Journal of Molecular Structure 1129 (2017) 98e104

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Computational study on fused ve membered heterocyclic

compounds containing tertiary oxygen
Yujie Dai a, *, Tongcun Zhang a, b, Ying'ai Piao a, Xiuli Zhang a, **, Yanying Hu a,
Liming Zhang a, Shiru Jia a, Huixin He c
a
Key Laboratory of Industrial Fermentation Microbiology (Tianjin University of Science & Technology), Ministry of Education, College of Bioengineering,
Tianjin University of Science and Technology, No. 29 of 13th Street, TEDA, Tianjin 300457, PR China
b
Institute of Biology and Medicine, Wuhan University of Science and Technology, Huangjiahu Campus, Wuhan 430000, PR China
c
Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ 07102, United States

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 24 June 2016
Received in revised form
29 August 2016
Accepted 20 September 2016
Available online 21 September 2016

The structure, stability and electronic properties of two fused ve membered heterocyclic compounds
containing tertiary oxygen have been investigated with quantum chemistry computation. The results
show that 3H-4l3-furo[1,2-a]furan (M1) and 2a1l4-oxacyclopenta[cd]pentalene (M2) both own three
CeO bonds and especially in M2 the three CeO bonds and angles are approximately identical. The two
compounds are comparatively stable and M2 with three pentacycles is more stable than compound M1
according to the CeO bond lengths, bond orders, Egap, electronegativity (c), hardness (h), electrophilicity
(u), and aromaticity indexes. The aromaticity indexes such as NICS(0), NICS(1) and NICS(1)zz show that
they both have strong aromaticity. The natural bonding orbital (NBO) analysis shows that oxygen atom
takes hybrid orbitals composed of s and p orbital components to form s(CeO) bonds in compounds M1
and M2. The second order perturbation analysis shows that the occurrence of intramolecular charge
transfer within the molecule exists in compound M1.
2016 Elsevier B.V. All rights reserved.

Keywords:
Fused ve membered heterocyclic
compounds
Tertiary oxygen
MP2
Aromaticity
InChIKeys:
LQGQFMRQUDZBQG-UHFFFAOYSA-N
BIBDIGJDELBXGK-AYMMMOKOSA-N

1. Introduction
Whenever a novel chemical structure is discovered or put forward, it has greatly promoted the development of chemistry. In the
19th century chemists puzzled that benzene could be so unreactive
toward addition reactions, which was contrary to presumed high

rst proposed
degree of unsaturation. In 1865 [1,2], August Kekule
the cyclohexatriene structure for benzene and the raise of the
Kekule structure enhanced the knowledge about the aromatic
compounds. It was quick to be accepted by most chemists since it
can interpret most of the known isomeric relationships of aromatic
chemistry. The hexagonal structure explains well why only one
isomer of benzene exists and why disubstituted compounds have
three isomers at that time [3]. The exceptional stability or aromaticity of the benzene was rst modeled by Hckel [4] in 1931 with

* Corresponding author.
** Corresponding author.
E-mail addresses: yjdai@126.com (Y. Dai), zxl1966@hotmail.com (X. Zhang).
http://dx.doi.org/10.1016/j.molstruc.2016.09.058
0022-2860/ 2016 Elsevier B.V. All rights reserved.

the quantum chemistry. He was the rst to separate the bonding

electrons into s and p electrons and in 1951, Doering [5] proposed
the famous 4n2 rule for the stability of the aryl compounds with
cyclic p electrons. Thereafter, the discovery of ferrocene further
deepened the understanding of the structure and composition of
the aromatic compounds [6].
Aromaticity is a valuable concept and plays a key role in the
modern chemistry for exploring the structures, stabilities and
reactivity of different molecules [7,8]. It is closely related to pelectron delocalization for a given ring which brings about extra
stability of the ring [9]. Since aromaticity could not be directly
observed, it is conventionally assessed indirectly by computing
some properties that reect the aromatic character of the whole
or parts of the molecule [10]. At present, the aromaticity mainly
evaluated by aromaticity indices based on the molecular properties. All existent aromaticity criteria are derived from a few
basic categories such energetic, structural, magnetic, electronic
etc [11].
As a kind of important aromatic compounds, the heterocyclic

Y. Dai et al. / Journal of Molecular Structure 1129 (2017) 98e104

compounds change in structure and composition diversely [12].

The common hetero atoms are nitrogen, oxygen, sulfur and so on.
The atom numbers of heterocycles are usually 5 and 6. In nature,
the ve-membered heterocycles of pyrrole, furan, thiophene, sixmembered heterocyclic compound of pyridine and their fused
benzene ring derivatives are widely existed in coal, fossil oil [13],
plants and animals. Heterocyclic compounds have many applications and are inextricably woven into the life processes [14]. For
example, guanine adenine thymine and cytosine are important
components in nucleic acids. Besides the natural heterocyclic
compounds, there are many synthesized heterocyclic compounds
reported these years and more than 90% of new drugs contain
heterocycles [15e17]. Thus, the discovery of heterocyclic compounds with novel structure may promotes discovery of new drugs
and treatment of stubborn diseases.
Due to the difference of electronic structure between the carbon
and heteroatoms, heterocyclic compounds have different electronic
structure, stability and reactivity compared with the benzene and
some fused aromatic hydrocarbons. In recent years, computational
chemistry has been an important technique for the investigation of
the electronic structure and properties of heterocyclic compounds.
In 2009, Vektariene et al. [18] computated the nucleophilic
behavior of benzofused thieno[3,2-b]furans according to the energy
of highest occupied molecular orbitals (EHOMO), hardness (h),
electronegativity (c) and electrophilicity (u), etc. using DFT and HF
theory. Garca-Cruz et al. [19] studied the electronic structure of a
series of dibenzofurane and dibenzothiophene derivatives and
predicted their reactivities by analyzing the frontier orbitals
together with the aromaticities. Valencia et al. [20] computed
aromaticity of ve- and six-membered heterocycles present in
crude oils. Aromatic stabilization energy (ASE) was calculated by
homodesmotic chemical reactions for all heterocyclic compounds.
The energetic trends for protonated and unprotonated compounds
conrm the less reactivity of dibenzo-compounds in the hydrotreatment process and catalyst's poisoning by pyridine derivatives
present in crude oils.
Natural bond orbital (NBO) analysis is a useful tool for examining the bond-antibond stabilization energies within the object
compound, interaction among bonds, and the charge transfer or
conjugative interaction in molecular systems [21]. The Mayer bond
order (MBO) [22], which shows the strength of the bond character,
can also be obtained by computation from the treatment of the G09
computation result of NBO analysis using Multiwfn [23]. The
electron localization function (ELF) was introduced by Becke and
Edgecombe as a simple measure of electron localization in atomic
and molecular systems [24]. They associated the localization of an
electron with the probability density for nding a second like-spin
electron near the reference point. ELF is a measure of the likelihood
of nding an electron in the neighborhood space of a reference
electron located at a given point and with the same spin. In this
study, the technique of NBO analysis and the physical parameters
MBO and ELF were used to examine the bonding situation and
stability of the object heterocyclic compounds.
Neutral oxygen atom normally combines with two other
atoms to form two covalent bonds at most in ordinary compounds. Though there are four hydrogen atoms surrounding one
oxygen atom in ice, only two are covalent bonds and the others
are hydrogen bonds. Under some circumstances, oxygen can
form more than two covalent bonds with other atoms. In oxonium ions, more than two covalent bonds can exist between
oxygen and other atoms [25,26]. For trimethyloxonium ion, it
contains three equivalent CeO single s bonds. The oxonium ion
can be thought as an oxygen cation interacting with three atoms
or groups. So far, however, whether there exists some stable
compounds containing a neutral oxygen (not an oxygen cation),

99

which can form three covalent bonds with other atoms or

groups, is not known. In this study, two neutral fused ve
membered heterocyclic compounds containing tertiary oxygen
groups in the center of the molecule, 3H-4l3-furo[1,2-a]furan
(M1) and 2a1l4-oxacyclopenta[cd]pentalene (M2) with the
structures shown in Scheme S1 (M1 and M2) were investigated
and their structure, stability, aromaticity and electronic properties were characterized with MP2. As comparison, furan (M3),
oxonium (M4) and trimethyloxonium ions (M5) were also
computed and discussed.
2. Computational details
All the geometry optimization calculations were conducted
using MP2 included in the Gaussian 09 (G09) program package [27]
at 6-311G(d,p) base set level. The nature of the stationary points
was conrmed by frequency analysis at the same computational
level with no virtual frequencies are observed for the considered
structures. The GaussView 5.0 software [28] has been used for
visualization of different calculated parameters, for instant, the
optimized structures, the harmonic vibrational normal modes, the
MO surfaces, etc.
The energy separation between the highest occupied molecular
orbitals (HOMOs) and lowest unoccupied molecular orbitals
(LUMOs), Egap, was used as a valuable parameter to evaluate the
stability of the compounds. The adiabatic electron afnity (AEA)
was computed as the energy difference between total energies of
neutral and the corresponding anion energy at their respective
ground state geometries and the adiabatic ionization energy (AIP)
were calculated as the energy difference between total energies of a
cation and corresponding neutral species at their respective ground
state spin multiplicity and geometry. Global reactivity descriptors,
such as electronegativity (c) [29], hardness (h) [30], and electrophilicity (u) [31] are employed as indexes for analyzing the stability
and reactivity of the object compounds using MP2 method at 6311G(d,p) level. The denitions of these descriptors can be
found subsequently. For a system having N electrons with total
energy E, the electronegativity (c) and hardness (h) can be obtained
as follows [32].


vE
h
vN nr

v2 E
vN

!
nr

where v(r) is the external potential.

The vertical electron afnity (VEA) is the energy difference between the neutral and the anion state restricted to the optimized
geometry of the neutral state. The vertical rst ionization potential
(VIP) is the energy difference between the cation and the neutral
state according to the optimized geometry of the neutral state. VEA
and VIP are computed as stated in literature [33]. If VIP and VEA are
calculated using Koopman's theorem [34], then h is expressed as

1
2

h VIP  VEA

(1)

and c can be expressed as,

VIP VEA
2

(2)

Electrophilicity (u), is dened as,

c2
2h

(3)

In this investigation, the aromaticity of the object compounds

100

Y. Dai et al. / Journal of Molecular Structure 1129 (2017) 98e104

M1 and M2 were characterized by nucleus-independent chemical

shift (NICS) as a magnetic based aromaticity index [35]. NICSs of the
p ring system were obtained by using Multiwfn 3.3.8 program [23]
to treat computation results from Gaussian 09 package. The obtained negative values of the absolute shielding at the center of the
ring is noted as NICS(0). In addition, NICS(1) is the negative value of
the absolute magnetic shielding at 1 over the ring plane. Moreover, the NICS component perpendicular to the plane of the
molecule can be dened as NICS(1)zz to measure the sole effect of
p-electrons on the aromatic character of a system [36]. The ab initio
theory with 6e311G(d,p) level were applied to calculate the
these indexes' values based on the gauge-independent atomic
orbital (GIAO) formalism [37].
Natural bond orbital (NBO) analysis is a useful tool for examining the bond-antibond stabilization energies within the object
compound, interaction among bonds, and the charge transfer or
conjugative interaction in molecular systems [21]. The NBO calculations were conducted via NBO 3.1 program [38] as implemented
in the Gaussian 09 package at MP2/6-311G(d,p) level. The second order perturbation approach is used to evaluate the donor (i)
and acceptor (j) interaction in the NBO basis [39]. The nature of
charge transfer interaction between the adjacent atoms was
analyzed and the two-dimensional gures for electron localization
function (ELF) of the neutral compounds M1 and M2 were made
employing Multiwfn 3.3.8 program [23].
In order to quantitatively investigate the strength of the bonding
between the central atom and the adjacent carbon atoms, we used
the Mayer bond-order (MBO) values between atoms. This approach
has been extensively used in many researches. The denition of
Mayer bond order was dened in Ref. [22]. The Mayer bond order
was reliable to evaluate the bond strength [40]. Generally, for the
same kind of bond in different chemical environment, a higher
bond order means a higher bond strength [40,41]. Besides, the
analysis of the geometry data of the above models also provides
further information of bond strength and thermal stability [42].
3. Results and discussion
3.1. Optimized geometry
The neutral structure of compounds M1 and M2 shown in
Scheme S1 including furan, oxonium and trimethyloxonium ions
optimized with MP2 method at 6-311G(d,p) base set level. The
optimized structural parameters of the oxygen atom and adjacent
carbon atoms for compounds M1 and M2 obtained from MP2
methods are presented in Table 1, and the optimized geometry are
shown in Fig. 1. (The optimized geometry of other compounds is
shown in Fig. S1). The complete structure parameters such as bond
lengths, bond angles and dihedral angles for the geometry of M1M5 are listed in Table S1eS5.
In compound M1, the CeO bond lengths (1.421 ) for C2 and C8
are identical. However, the CeO bond length (1.461 ) between O1
and C5 is different from them. It is noteworthy that the three CeO

bond lengths (1.419 ) are same and angles (115.78 ) between

them are identical in compound M2, from which we might imagine
that compound M2 were in good symmetry under the ground state.
However, no reasonable optimized structure with D3h or C3v
symmetry was gained. They are both in C1 geometry. There are
some distortions about the optimized structures of compounds M1
and M2 and the geometry of compound M2 has a quaquaversal
structure with the oxygen atom at the apex. It is interesting for the
oxygen atom bonding state in compounds M1 and M2 that each
oxygen atom don't approach only two carbon atoms to form two
CeO bonds and depart from the third adjacent carbon atom. It
combines as many as three carbon atoms, which conicts with the
common sense about a neutral oxygen atom which can only form
two covalent bonds with other atoms or groups. The CeO bond
length calculated from MP2 method in compound M2 is 1.419 ,
which is similar to the typical CeO single bond length in ether
(1.42 ) [43]. But they are longer than that in furan (1.36 ) [44],
indicating CeO bond strength may weaker than that in furan.
Furthermore, compound M1 possesses longer CeO bond lengths
(1.461 ) than CeO single bond in ether, but they are in the
acceptable range of CeO single bond lengths just as that in oxonium
and trimethyloxonium ions (1.488 and 1.477 respectively listed
in Tables S4eS5). As a whole, the central oxygen atom can form
three bonds with the adjacent carbon atoms within the range of
normal single CeO bond lengths.
3.2. Molecular stability and reactivity
The energy separation between the highest occupied molecular
orbitals (HOMOs) and the lowest unoccupied molecular orbitals
(LUMOs), Egap, was used as a valuable parameter to evaluate the
stability of the compounds. In general, smaller the Egap is, lower
the energy is required to motivate the electrons from valence band
to the non-bonding or anti-bonding orbitals, which corresponds to
higher chemical activity of electronic structure to some extent. The
computed Egap of the neutral compounds M1 and M2 are provided
in Table 2. The ionization potential (IP) and electron afnity (EA) are
used as important properties which reect the ability of the compound releasing and attracting an electron [45]. The computed IP
and EA values of compounds M1 and M2 according to MP2/6311G(d,p) are shown in Table 2. Compound M2 has higher VIP
(45.247 eV) and AIP (8.567 eV) values, which shows the lower
electron releasing ability than compound M1. On the other hand,
the AEAs and VEAs, which reect the ability of attracting electrons,
also change drastically for the different compounds. The negative
values indicate that it requires energy not releasing energy for them
to obtain electrons to change to anions. As comparison, M2 has
lower AEA and VEA values, which shows that its not easier to
obtain electron than M1.
Global reactivity descriptors, such as electronegativity (c),
hardness (h), and electrophilicity (u) are introduced as indices for
analyzing the stability and reactivity of the object compounds. h, c,
u can be obtained according to ref. [32] with the computation of

Table 1
Structural parameters on the central oxygen atoms and adjacent carbon atoms calculated by MP2/6-311G(d,p) for the neutral compounds M1 and M2.
Molecule

Multi.

Bond length()

M1(C6H6O)

M2(C9H6O)

C2eO1
C5eO1
C8eO1
C2eO1
C5eO1
C8eO1

Obtained from the Multiwfn treatment of G09 computation.

Angle( )
1.421
1.461
1.421
1.419
1.419
1.419

C8eO1eC5
C8eO1eC2
C5eO1eC2
C5eO1eC8
C2eO1eC5
C2eO1eC8

Mayer bond ordera

110.42
137.830
110.42
115.78
115.78
115.78

0.4997
0.6303
0.4998
0.5726
0.5729
0.5730

Y. Dai et al. / Journal of Molecular Structure 1129 (2017) 98e104

101

Fig. 1. Optimized structures of M1 (A) and M2 (B) using G09 at MP2/6-311G (d, p) level. (The atoms in red present oxygen atoms. The atoms in gray standard carbon atoms, and
others in white are hydrogen atoms. The ring numbers are ordered due to the sum of the whole atom numbers included in them.). (For interpretation of the references to colour in
this gure legend, the reader is referred to the web version of this article.)

Table 2
The computed results of Egap, IP and EA for compounds M1 and M2.
Molecule

IP (eV)

M1
M2

EA (eV)

VIP

AIP

VEA

AEA

36.274
45.247

7.264
8.567

32.872
40.690

33.950
40.772

MP2 method at 6-311G(d,p) level. Structures with larger hardness values are often considered to be harder, i.e., they are less
reactive toward changing in the number of electrons. The values of
hardness obtained in our calculations are shown in Table 2.
Comparatively, compound M2 has the higher hardness values
(34.573 eV), which reects that it is the inerter one for chemical
reaction.
The electronegativity (c) of a molecule is the power with which
it attracts electrons to itself and the electrophilicity (u), is the
measure of its reactivity toward attracting electrons from a nucleophile to form bonds. It shows that compound M2 has higher c and
u values (2.279 eV and 0.060 eV), which suggests compound M2 in
general is more likely to attract electrons from a nucleophile
compared with compound M1.
The Egap value of compound M2 (8.260 eV) is higher than that
(7.275 eV) of compound M1 which indicates that chemical reactions may be more difcult for compound M2. Moreover, both
compound M1 and M2 have larger Egap values than nitrobenzene
[46] also calculated by MP2 shows that they both may be more
stable than nitrobenzene.
There is closed relation between the molecule stability and
aromaticity of the cyclic conjugated system of the cyclic compounds. In this study, nucleus-independent chemical shift (NICS)
indices [35,47] such as NICS(0) NICS(1) NICS(1)zz were employed
and computed with ab initio method at 6-311G(d,p) level. The

Table 3
The obtained aromaticity indices for each ring of the considered compounds.
Compound

Cycle

Nics(0) (ppm)

Nics(1) (ppm)

Nics(1)zz(ppm)

M1

I
II
I
II
III

11.191
11.191
20.485
20.486
20.487
7.955

6.257
6.288
12.940
12.941
12.940
10.210

17.750
17.909
35.834
35.834
36.116
29.738

M2

Benzene

Egap (eV)

h (eV)

c (eV)

u (eV)

7.275
8.260

34.573
42.968

1.701
2.279

0.042
0.060

negative and positive of these NICS indices' values indicate aromatic and anti-aromatic rings, respectively. The obtained aromaticity indices for each compound are listed in Table 3. For
comparison, the obtained aromaticity indices for benzene ring
were also presented in the table. The impact of the different central
atoms, ring sizes and numbers on local aromaticity of compounds
M1 and M2 are investigated separately in details. The results
indicate that the aromaticity indices for the rings around the central atom in a molecule are very similar and both the two compounds are aromatic. The most fascinating result from Table 3 is
that compound M2 has the strongest aromaticity because the three
rings of it has the higher minus aromaticity indices and their values
are far greater than that of benzene (NICS(0) -7.955 ppm,
NICS(1) -10.210 ppm and NICS(1)zz -29.738 ppm).
3.3. NBO analyses
In order to understand the nature of bonding and charge state of
compounds M1 and M2, we performed natural bond orbital (NBO)
analysis for the lowest energy state of neutral and charged M1 and
M2. The results are summarized in Table 4. It can be seen that the

Table 4
The computed natural charges (q) and natural electron conguration (e) on the
central hybrid atoms (R) and adjacent carbon (AC) for the neutral compounds M1
and M2.
Compound

Atom

e(R)

q(R)a.u.

M1

O1
C2
C5
C8
O1
C2
C5
C8

2S1.512p4.953p0.014p0.01
2S0.952p3.033p0.013d0.01
2S0.882p2.643d0.014p0.01
2S0.952p3.033p0.013d0.01
2S1.522p4.933p0.01
2S0.872p2.833d0.014p0.01
2S0.872p2.833d0.014p0.01
2S0.872p2.833d0.014p0.01

0.476
0.003
0.450
0.003
0.474
0.268
0.268
0.268

M2

102

Y. Dai et al. / Journal of Molecular Structure 1129 (2017) 98e104

C5eC6 and LP(1) O1/BD*(2) C7eC8. Additionally, there are plenty

of charge transfers from CeH bond orbitals to CeO antibonding
orbitals in compound M1. For compound M2, one main intramolecule charge transfer from LP(1)O1 to LP(1)C5 has the stabilization energy of 22.27 kcal mol1, and from LP(1) O1 to BD*(2)
C2eC10 and BD*(2) C8eC9 antibonding orbitals with stabilization
energies of 12.83 kcal mol1. The larger the E(2) value is, the more
intensive the interaction is between electron donors and electron
acceptors, i.e. the more donating tendency from electron donors to
electron acceptors and the greater the extent of conjugation of the
whole system.

central oxygen atom negative charged but the adjacent atoms are
positive charged from the result of NBO natural charges (q). AlLaham et al. [48] found atomic charge (0.2e0.6 a.u.) means covalent bonding and 0.9 a.u. means more ionic characteristic. The NBO
charges of all the central atoms and their adjacent carbon atoms in
compounds M1 and M2 are in the range of 0.2e0.6 a.u., which indicates that the dominant interaction among these atoms is covalent bonding. And from NBO analysis the natural hybrid orbital the
central atom is mainly composed of s and p orbitals.
The stabilizing effect from the delocalization interactions will be
quantitatively obtained as a second perturbation estimate of the
corresponding bonding-anti-bonding interactions, according to
which the electronic population in a molecular system should be
distributed over a set of localized one-center (lone pair), two
center (bond) and three center orbitals, leading to a localized
description which closely simulates a classical Lewis-type picture of
the electronic system. With this background, the delocalization
effects can be evaluated by small occupancies of the set of antibonding orbitals.
Some selected results from the NBO and the second order
perturbation stabilization theory analyses were collected in
Tables 5 and 6 respectively. The NBO results conrm the tertiary
oxygen structure in molecules M1 and M2, which comprises three
sO-C bonds and some lone pairs of electrons on the oxygen atom
(Table 5). For compound M1, both the occupation of sO-C bonds
and the orbital composition of BD(1) O1eC2 and BD(1) O1eC8 are
identical. However, BD(1) O1eC5(1.987) showed some differences
from them. For compound M2, the composition of the three sO-C
bonds (BD(1) O1eC2, O1eC5 and O1eC8) are identical in occupation and the oxygen uses three sp2.23 hybrid orbitals to form the
three sO-C bonds. The occupation of the three sO-C bonds are all
over 1.980 indicates the strong bond strength of them. The
contribution of the atoms to the orbital of both compound M1 and
M2 shows that the sO-C bond is a strong polarized bond, which is
composed over 75% of oxygen orbitals but less than 25% of carbon
orbitals. Additionally there is one lone pairs on oxygen, LP(1)O1,
with nearly pure 2p character.
Table 6 gives the main results from the second order perturbation analysis of the Fock matrix for the central oxygen atom related
bonds. There are many miner intramolecule charge transfers between the oxygen atom or related bond orbitals and the adjacent
atom or bond orbitals, which makes electrons delocalized and the
molecule energy further decreased [49]. It can be seen that the
oxygen atom can take part in the intramolecule charge transfer. In
compound M1, there exists the possibility for delocalization of
oxygen lone pair LP(1) O1/BD*(2) C2eC3, LP(1) O1/BD*(2)

3.4. Mayer bond order

The bond strength and the stabilities of compounds M1 and M2
can be quantitatively considered and evaluated by the natural bond
orbital theory [50]. In continue, the Mayer bond order (MBO) [22],
which shows the strength of the bond character, is also computed.
The MBO can be obtained from the treatment of the G09 computation result of NBO analysis using Multiwfn [23]. MBO closely relates to the bond strength, and the larger MBO values imply the
stronger bond character. The MBO bond orders related to oxygen
atoms in compounds M1 and M2 are shown in Table 1. As can be
seen, the MBOs of CeO bonds vary from 0.4997 to 0.6303, indicating that the characteristic OeC bonds of compounds M1 and M2
are different from each other. MBO values decrease from compounds M2 to M1, which are in accord with the order of their
stability indices discussed previously. Additionally, the MBOs for
three CeO bonds of M2 are nearly identical, showing that the oxygen atom forms three nearly identical bonds with three adjacent
atoms though the Mayer bond orders are smaller than 1.
3.5. Electron localization function (ELF)
To verify the nature of interaction between the carbon atom and
the oxygen atoms, we plotted two-dimensional gures for electron
localization function (ELF) of the neutral compounds using Multiwfn 3.3.8 program [23] which are shown in Fig. 2. In quantum
chemistry, the ELF is employed to measure the possibility of nding
an electron in the neighborhood space of a reference electron
located at a given point and with the same spin. In the ELF maps,
each atom is surrounded by an annular region where the value of
ELF is close to 1.0, which is evident by red color. Additionally, the
ELF values in the midpoint between the central oxygen and adjacent carbon atoms are almost close to 0.5 (identied from the
yellow color), indicating the strong electron delocalization for

Table 5
Characteristics of central atom related bonding orbitals in compounds M1 and M2 based on the natural population analysis.
Compound

Orbital

Occupation

Atom

Composition%
s

M1

BD(1) O1eC2

1.992

BD(1) O1eC5

1.987

BD(1) O1eC8

1.992

LP(1) O1
BD(1) O1eC2

1.857
1.987

BD(1) O1eC5

1.987

BD(1) O1eC8

1.987

LP(1) O1

1.872

O1
C2
O1
C5
O1
C8
O1
O1
C2
O1
C5
O1
C8
O1

34.40
19.45
30.07
15.12
34.40
19.45
1.10
30.91
14.51
30.91
14.46
30.91
14.50
7.23

65.56
80.08
69.89
84.35
65.56
80.08
98.90
69.04
84.96
69.03
85.01
69.04
84.96
92.76

0.04
0.48
0.04
0.53
0.04
0.48
0.00
0.05
0.54
0.05
0.53
0.05
0.54
0.01

M2

Hybrid

Contributions of atoms to the orbital (%)

sp1.91
sp4.12d0.02
sp2.32
sp5.58
sp1.91
sp4.12d0.02
sp98.90
sp2.23
Sp5.86d0.04
sp2.23
Sp5.88d0.04
sp2.23
Sp5.86d0.04
sp12.83

76.53
23.47
77.30
22.70
76.53
23.47
100.00
76.57
23.43
76.56
23.44
76.57
23.43
100.00

Y. Dai et al. / Journal of Molecular Structure 1129 (2017) 98e104

103

Table 6
Second order perturbation theory analysis of Fock matrix of compounds M1 and M2 by NBO method using MP2/6-311G(d,p) level.a
Compound

Donor NBO(i)

Acceptor NBO(j)

E(2) (kcal/mol)

E(j)E(i) (a.u.)

Fij(a.u.)

M1

BD(1)C4eH11
BD(1)C6eH12
LP(1)O1
LP(1)O1
LP(1)O1
LP(1)O1
LP(1)O1
LP(1)O1

BD*(1)O1eC5
BD*(1)O1eC5
BD*(2)C2eC3
BD*(2)C5eC6
BD*(2)C7eC8
LP(1)C5
BD*(2)C2eC10
BD*(2)C8eC9

4.93
4.93
14.05
18.75
14.05
22.27
12.83
12.83

1.17
1.17
0.75
0.73
0.75
0.52
0.77
0.77

0.068
0.068
0.096
0.115
0.096
0.137
0.099
0.099

M2

Abbreviations: LP: lone pair; BD: bonding; * antibonding.

a
Only the data with E(2) higher than 4 kcal/mol for M1 and M2.

Fig. 2. Two-dimensional ELF maps in the plane through the middle height of the compounds. (A: the ELF map of M1; B: the ELF map of M2).

them. The delocalization effect increases the CeO bonding just like
the two adjacent carbon atoms, which brings about extra stability
for the system.
In this work, we have conducted a theoretical investigation on
the geometries, stabilities and electronic properties of some ve
membered heterocyclic compounds containing tertiary oxygen
using MP2 at 6-311G(d,p) level. The optimum geometries show
the geometries of compounds M1 and M2 like curved surfaces. Both
M1 and M2 contain three CeO bonds combining to one oxygen
atom. Especially there are nearly three identical CeO bond lengths
and CeOeC angles in M2. Their stability and electronic properties
were evaluated by Egap, Mayer bond orders, ionization potential
(IP), electron afnity (EA), electronegativity (c), hardness (h),
electrophilicity (u), and aromaticity. The results showed the both
the two compounds are comparatively stable. As comparison,
compound M2 is more stable than M1 due to its higher Egap, IP, h
and lower EA values. The aromaticity indexes show both compounds M1 and M2 have strong aromaticity and M2 is even strong
than benzene.
Tertiary oxygen heterocyclic compounds do not accord with the
classical valence bond theory. The bonding state can be explained
by the natural bonding orbitals analysis and the second order
perturbation theory. All the tertiary oxygen in compounds M1 and
M2 take the hybrid orbital mainly composed of s and p components. In the work with the computation of MP2 theory at 6311G(d,p) level, we found that the oxygen atom in tertiary oxygen heterocyclic compounds M1 and M2 can combine with three
adjacent carbon atoms, which has not been reported previously,
This study gives a new vision for us to recomprehend the oxygen
bonding formation.

Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Grant No. 21272171) and the Super Computational Science Application Research Project, NSFC-Guangdong
Joint Fund and supported by National Supercomputer Center in
Guangzhou.
Appendix A. Supplementary data
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.molstruc.2016.09.
058. These data include MOL les and InChiKeys of the most
important compounds described in this article.
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