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Planar tetracoordinate carbons with a double

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bond in CAl3E clusters

Cite this: Phys. Chem. Chem. Phys.,
2015, 17, 8769
Zhong-hua Cui,a Yi-hong Ding,*a Jose Luis Cabellos,b Edison Osorio,c Rafael Islas,d
Albeiro Restrepoe and Gabriel Merino*b

Received 7th December 2014,
Accepted 19th February 2015
DOI: 10.1039/c4cp05707d
www.rsc.org/pccp
The potential energy surfaces of a series of clusters with the formula CAl3E (E = P, As, Sb, Bi) are
systematically explored using density functional theory and high level ab initio calculations. The global
minimum structure of these clusters contains a planar tetracoordinate carbon atom. The presence of a
CQE double bond is supported by the Wiberg bond indices, the adaptive natural density partitioning
analysis, and the magnetic response. Our results show that these planar tetracoordinate carbon clusters
are both thermodynamically and kinetically viable species in the gas phase.

Introduction geometries to be stable and energetically preferred over tetra-

Forty-five years ago, Homann, Alder, and Wilcox (HAW) out-
lined a way to stabilize a planar tetracoordinate carbon (ptC)
atom using planar methane as a model, so that it could serve as
a thermally accessible transition state for racemization.1 Given
the symmetry of planar methane, the carbon atom has a pure
2p lone pair perpendicular to the molecular plane. In order to
stabilize the ptC form, and thus to reduce the lifetime of
racemization, the authors suggested delocalizing the lone pair
either by attaching electron acceptor substituents to the central
carbon or by incorporating the lone pair as part of a (4n + 2) p
system. Despite the fact that this idea was originally suggested
to stabilize a transition state (not a local minimum), these two
suggestions laid the foundation for ptC chemistry. The number
of synthesized or in silico ptC molecules is still small, but the
majority satisfy the HAW rule.26
In 1991, Schleyer and Boldyrev suggested a couple of pentaatomic
clusters containing a ptC atom (cis-CSi2Al2 and trans-CSi2Al2).7 Later,
Boldyrev and Simons re-examined these structures and proposed
that the presence of 18 valence electrons is crucial for planar
a
State Key Laboratory of Theoretical and Computational Chemistry,
Institute of Theoretical Chemistry, Jilin University, Changchun 130023,
Peoples Republic of China. E-mail: yhdd@mail.jlu.edu.cn
b
Departamento de Fsica Aplicada, Centro de Investigacion y de Estudios
Avanzados Unidad Merida, km 6 Antigua carretera a Progreso. Apdo. Postal 73,
Cordemex, 97310, Merida, Yuc., Mexico. E-mail: gmerino@mda.cinvestav.mx
c
Departamento de Ciencias Basicas, Fundacion Universitaria Luis Amigo, SISCO,
Transversal 51A # 67B 90, Medelln, Colombia
d
Departamento de Ciencias Qumicas, Facultad de Ciencias Exactas, Universidad
Andres Bello, Avenida Republica 275, Santiago, Chile
e
Instituto de Qumica, Universidad de Antioquia UdeA, Calle 70 No. 52-21,
Medelln, Colombia
Electronic supplementary information (ESI) available. See DOI: 10.1039/
c4cp05707d
hedral forms.8 In 2000, the groups of Wang and Boldyrev
detected the CAl4Na cluster in the gas phase.9 This cluster
contains a ptC atom surrounded by four Al atoms, nicely
satisfying both the HAW and the 18 valence electron rules. The
substitution of Al by other electropositive atoms in the CAl42
framework, preserving the 18 valence electrons, provides an
interesting series of planar hypercoordinate carbon systems.1015
Particularly, Cui et al. found that the substitution of one Al atom
by N in CAl42 to yield CAl3N maintains the planar framework.16
Given the difference in electronegativities, an electron density
localization between C and N is induced, leading to the formation
of a double CQN bond. CQN bonds are common in chemistry,
but they are not expected to be involved in a planar hypercoordinate
carbon system, where delocalization is essential.
What happens if N is substituted by a heavier group 15
element? The answer is not simple if one considers that
molecules containing CQE double bonds (E = P, As, Sb, Bi)
are not so stable and bulky substituents are necessary in order
to stabilize such systems. Among the molecules containing a
CQE double bond, CQP species are the most abundant,17,18
whereas those exhibiting CQAs19,20 or CQSb21,22 double bonds
are scarce and, to the best of our knowledge, not a single case of
a CQBi double bond has been reported. Clearly, the ability to
form a CQE double bond decreases from P to Bi.
In this article, we systematically explore the potential energy
surfaces of a series of clusters with the formula CAl3E (E = P, As, Sb,
Bi) using density functional theory (DFT) and ab initio calculations.
Interestingly, in all cases, the global minimum has a ptC atom.
Bonding is analyzed via the Adaptive Natural Density Partitioning
(AdNDP) and the Natural Bond Orbital (NBO) approaches.
Both analyses show a p-localization between the C and E atoms.
Additionally, BornOppenheimer molecular dynamics (BO-MD)
simulations support the kinetic stability of these clusters.

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Computational details
In order to systematically explore the potential energy surfaces
(PESs) of the CAl3E clusters (E = P, As, Sb, Bi), a grid-based
comprehensive isomeric search23 strategy is employed to generate
the starting structures. Both the singlet and the triplet state PESs
are analyzed. The initial screening is carried out at the B3LYP24,25
level in conjunction with a 6-311+G(d) basis set for C, Al, P, and As,
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and a LANL2DZ basis set for Sb and Bi. The structures found by
the initial screening are re-optimized and characterized using the
B3LYP approach and an aug-cc-pVTZ basis set (aug-cc-pVTZ-PP for
Sb and Bi). This level is also employed to find the corresponding
transition states connecting the dierent local minima. Intrinsic
reaction coordinate (IRC)26 calculations ensure that the TSs are
connected to the designated reactants and products. The total
energies are estimated at the CCSD(T)27/aug-cc-pVTZ//B3LYP/
aug-cc-pVTZ level of theory, including the Zero Point Energy
(ZPE) correction computed at the B3LYP/aug-cc-pVTZ level. Only
global minima are re-optimized at the CCSD(T)/aug-cc-pVTZ level.
In order to judge the reliability of our DFT and CCSD(T) calcula-
tions, we used the T1 diagnostic.28 Empirically, if T1 is smaller
than 0.02 then a CCSD result is reliable. The T1 values computed
for the global minima and the closest isomers are below 0.02,
indicating that accurate mono-determinantal methodologies like
DFT and/or CCSD(T) can be safely employed. All of these calcula-
tions are carried out using the Gaussian 09 program.29
For the global minima, chemical bonding is analyzed in terms
of the NBO30 and AdNDP31 schemes using the B3LYP/aug-cc-pVTZ
geometries. Particularly, the AdNDP approach leads to a partition-
ing of the charge density into elements with the lowest possible
number of atomic centers per electron pair: n-center-two-electron
(nc-2e) bonds, including core electrons, lone pairs, 2c-2e bonds,
and so on. AdNDP accepts only those bonding elements whose
occupation numbers (ON) exceed a specified threshold value,
which is usually chosen to be close to 2.00 |e|.
In order to study electron delocalization, the induced mag-
netic field (Bind)3234 is computed at the PW9135/DZVP36 level in
deMon2K37 (except for the Bi cluster). Shielding tensors are
calculated using the IGLO approach. Structures are placed in
such a way that the origin of coordinates is located at the carbon
atom and the z-axis is that perpendicular to the molecular plane.
Structures and energetics
For each cluster, both the singlet and the triplet state potential
energy surfaces were explored. Gratifyingly, in all cases the
Table 1 Smallest frequencies (nmin, cm 1), NPA charges on ptC (q(C), |e|), NPA charges on E (q(E), |e|), Wiberg bond indices of the CE bond (WBICE),
Wiberg bond indices of the AlAl bond (WBIAlAl), carbon valence populations (Pop), HOMO energies (EHOMO, eV), HOMOLUMO gaps (Gap, eV).
All values have been computed at the B3LYP/aug-cc-pVTZ level
Cluster nmin q(C) q(E) WBICE
CAl3P 75 2.13 0.14 1.82
CAl3As 54 2.24 0.26 1.72
CAl3Sb 28 2.44 0.52 1.51
CAl3Bi 18 2.44 0.56 1.46
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most stable form of the CAl3E clusters is a singlet planar C2v
structure (1), which contains a ptC atom. Vibrational analysis
shows that structure 1 is a minimum for all the CAl3E species,
and the smallest vibrational frequency (see Table 1) corre-
sponds to a soft mode lower than 76 cm 1 assigned to a central
atom movement out of the molecular plane. Fig. 1 summarizes
the most relevant geometrical parameters of 1 computed at the
B3LYP and CCSD(T) levels, using the aug-cc-pVTZ basis set.
The geometrical variations between both methods are almost
negligible (less than 0.015 ). It is apparent from Fig. 1 that the
increase in the size (and electronegativity) of the E atoms alters
the CAl3 skeleton. While the CAl bond lengths perpendicular
to the CE bonds systematically decrease in going from P (2.127 )
to Bi (2.082 ), the parallel CAl bond lengths increase.
Fig. 2 shows the local minima found for CAl3E in a range of
roughly 50 kcal mol 1 above the global minimum. Around 15
dierent arrangements (singlets and triplets) were found in this
range. For CAl3P, CAl3As, and CAl3Sb, the second most stable
structure is also a singlet planar form, but it bears a tricoordinate
carbon atom because one of the aluminum atoms is now inter-
acting with one of the EAl sides. Note that the energy differences
between the global minima and the second lying energy structure
are appreciably high (16.5 (P), 15.8 (As), and 14.7 (Sb) kcal mol 1,
computed at the CCSD(T)//B3LYP level). In the case of CAl3Bi, the
second most stable structure is a triplet planar form also contain-
ing a ptC atom. The energy gap between these structures is only
8.0 kcal mol 1. Thus, the PESs of the CAl3E clusters are complex,
but they comprise a deep ptC global minimum.
Fig. 1 Global minimum structure of the CAl3E (E = P, As, Sb, Bi) clusters.
The optimized geometries are computed at the B3LYP and CCSD(T)
(in parentheses) levels. Bond lengths are given in .
WBIAlAl Pop EHOMO Gap
0.15 2s1.592px1.502py1.752pz1.17 5.6 2.3
0.17 2s1.642px1.502py1.782pz1.22 5.5 2.0
0.22 2s1.682px1.542py1.802pz1.30 5.4 1.7
0.23 2s1.702px1.512py1.812pz1.33 5.2 1.5
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Fig. 2 Local minima for the CAl3E (E = P, As, Sb, Bi) clusters in a range of roughly 50 kcal mol 1 above the global minimum. The energy dierences in
kcal mol 1 are computed at the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ level of theory, including the ZPE correction.

Bonding
Fig. 3 depicts the valence molecular orbitals (MOs) of the most
stable form of CAl3P. The HOMO is a combination of the 2px
orbital of carbon and the valence s orbitals of two Al atoms to
form a three-center bonding orbital. The HOMO energy is
almost constant, but the HOMOLUMO gap decreases drasti-
cally from P to Bi, implying a decrease of stability according to
the principle of maximum hardness (see Table 1). One expects
the p-orbital to be fully delocalized into the five atoms, but this
is not the case. The p-bonding orbital (HOMO-4) is predomi-
nantly located on the CP bond. So, in principle, the CP bond
can be classified as a double bond. The same localization is
perceived in the heavier congeners. All of this is consistent with
the computed Wiberg bond indices (WBIs),38 whose values are
1.82 (P), 1.72 (As), 1.51 (Sb), and 1.46 (Bi). Note that the WBI
values diminish gradually in going from P to Bi, showing a
decrease in the ability to form a CQE double bond with heavier
atoms. It is important to recall that the one ligandligand
bonding orbital (HOMO-1), which is essential to preserve the
square-planar geometry, is preserved.
Natural population analysis (NPA) charges indicate a consi-
derable electron transfer from the peripheral atoms to the carbon.
The electron transfer from the Al atoms to C (Al - C) is more
significant in the case of the P and As clusters (see Table 1),

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Fig. 3 Valence molecular orbitals of CAl3P.

but for Sb and Bi, the E - C transfer is competitive with the

Al - C one. The charge on the carbon varies in the 2.13 (P) to
2.44 (Bi) |e| range. The decrease in the peripheral AlAl bonds
is a consequence of this electron transfer, which is also revealed
by the WBIAlAl indices. The carbon atom acts as a s-acceptor;
this charge acceptance is balanced by the donation of the 2pz
electrons to the p-orbital (see Table 1). The occupancies of the
2pz orbitals are lower than those of the 2px and 2py orbitals
for the P, As, Sb and Bi clusters, which is a manifestation of a
back-donation.
The bonding pattern of the CAl3E clusters, revealed by the
AdNDP analysis, is summarized in Fig. 4. AdNDP shows the
presence of four lone pairs located at the peripheral atoms
with occupation numbers (ON) in the range between 1.86 and
1.95 |e|. Additionally, there are one 2c-2e CE s-bond, two 3c-2e
AlCAl s-bonds, and one 5c-2e s-bond. Remarkably, AdNDP
also supports the localization of a p-orbital at the CE bond, in
agreement with the WBI indices. Hence, the CE bonds in the
CAl3E clusters can be safely classified as double bonds. Note that
ON decrease from P to Bi, indicating again that the capacity to
form a CQE double bond decrease for heavier congeners.

Magnetic response
The magnetic response of a planar hypercoordinate carbon
system is typically diatropic, with a s-skeleton contribution
stronger than the p-response.10,15,3941 Fig. 5 depicts the
z-component of the induced magnetic field (Bind z ) contour lines
of the CAl3E clusters, showing the regions where the magnetic
response is shielding (diatropic) or enforcing (paratropic) the
external field. For a ptC atom embedded in a symmetrical
environment, such as CAl42 , it is obvious that the magnetic
response should be symmetry adapted. Similar magnetic behavior
is expected when the electronegativity difference among the
peripheral atoms is small. In our case, the s-response is also more
intense than the p one. It is also apparent from Fig. 5 that the
s-electrons are fully delocalized, meaning that the presence of Fig. 4 Bonds recovered by the AdNDP analysis for the CAl3E (E = P, As, Sb,
a group 15 element does not alter the s-electron distribution. Bi) clusters. The values in |e| are the occupation numbers.

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Fig. 5 Contour lines of the z-component of the induced magnetic field (Bind z ) for CAl3P in the molecular plane and perpendicular to the molecular plane
through the origin. The scale is given in ppm (or mT for an external field of 1 T).

In contrast, the p-response for CAl3P is localized around the CP
bond, supporting the presence of a double bond. For CAl3As and
CAl3Sb, the localization is more pronounced around the E atom,
but again there is no sign of p-electron delocalization (see Fig. S1,
ESI).
Kinetic stability
In order to gain further insight into the kinetic stability of the
CAl3E clusters, we have found the corresponding transition
states connecting the local minima on the singlet PESs (Fig. 6).

1
Fig. 6 Energy profiles for the isomerization of the CAl3E (E = P, As, Sb, Bi) clusters. The energy dierences in kcal mol are computed at the B3LYP/aug-
cc-pVTZ level and the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ (in parentheses) level of theory.

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Let us concentrate on the first two lowest barriers. The transi-
tion barriers for the P and As systems are related to the
formation of structures 2 and 3 (see Fig. 2) via TS12 and TS13,
respectively. In both cases, the lowest barrier connects 1 with the
planar tricoordinate carbon system 3. This transformation has a
20.6 (P) and 21.9 (As) kcal mol 1 activation energy (at the
CCSD(T)//B3LYP level). The distribution of the local minima
changes in the case of the Sb and Bi clusters and it is also
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reflected in the kinetic stability. The activation energy related to
the isomerization between structures 1 and 3 is comparable to
that of their lightest analogues. However, for Sb and Bi, the
lowest barrier (17.2 and 21.5 kcal mol 1, respectively) corresponds
to the rearrangement of 1 leading to 5. The transformation of 1
into 2 involves barriers of 24.9 (Sb) and 25.1 (Bi) kcal mol 1. These
results indicate that the CAl3E clusters seem to be thermo-
dynamically and kinetically viable in the gas phase. Of course,
other competitive processes like dimerization or oxidation could
prevent their formation.
The kinetic stability of these ptC clusters is reinforced by the
BO-MD simulations. At 323 and 373 K, the root-mean-square
deviation (RMSD) fluctuations computed at the B3LYP/6-31G(d)
level are small (see Fig. S2, ESI), indicating that the ptC
structure with a CQE double bond is persistent at least
for 30 ps.
Summary and outlook
Our calculations show that the global minimum structure of
the CAl3E (E = P, As, Sb, Bi) clusters contains a planar tetra-
coordinate carbon atom. These ptC clusters are both thermo-
dynamically and kinetically viable species in the gas phase. Cui
et al. coined the term unbalanced ligand environment in
order to explain the localization in CAl3N.16 The substitution of
N by other group 15 elements also induces an unbalanced 18 P. Le Floch, Coord. Chem. Rev., 2006, 250, 627.
environment, leading to the formation of a CQE double bond
in these 18 valence electron ptC species. The presence of a CQE
double bond is supported by the Wiberg bond indices, the
AdNDP analysis, and the magnetic response. The ability to form
a CQE double bond clearly decreases down group 15. These
analyses also reveal that the presence of a group 15 element
does not alter the s-electron distribution. These ptC systems
do not delocalize the lone pair at all. In other words, for an 18
valence electron ptC cluster, while the s-electron distribution
remains, it is not necessary to fully delocalize the 2pz carbon
orbital; it is enough to form a localized double bond.
Acknowledgements
This work was funded by the National Natural Science Founda-
tion of China (No. 21273093, 21473069, 21073074). The work
in Merida was supported by the Moshinsky Foundation. RI
acknowledges Fondecyt for the financial support via the project
No. 3140439. We thank Prof. Zhi-Xiang Wang for providing us
with the BOMD analysis code.
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