, S, Se
shows the effect in the increase in NH BDE of the substituent.
The presence of substituents at position Y of the radicals H2NC(=X)YR stabilizes the respective radical with respect to the unsubstituted counterpart with the exception of R = F, Cl, NH2 with
X = O and Y = O. The magnitude of RE values is less than |ME| in a
large number of cases. The RE values are lower in comparison
with respective values for nitrogen-substituted radicals. The RE
values of HNC(=X)YR radicals when X = O, S, Se and Y = O range
from 5.79 to 10.55 kcal/mol. The RE values range from 1.42 to

9.62 kcal/mol when X = O, S, Se and Y = S and from 0.62 to

9.67 kcal/mol when X = O, S, Se and Y = Se. The trends of variation
in ME and RE values of (R)(H)NC(=X)YH and H2NC(=X)Y-R (X, Y = O,
S, Se; R = H, F, Cl, CH3, NH2) molecules are depicted in Figs. 36.
As the positive ME tends to enhance the BDE, while positive RE
favors a decrease in BDE, the total stabilization effect (RE ME)
gives the expected change in BDE. The comparison of the total
stabilization effect with BDE (as dened earlier) shows a perfect
match between the two in most of the cases with three exceptions
where only small deviations have been observed. The BDE values
are higher in the case of nitrogen-substituted carbamates than of
Y-substituted carbamates.

Discussion
Electron delocalization and ME
Our earlier results on the stability of carbamic acid indicated
the role of extended conjugation resulting from electron delocalization of lone pairs of electrons present on nitrogen, X, and Y.55
The substituents at the nitrogen or Y position can alter the electron delocalization. To explore the variation in electron delocalPublished by NRC Research Press

= 0.94(), 0.72(); (N5) = 1.00().

= [0.77].
b(Cl)

NH2

CH3

Cl

a(N4)

2(Se)

0.97
(0.95)
[0.95]
0.96
(0.97)
[0.97]
0.96
(0.97)
[]
0.97
(0.98)
[0.97]
0.96
(0.95)
[0.97]
0.97, 0.97
(0.97) (0.95)
[0.96] [0.95]
0.95, 0.96
(0.95) (0.97)
[0.95] [0.97]
0.96, 0.96
(0.96), (0.97)
[0.94], []
0.96, 0.97
(0.95), (0.98)
[0.94], [0.97]
0.96, 096
(0.96), (0.95)
[0.94], [0.97]

1(N) ,
(Y) ,

0.94, 0.97
(0.97), (0.96)
[0.96] [0.96]
0.96, 0.98
(0.92), (0.94)
[0.95], [0.97]
0.94, 0.97
(0.94) (0.96)
[0.97] []
0.92, 0.96
(0.94), (0.96)
[0.95], [0.95]
0.94, 0.94
(0.95), (0.95)
[0.95], [0.96]
0.98, 0.98
(0.99), (0.95)
[0.98], [0.95]
0.98, 0.97
(0.98), (0.96)
[0.97], [0.97]
0.97, 0.97a
(0.97), (0.97)
[0.93], [0.95]
0.98, 0.98
(0.99), (0.98)
[0.99], [0.97]
0.98, 0.95
(0.98), (0.95)
[0.99], [0.97]

(Se) ,
2(S)

0.95
(0.95)
[0.95]
0.95
(0.96)
[0.94]
0.95
(0.96)
[0.95]
0.96
(0.97)
[0.94]
0.95
(0.97)
[0.86]
0.96, 0.96
(0.97), (0.96)
[0.96], [0.96]
0.96, 0.95
(0.96), (0.96)
[0.96], [0.96]
0.96, 0.95
(0.96), (0.96)
[0.96], [0.96]
0.95, 0.95
(0.95), (0.95)
[0.96], [0.96]
0.96, 0.95
(0.94), (0.95)
[0.98], [0.95]

1(N) ,
(Y) ,

0.95, 0.95
(0.96), (0.96)
[0.96], [0.96]
0.96, 0.99
(0.93), (0.96)
[0.96], [0.96]
0.95, 0.95
(0.94), (0.97)
[0.96], [0.96]
0.94, 0.94
(0.99), (0.99)
[0.98], [0.93]
0.94, 0.94
(0.95), (0.97)
[0.86], []
0.98, 0.94
(0.98), (0.94)
[0.98], [0.94]
0.98, 0.95
(0.97), (0.96)
[0.98], [0.93]
0.98, 0.95
(0.97), (0.97)
[0.98], [0.94]
0.98, 0.96
(0.98), (0.98)
[0.98], [0.92]
0.98, 0.94b
(0.98), (0.98)
[0.92], [0.93]

(S) ,
1(N) ,

0.98, 0.96
(0.98), (0.98)
[0.96], [0.98]
0.97, 0.96
(0.98), (0.98)
[0.98], []
0.98, 0.96
(0.98), (0.98)
[], []
0.98, 0.97
(0.98), (0.96)
[0.99], [0.98]
0.98, 0.97
(0.98), (0.96)
[], []
0.94, 0.94
(0.94), (0.94)
[0.95], [0.95]
0.96, 0.96
(0.93), (0.92)
[0.94], [0.95]
0.95, 0.95
(0.94), (0.94)
[], []
0.92, 0.93
(0.93), (0.92)
[0.93], [0.93]
0.93, 0.93
(0.94), (0.94)
[], []

(Y) ,

0.95
(0.95)
[0.96]
0.96
(0.94)
[0.82]
0.95
(0.94)
[]
0.95
(0.95)
[0.94]
0.95
(0.95)
[]

(O) ,

0.94, 0.93
(0.94), (0.94)
[0.94], [0.93]
0.93, 0.92
(0.93), (0.93)
[0.97], [0.88]
0.94, 0.92
(0.93), (0.93)
[], []
0.94, 0.93
(0.94), (0.94)
[0.94], [0.94]
0.94, 0.93
(0.94), (0.94)
[], []

2(N)

HNC(=S)YR

Electron delocalization and RE

The E(2) values from NBO analysis (Tables S7S12) of radicals
(R)NC(=X)YH (X, Y = O, S, Se; R = H, F, Cl, CH3, NH2) suggest that on
radical formation, nN *CO/*CO delocalization decreases or is
absent, which is understandable in terms of the presence of an
unpaired electron at the nitrogen restricting the delocalization of
the lone pair of electrons of the nitrogen. The E(2) values for nX
*CN and nX *CY electron delocalization in the radicals
(R)NC(=X)YH (X,Y = O, S, Se) reect only small variation with
substituents. This is supported by the lone pair occupancies listed
in Tables 7 and 8. In the radicals of molecules (R)(H)NC(=X)YH (X =
S, Se; Y = O, S, Se), the orbital interactions nX *CY,nN *CS,
and nY *CX are absent, while nY *CN becomes operative
with the exception of R = NH2. The molecular orbitals in the NBO
analysis suggest the formation of a CN bond in (R)NC(=X)YH
(X = S, Se; Y = O, S, Se) that is absent in the case of (R)NC(=X)YH
radicals with X = O.
The energy of unpaired electron at the nitrogen matches the
energy of the CO molecular orbital, thereby indicating the
probability of stabilization of the radical center through interaction of the unpaired electron with the electron, thereby resulting in positive RE values for RNC(=O)H radicals. Indeed, the C2O1
bond is strengthened upon radical formation. In the case of
(R)NC(=X)YH (X = S, Se; Y = O, S, Se) radicals, the molecular orbital
analysis indicates the shift of the radical center to X and the
presence of a CN bond in place of a CX bond in the respective molecules. The geometrical parameters also support the inference.

HNC(=O)YR

ization as a result of nitrogen and Y substitution, NBO analysis of

all of the molecules under study has been carried out at the MP2/
6-31+G* theoretical level.57 Important lone pair occupancies of
nitrogen- and Y-substituted carbamates are listed in Table 6 and
second-order stabilization energy E(2) values for different electron
delocalizations are reported in the supplementary data (Tables S1
S6) (see Supplementary material section). The E(2) values for nN
*CX, nN *CX, nX *CN, and nY *CX orbital interactions
reect the importance of conjugative interactions in the carbamic
acid molecule and its thio and seleno analogs. The nN *CX and
nY *CX interactions involve a shift of electron density to the
same acceptor orbital; with the change in X from oxygen to selenium through sulfur, there is increase in E(2) values for both the
types of interactions. The trend can be rationalized in terms of
larger size and polarizability of the chalcogen atom.
The electron delocalization can also be depicted from the lone
pair occupancies (N) in Table 6. As can be seen from the table, the
lone pair of electrons present at the nitrogen is the most delocalized. The (N) increases in the order of X as O > S > Se in the
nitrogen-substituted molecules. There is decrease in (N) with CH3
and NH2 as substituent, while there is relative increase in (N)
with R = F, Cl, suggesting an increase in electron delocalization
with R = CH3 and NH2 and a decrease in electron delocalization of
the lone pair of electrons present at the nitrogen in the latter.
There is negligible to small change in (X) with substitution
at the nitrogen but (Y) undergoes a decrease in the case of R = F, Cl.
These variations along with ME values explain that ME variations
arise as a result of change in conjugative interactions. The lone
pair occupancies of the H2NC(=X)YR molecules also reect the
variation in conjugative interactions arising as a result of substitution at position Y. In spite of the presence of substituents at
position Y, the lone pair occupancy of nitrogen is decreased further. In the case of R = F, X = S, and Y = O, S, Se, the lone pairs
present at the sulfur are also further delocalized, thereby stabilizing the molecule. In the case of X = Se, Y = O, S, Se, and R = F, all of
the lone pairs of electrons present at X, Y, and nitrogen undergo a
decrease, thereby resulting in the highest ME values in these molecules.

Can. J. Chem. Vol. 93, 2015

Table 8. Lone pair occupancies on oxygen, Y, and nitrogen atoms for HNC(=X)YR (X, Y = O, (S), [Se]; R = H, F, Cl, CH3, NH2) radicals at the MP2/6-31+G* theoretical level.

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

286

Published by NRC Research Press

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

Kaur et al.

In the case of HNC(=O)YR radicals, there is a considerable decrease in nN *CX delocalization on radical formation in all of
these substituted carbamates, as indicated by the E(2) values, while
an increase in E(2) values of nY *CX delocalization is observed
on radical formation. The new orbital interaction nY *CN
arises on radical formation in Y-substituted molecules also. Other
orbital interactions undergo only small variations. This is reected by the lone pair occupancies.
The occupancies of some important and spin orbitals of the
radicals are reported in Tables 7 and 8. The analysis of occupancies
of and spin orbitals of the radicals indicate that the unpaired
electron resides at the nitrogen atom with X = O but is at X in the
case of X = S or Se. Thus, the positive RE values in (R)NC(=X)YH (X =
S, Se; Y = O, S, Se) can be rationalized in terms of difference in
stability of the CN bond and CX bond. The extraordinarily
high RE value of R = NH2 in the case of X, Y = O, S, Se results as the
lone pair of electrons present on the substituent nitrogen interact
with the unpaired radical center on the nitrogen in RN()C(=O)YH,
thereby stabilizing the radical considerably.
The decrease in NH BDE of R(H)NC(=X)YH with X, Y = O, S, Se
and R = F, Cl arises with respect to unsubstituted H2NC(=X)YH
because of decreasing molecular stability and increasing radical
stability With R = CH3, NH2, it is mainly the increase in radical
stability that causes the decrease in NH BDE.
On the contrary, with the substitution at Y, the variations in
NH BDEs are smaller with respect to unsubstituted H2NC(=X)YH.
With Y = S, Se and X = O, S, Se and Y = O and X = S, Se, both ME and
RE values are positive but the magnitude of RE is lower than that
of ME in most of the cases, hence causing an increase in BDE.

Conclusions
BDE is considered to be representative of bond strength. The
present study highlights the role of substituents on the relative stability of a molecule and the corresponding radical in
(R)(H)NC(=X)YH and NH2C(=X)Y-R molecules. The following factors
are observed to contribute towards the NH BDEs: (i) variation in
electron delocalization as the result of stabilization in the
molecules and radicals, (ii) change in hybridization upon radical
formation, (iii) reorganization of the geometry upon radical formation, (iv) unpaired electron delocalization through conjugative
and inductive effects, and (v) shift of the radical center.
Important observations in the present study are:
(1) In nitrogen-substituted or Y-substituted carbamates, the NH
BDE decreases in the order of X as O > S > Se for each value of
Y. The NH BDEs follow the same trend with change in Y from
O to S and Se but the magnitude is comparatively smaller in
comparison with that with X.
(2) The effect of substituent on NH BDE is more pronounced
when the substituent is present at the nitrogen in R(H)NC(=X)YH
molecules. The change in NH BDE does not follow any trend
with electronegativity of the substituent, indicating the role
of several factors rather than only the inductive effect.
(3) The molecule stabilization energy as the result of substitution
at the nitrogen can be rationalized in terms of variation in
electron delocalization of the lone pairs of electrons present
at X, Y, and nitrogen.
(4) The change in molecular stabilization using isodesmic reactions (ME) suggests destabilization in molecules R(H)NC(=X)YH
(X, Y = O, S, Se; R = F, Cl), while stabilization results in molecules R(H)NC(=X)YH (X, Y = O, S, Se; R = CH3, NH2). The RE
values reect stabilization of radicals for each X, Y, and R.
Thus, the decrease in BDE in the case of R = CH3, NH2 is dueto
enhanced radical stabilization, while for R = F, Cl, both ME
and RE contribute to the decrease in BDE.
(5) For H2NC(=X)YR molecules, stabilization resulted with all the
four substituents when X, Y = S, Se X = O Y = S, Se but ME
values are lower in magnitude in comparison with the values

287

in the case of R(H)NC(=X)YH molecules. The RE values for the

radicals (H)NC(=X)YR (X, Y = O, S, Se; R = F, Cl, CH3, NH2) also
reect stabilization. As the combined effect of ME and RE, the
BDE values are increased for R = F, Cl with few exceptions.
(6) The NBO analysis helped in rationalizing the ME and RE values in terms of change in electron delocalization, shift in the
radical center, and stabilization resulting as interaction of an
unpaired electron with the substituent.

Supplementary material
Supplementary material is available with the article through the
journal Web site at http://nrcresearchpress.com/doi/suppl/10.1139/
cjc-2014-0326. Supplementary information includes second-order
delocalization energies E(2) (in kcal/mol) for the orbital interactions in (R)(H)NC(=X)YH and H2NC(=X)YR (X, Y = O, S, Se; R = H, F,
Cl, CH3, NH2) molecules and their radicals at the MP2/6-31+G*
theoretical level in Tables S1S12. Figures S1S3 incude the most
stable comformations of (R)(H)NC(=X)YH and H2NC(=X)YR (X, Y =
O, S, Se; R = H, F, Cl, CH3, NH2) molecules.

Acknowledgement
The authors are very thankful to the Council of Scientic and
Industrial Research, New Delhi, for nancial assistance.

References
(1) Fattahi, A.; Kass, S. R. J. Org. Chem. 2004, 69, 9176. doi:10.1021/jo0488964.
(2) Benson, S. W. Thermochemical Kinetics, 2nd ed.; Wiley-Interscience: New York,
1976.
(3) Gomes, J. R. B.; Ribeiro da Silva, M. D. M. C.; Ribeiro da Silva, M. A. V. J. Phys.
Chem. A 2004, 108, 2119. doi:10.1021/jp037996v.
(4) Izgorodina, E. I.; Coote, M. L.; Radom, L. J. Phys. Chem. A 2005, 109, 7558.
doi:10.1021/jp052021r.
(5) Buettner, G. R. Arch. Biochem. Biophys. 1993, 300, 535. doi:10.1006/abbi.1993.
1074.
(6) Mandalo, M.; Grana, A. M.; Mosquera, R. A. Chem. Phys. Lett. 2004, 400, 169.
doi:10.1016/j.cplett.2004.10.097.
(7) Densiov, E. T. Polym. Degrad. Stab. 1995, 49, 71. doi:10.1016/0141-3910(95)
00037-M.
(8) Burrows, C. J.; Muller, J. G. Chem. Rev. 1998, 98, 1109. doi:10.1021/cr960421s.
(9) Lai, W.; Li, C.; Chen, H.; Shaik, S. Angew. Chem. Int. Ed. 2012, 51, 5556. doi:10.
1002/anie.201108398.
(10) Schaerer, O. D. Angew. Chem. Int. Ed. 2003, 42, 2946. doi:10.1002/anie.
200200523.
(11) Coote, M. L. J. Phys. Chem. A 2004, 108, 3865. doi:10.1021/jp049863v.
(12) Stadtman, E. R.; Berlett, B. S. Chem. Res. Toxicol. 1997, 10, 485. doi:10.1021/
tx960133r.
(13) Beckman, K. B.; Ames, B. N. Physiol. Rev. 1998, 78, 547.
(14) Fu, S.; Davies, M. J.; Stocker, R.; Dean, R. T. Biochem. J. 1998, 333, 519.
(15) Linton, S.; Davies, M. J.; Dean, R. T. Exp. Gerontol. 2001, 36, 1503. doi:10.1016/
S0531-5565(01)00136-X.
(16) Dean, R. T.; Fu, S.; Stocker, R.; Davies, M. J. Biochem. J. 1997, 324, 1.
(17) Brunelle, P.; Rauk, A. J. Alzheimers Dis. 2002, 4, 283.
(18) Rauk, A.; Fairlie, D. P.; Reid, D. L.; Armstrong, D. A. Mechanisms of Oxidative
Damage in Ab of Alzheimers Disease; Gordon Conference on Free Radical
Reactions, Holderness, NH, 2001.
(19) Rauk, A.; Armstrong, D. A.; Fairhe, D. P. J. Am. Chem. Soc. 2000, 122, 9761.
doi:10.1021/ja994436u.
(20) Gilman, A. G.; Rall, T. W.; Nies, A. S.; Taylor, P. The Pharmacological Basis of
Therapeutics, 8th ed.; Pergamon Press: New York, 1990.
(21) Lucarini, M.; Pedrielli, P.; Pedulli, G. F.; Valgimigli, D.; Gigmes, P.; Tordo, P.
J. Am. Chem. Soc. 1999, 121, 11546. doi:10.1021/ja992904u.
(22) Wlodek, S. T.; Antosiewicz, J.; Briggs, J. M. J. Am. Chem. Soc. 1997, 119, 8159.
doi:10.1021/ja970395v.
(23) Harel, M.; Quinn, D. M.; Nair, H. K.; Silman, I.; Sussman, J. L. J. Am. Chem. Soc.
1996, 118, 2340. doi:10.1021/ja952232h.
(24) Zwirner-Baier, I.; Neumann, H. G. Arch. Toxicol. 1998, 72, 499. doi:10.1007/
s002040050534.
(25) Valentovic, M. A.; Yahia, T.; Ball, J. G.; Hong, S. K.; Brown, P. L.;
Rankin, G. O. Toxicology 1997, 124, 125. doi:10.1016/S0300-483X(97)00143-1.
(26) Okumura, F.; Ueda, O.; Kitamura, S.; Tatsumi, K. Carcinogenesis 1995, 16, 71.
doi:10.1093/carcin/16.1.71.
(27) Jonsson, M.; Lind, J.; Eriksen, T. E.; Merenyi, G. J. Am. Chem. Soc. 1994, 116,
1423. doi:10.1021/ja00083a030.
(28) Jonsson, M.; Lind, J.; Eriksen, T. E.; Merenyi, G. J. Chem. Soc. Perkin Trans. 2
1995, 61. doi:10.1039/P29950000061.
(29) Yamamura, T.; Suzuki, K.; Yamaguchi, T.; Nishiyama, T. Bull. Chem. Soc. Jpn.
1997, 70, 413. doi:10.1246/bcsj.70.413.
Published by NRC Research Press

Can. J. Chem. Downloaded from www.nrcresearchpress.com by CSP Staff on 03/13/15

For personal use only.

288

(30) Koch, K. R. Coord. Chem. Rev. 2001, 216, 473. doi:10.1016/S0010-8545(01)

00337-X.
(31) Zollinger, H. Color Chemistry Syntheses, Properties and Applications of Organic
Dyes and Pigments, 2nd ed.; Wiley-VCH: Weinheim, Germany, 1991.
(32) Wilson, L. B.; Bergmann, F.; Nachmansohn, D. J. Biol. Chem. 1950, 186, 781.
(33) Kovacic, P.; Lowery, M. K.; Field, K. W. Chem. Rev. 1970, 70, 639. doi:10.1021/
cr60268a002.
(34) Stella, L. Angew. Chem. Int. Ed. 1983, 22, 337. doi:10.1002/anie.198303373.
(35) Percec, V.; Grigoras, C. J. Polym. Sci. Part A: Polym. Chem. 2005, 43, 5283.
doi:10.1002/pola.21060.
(36) Baron, R. L. Environ. Health Perspect. Suppl. 1994, 102, 23. doi:10.2307/3432146,
10.1289/ehp.94102s1123.
(37) Casadei, M. A.; Zappia, F. M. M. G. J. Org. Chem. 1997, 62, 6754. doi:10.1021/
jo970308h.
(38) Pilli, G.; Erdogan, H.; Safak, C.; Calis, U.; Sunal, R. Arch. Pharm. 1992, 325, 537.
doi:10.1002/ardp.19923250815.
(39) Berry, R. J.; Wilson, A. L.; Schwartz, M. J. Mol. Struct. (THEOCHEM) 2000, 496,
121. doi:10.1016/S0166-1280(99)00181-5.
(40) Duca, M.; Arimondo, P. B.; Leonce, S.; Pierre, A.; Pfeiffer, B.; Monneret, C.;
Dauzonne, D. Org. Biomol. Chem. 2005, 3, 1074. doi:10.1039/B416862C.
(41) Olah, G. A.; Heiner, T.; Rasul, G.; Surya Prakash, G. K. J. Org. Chem. 1998, 63,
7993. doi:10.1021/jo9814804.
(42) Greene, W. T.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.;
Wiley: New York, 1991; pp. 327.
(43) Atanasov, A. G.; Tam, S.; Rocken, J. M.; Baker, M. E.; Odermatt, A. Biochem.
Biophys. Res. Commun. 2003, 308, 257. doi:10.1016/S0006-291X(03)01359-7.
(44) Gomes, J. R. B. J. Phys. Chem. A 2009, 113, 1628. doi:10.1021/jp8101354.
(45) Boyd, S. L.; Boyd, R. J. J. Am. Chem. Soc. 1997, 119, 4214. doi:10.1021/ja9619770.
(46) Griller, D.; Ingold, K. U. Acc. Chem. Res. 1976, 9, 13. doi:10.1021/ar50097a003.
(47) Viehe, H. G.; Janousek, Z.; Merenyi, R. Acc. Chem. Res. 1985, 18, 148. doi:10.
1021/ar00113a004.

Can. J. Chem. Vol. 93, 2015

(48) Frisch, M. J.; Trucks, G. W.; Schlegal, H. B.; Scuseria, G. E.; Robb, M. A.;
Cheeseman, J. A.; Zarkrzewski, V. G.; Montgomery, J.A., Jr.; Stratman, R. A.;
Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudinm, K. M.;
Strain, M. C.; Farkas, O.; Tomasi, J.; Baroni, V.; Cossi, M.; Cammi, R.;
Mannuci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.;
Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Raghvachari, K.; Foresman, J. B.;
Oritz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.;
Kamaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.;
Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.;
Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.;
Head-Gordon, M.; Replogei, E. S.; Pople, J. A. Gaussian 98, Revision-A.11.2;
Gaussian Inc.: Pittsburgh, PA, 2001.
(49) Foresman, J. B.; Frisch, E. Exploring Chemistry with Electronic Structure Methods,
2nd ed.; Gaussian Inc.: Pittsburgh, PA, 1996.
(50) Merrick, J. P.; Moran, D.; Radom, L. J. Phys. Chem. A 2007, 111, 11683. doi:10.
1021/jp073974n.
(51) Scott, A. P.; Radom, L. J. Phys. Chem. 1996, 100, 16502. doi:10.1021/jp960976r.
(52) Jursic, B. S.; Martin, R. M. Int. J. Quantum Chem. 1996, 59, 495. doi:10.1002/
(SICI)1097-461X(1996)59:6<495::AID-QUA7>3.0.CO;2-T.
(53) Pople, J. A.; Gordon, M. H.; Fox, D. J.; Raghavchari, K.; Curtiss, L. A. J. Chem.
Phys. 1989, 10, 5622. doi:10.1063/1.456415.
(54) DiLabio, G. A.; Pratt, D. A. J. Phys. Chem. A 2000, 104, 1938. doi:10.1021/
jp9938617.
(55) Kaur, D.; Kaur, R. P.; Kaur, P. Bull. Chem. Soc. Jpn. 2006, 79, 1869. doi:10.1246/
bcsj.79.1869.
(56) Kaur, D.; Kaur, R. P.; Kohli, R. Int. J. Quantum Chem. 2009, 109, 559. doi:10.
1002/qua.21824.
(57) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899. doi:10.1021/
cr00088a005.

Published by NRC Research Press