Accepted Article

Title: Stable Noble Gas Compounds Based on Superelectrophilic

Anions [B12(BO)11]- and [B12(OBO)11]-

Authors: Tao Yang, Jianzhi Xu, Mengyang Li, Song Xu, Gerui Pei,
Xintian Zhao, Chuncai Kong, Zhimao Yang, and Gao-Lei Hou

This manuscript has been accepted after peer review and appears as an
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content of this Accepted Article.

To be cited as: ChemPhysChem 10.1002/cphc.202100391

Link to VoR: https://doi.org/10.1002/cphc.202100391

01/2020
ChemPhysChem
ARTICLE
Stable Noble Gas Compounds Based on Superelectrophilic Anions
[B12(BO)11]− and [B12(OBO)11]−
Jianzhi Xu,‡[a] Mengyang Li,‡[a] Song Xu,[a] Gerui Pei,[a] Xintian Zhao,[a] Chuncai Kong,[a] Zhimao Yang,[a]
Tao Yang*[a] and Gao-Lei Hou*[a,b]
[a] MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi’an Jiaotong University, Xi’an 710049,
Shaanxi, China. Email: taoyang1@xjtu.edu.cn
[b] Quantum Solid-State Physics, Department of Physics and Astronomy, KU Leuven, Celestijnenlaan 200D, 3001 Leuven, Belgium. Email:
gaolei.hou@kuleuven.be
‡ These authors contributed equally.
Abstract: Superelectrophilic monoanions [B12(BO)11]− and
[B12(OBO)11]−, generated from stable dianions [B12(BO)12]2− and
[B12(OBO)12]2−, show great potential to bind noble gases (Ngs). The
binding energies, quantum theory of atoms in molecules (QTAIM),
natural population analysis (NPA), energy decomposition analysis
(EDA), and electron localization function (ELF) were carried out to
understand the B−Ng bond in [B12(BO)11Ng]− and [B12(OBO)11Ng]−.
The calculated results reveal that heavier noble gases (Ar, Kr, and
Xe) bind covalently with both [B12(BO)11]− and [B12(OBO)11]− with large
binding energies, making them potentially to be prepared in
experiments. Only [B12(OBO)11]− could form a covalent bond with
helium or neon, however, the small binding energy of [B12(OBO)11He]−
may pose a challenge for its detection in the experiment.
Introduction
Noble gases (Ngs) are the least reactive elements that hardly
form chemical bonds with other atoms in the periodic table,
because Ngs have their valence electron shells fully filled.
Prediction and synthesis of stable Ng-containing compounds are
the hot research spots in past decades. [1] In 1962, Bartlett
synthesized the first Ng compound XePtF6,[2] and later the new
field “Noble Gas Chemistry” emerges. A number of compounds
containing heavier Ngs (Kr, Xe, and Rn) have been predicted
theoretically and synthesized experimentally. [3−6] In 2000,
Khriachtchev et al.[7] reported the first neutral stable argon
compound, HArF, which shows strong covalent bond between H
and Ar atoms but ionic character between Ar and F atoms. [8]
Thereafter, several argon-containing cationic compounds,
including [ArB3O4]+, [ArB3O5]+, [ArB4O6]+, and [ArB5O7]+ were
successfully prepared,[9] which leaves helium and neon the
remaining elements whose stable complexes under atmospheric
pressure have not been reported.
Helium (He) possesses the smallest atomic radius, lowest
polarizability, and highest ionization energy among all the Ngs. To
date, only a few compounds directly involving helium have been
reported under extreme conditions like high pressure.[10−13] HeH+,
first observed in laboratory in the 1920s, [14] was recently detected
in space[15] and has been recognized as the first molecule after
Big Bang.[16] In 2017, Na2He with a fluorite-type structure was
synthesized under high pressure (>113 GPa), [10] and it shows that
high pressure drives electron shifting to be effective.[17] Other He-
containing compounds, such as He(N2)11[11] and FHeX– (X = O and
S)[12,13] have also been reported under extreme conditions.
Several examples of HHeF, FHeX–, and H3CHeF have shown that
1
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10.1002/cphc.202100391
Accepted Manuscript
when He is substituted by Ne atom, the Ne-containing compounds
are less stable than their He-containing counterparts.[18] Neon
possesses occupied p orbitals compared with helium, which
results in higher orbital repulsion and less electrostatic interaction.
That makes Ne-containing compounds unstable or only
marginally stable. A few weak Ne-containing complexes, such as
NeBeCO3, NeBeS, and NeBeSO2, have been observed in low-
temperature matrix experiments.[19−21] Whether it is possible to
prepare compounds containing helium or neon at atmospheric
pressure has aroused wide interest.
In recent years, superelectrophilic anions that can covalently
bind Ngs were discovered[22–25] and opened up new opportunities
for making Ng-containing compounds. A superelectrophilic anion,
negatively charged as a whole but positively charged at the
binding site, can bind a Ng atom. [24] For example, [B12Cl11]− can
form covalent compounds with Kr and Xe, [22] and
superelectrophilic monoanion [B12(CN)11]−, generated from the
most stable dianion [B12(CN)12]2− reported to date,[26] binding
argon via a covalent B−Ar bond was observed at room
temperature.[23] [B12(CN)11Ne]−, with a binding energy of 8.9
kJ/mol, gives the first example of Ne-containing anion within a
covalent B−Ne bond under atmospheric pressure. [25] In the case
of [B12(CN)11He]−, a binding energy of 1.3 kJ/mol may pose a
great challenge for its generation in experiment, however, the
B−He bond has been predicted to show some covalent character.
Recently, a systematical study on the reactivity of [B12X11]– (X = F,
Cl, Br, I, CN) towards Ngs were carried out and the results show
that Ng-independent reactivity trend follows the sequence:
[B12F11]– ≈ [B12I11]– < [B12Br11]– ≈ [B12Cl11]– << [B12CN11]–.[27] The
reactivity of those monoanions towards Ngs can be attributed to
binding-site boron atom in [B12X11]– and steric effects.
[B12(BO)12]2− has been studied theoretically with a second
electron binding energy of 5.89 eV, which is even higher than that
of [B12(CN)12]2− (ca. 5.28 eV).[28] The higher stability of
[B12(BO)12]2− compared to [B12(CN)12]2− is originated from the
larger highest occupied molecular orbital-lowest unoccupied
molecular orbital (HOMO-LUMO) gap and the weaker π orbital
interaction between B12-cage and the BO ligands. The more
stable the dianion is, the more supereletrophilic generated
monoanion is.[24] Such findings lend promising guidance to design
other superelectrophilic anions from their stable dianions, in
particular those B12-cage based ones.
In this study, we report two designer dianions [B12X12]2– (X =
BO, OBO (or BO2)) that are electronically stable. BO/BO– ligands
are isoelectronic to CN/CN– ligands and their remarkable
structural and chemical integrity as ligands have been
ChemPhysChem 10.1002/cphc.202100391

ARTICLE
systematically studied.[29] The negative ion photoelectron type.[52,53] As a supplement to further illustrate the bonding nature, electron
spectroscopy experiments of BO– and OBO– measured their localization function (ELF)[54] was presented to investigate electron
electron affinities respectively to be 2.51 and 4.46 eV, suggesting localization character. ELF is within the range of [0, 1], and a large ELF
value means that electrons are greatly localized, indicating that there is a
their great stabilities and possibilities as inorganic ligands. [30-33]
covalent bond, a lone pair, or inner shells of the atom involved.
Based on theoretical analysis of B−Ng bond, we found that both
[B12(BO)11]− and [B12(OBO)11]− can form covalent bonds with Ar,
Kr, and Xe. Only [B12(OBO)11]− can form covalently bonded
compounds with He and Ne, although the experimental
Results and Discussion
preparation of [B12(OBO)11He]− with small binding energy will be
The optimized geometries at the PBE0/6-311+G(2d) level are
challenging.
presented in Figure 1a–b. Their one-ligand loss monoanions and
corresponding neutrals are shown in Figure S1 in the SI. It is
found that the average B–B and B–O bond lengths in [B12(BO)12]2–
Computational Methods are 1.66 and 1.21 Å, respectively. Comparing with [B 12(BO)12]–

Accepted Manuscript
and B12(BO)12, the charge states have little effect on those bond
The geometry optimizations were carried out using Gaussian09 software
lengths, demonstrating the high rigidity and stability of the
package.[34] Hybrid density functional theory (DFT) with the PBE0
functional[35] and 6-311+G(2d) basis set were used for geometry framework. The ligands BO in [B12(BO)12]2– point radially from the
optimization of [B12(BO)12]2–/1–/0 and [B12(OBO)12]2–/1–/0. The PBE0 center to the outer. In [B12(OBO)12]2–, the ligands OBO bind the
functional was chosen because Warneke et al.[36] found that it can well B12-cage with ∠BOB of 136° (Figure 1b), and the ligand OBO
reproduce experimental geometries of B12-cage clusters, and the retains its integrity as a typical superhalogen.[55,56]
calculated vertical detachment energies also give better agreement with
the experimental trend. The geometries were plotted by using CYLview20
software.[37] The first electron affinity (EA1) and second electron affinity
(EA2) of B12(BO)12 and B12(OBO)12 were calculated based on the optimized
geometries. All clusters, except B12(BO)12, are free from imaginary
frequency. The imaginary frequency of B12(BO)12 has no influence on its
EA2, which assesses the electronic stability of its corresponding dianion.

The more stable parent dianions will generate the more electrophilic
monoanions to stabilize Ng-containing compounds. To understand the
dynamic stability of the dianions, ab initio molecular dynamics (AIMD)
simulations were performed using the Nose-Hoover heat bath scheme[38]
as implemented in the Vienna Ab-initio Simulation Package (VASP)[39,40]
with the average temperature of the system at 1000 K and time step of 1
femtosecond (fs).

The binding energies of [B12(BO)11]− with Ngs were calculated at

PBE0/6-311+G(2d), B3LYP/def2-TZVPPD,[41,42] ωB97XD/def2-
TZVPPD,[43,44] PBE0-GD3BJ/6-311+G(2d), B3LYP-GD3BJ/def2-TZVPPD,
and DLPNO-CCSD(T)/cc-pVTZ,[45,46] respectively. Our comparisons and
previous studies[23,25] suggested employing the exchange-correlation
functional B3LYP with D3 dispersion correction combined with the def2-
TZVPPD basis set to calculate the binding energies of Ngs to
[B12(OBO)11]−.

Quantum theory of atoms in molecules (QTAIM)[47] analysis was used

to investigate the bonding features between boron and Ng atoms. The
Multiwfn software[48] was used to calculate the electron density (ρbcp) and
energy density (Hbcp) at the bond critical points (BCPs). Also, the
delocalization index (δ) was discussed as a measure of covalent order.
Electron density was calculated with a step size of 0.1 Bohr. Natural
population analysis (NPA)[49] was used to obtain the atomic charge.
Energy decomposition analysis (EDA),[50] conducted with the
ADF2019 software package,[51] was employed at the B3LYP-D3BJ/TZ2P
level to partition the bonding interaction energy ΔEint. By using EDA, the
bonding interactions between two fragments could be divided into four
components (eq 1).
Δ𝐸int = Δ𝐸elstat + Δ𝐸Pauli + Δ𝐸orb + Δ𝐸disp (1)
The term ΔEorb is related to charge transfer, electron-pair bonding, and
polarization effects; ΔEelstat is classical electrostatic interaction among
fragments; ΔEdisp corresponds to dispersion forces between interacting
atoms; ΔEPauli is the repulsion among occupied orbitals. The EDA-NOCV
method, which combines the EDA with the natural orbitals for chemical
valence (NOCV) method, was employed to visualize the interaction
2
Figure 1. Optimized structures of the ground state of (a) [B12(BO)12]2− and (b)
[B12(OBO)12]2−. Temperature fluctuation, with respect to time, of an AIMD
simulation of (c) [B12(BO)12]2− and (d) [B12(OBO)12]2−. Total energy fluctuation,
with respect to time, of an AIMD simulation of (e) [B12(BO)12]2− and (f)
[B12(OBO)12]2−.
Table 1 summarizes the calculated EAs of B12(BO)12 and
B12(OBO)12. The experimentally measured EAs of CN, BO, and
OBO are 3.86, 2.51, and 4.46 eV, respectively.[30,57] From the
viewpoint of electron binding ability of the ligands, it is expected
that B12(OBO)12 has the highest EAs, while B12(BO)12 has the
lowest. Surprisingly, their calculated EAs show the reverse, and
the calculated EA2 are 5.94, 5.47, and 4.65 eV for B12(BO)12,
B12(CN)12, and B12(OBO)12, respectively. Such surprising
observation can be attributed to two reasons. First, B12(OBO)12
has a buckling structure compared with B12(BO)12. Second,

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ChemPhysChem 10.1002/cphc.202100391

ARTICLE
Table 1. Electron affinities (in eV) of the studied molecules at the PBE0/6- employ the B3LYP-D3BJ/def2-TZVPPD to calculate the binding
311+G(2d) level of theory. energies between Ngs and [B12(OBO)11]−.
Optimized geometries of [B12(BO)11Ng]− and [B12(OBO)11Ng]−
Species B12(CN)12 B12(BO)12 B12(OBO)12 are presented in Figure 2, and both [B12(BO)11]− and [B12(OBO)11]−
show strong binding ability with the heavier Ngs, including Ar, Kr,
EA1 8.81 (8.56[a]) 9.46(9.33[b]) 7.81
and Xe (Table 2). The bond lengths of heavier Ng−B are close to
EA2 5.47 (5.28[a]) 5.94(5.89[b]) 4.65 the sum of the covalent radii of Ng and B atoms (Figure 2 and
Table S3), indicating that the covalent interactions exist between
[a] The values are from ref. 26. [b] The values are from ref. 28. B and heavier Ng atoms. Notably, except helium atom, all the Ngs
bind more strongly to [B12(OBO)11]− than to [B12(BO)11]−, and the
charge population analysis (Table S2) suggests that the B 12-cage
binding energies of Ngs to [B12(OBO)11]− are close to those for
in B12(BO)12 tends to abstract more electron density from the BO
[B12(CN)11]− (Tables 2 and S7). Both [B12(CN)11Ar]− and
ligand, which makes the boron atom in B12-cage has negative
[B12(CN)11Ne]− have been observed experimentally in gas phase
charge distribution. On the contary, in B12(OBO)12, the OBO ligand

Accepted Manuscript
and characterized with covalent B–Ng bond.[23,25] Thus, it is
gains electron density from the B12-cage, leaving the B12-cage
expected that both [B12(OBO)11Ar]− and [B12(OBO)11Ne]− would
charged positive.
also be experimentally observable. More interestingly, the binding
To evaluate the thermodynamic stability of both dianions,
energies of He in both [B12(OBO)11He]− and [B12(BO)11He]− reach
AIMD simulations are performed. Figure 1c–f show that after 5000
−2.8 kJ/mol (Table 2), two times larger than that in [B12(CN)11He]−
simulation steps (5 picoseconds), the structures of both
(−1.3 kJ/mol).[25] The B–He bond length in [B12(OBO)11He]− is 1.50
[B12(BO)12]2– and [B12(OBO)12]2– only show slight deformation
Å, much smaller than that in [B12(BO)11He]− (2.51 Å) and slightly
compared to the ground state at 0 K, indicating their high
smaller than that in [B12(CN)11He]− (1.59 Å), as shown in Figure 2
thermodynamic stabilities. Temperature and energy fluctuate over
and Table S7. This bond length is larger than the sum of the
time in a steady-state, and after 1000 steps, the difference of the
covalent radii of B (0.84 Å) and He (0.28 Å),[59] but significantly
maximum and the minimum energies (ΔE) of [B12(BO)12]2− and
smaller than the sum of their van der Waals radii (B: 1.92 Å; He:
[B12(OBO)12]2− are 4.50 and 3.38 eV, respectively (Figure 1e and
1.40 Å).[60] Hence, it is expected that there is partial covalent
1f), further confirming their high-temperature stability.
bonding between B and He in [B12(OBO)11He]−. In addition, the
When a BO ligand in [B12(BO)12]2− or OBO ligand in
negative values of Gibbs free energy changes of these Ng-
[B12(OBO)12]2− precursors is removed, positively charged boron
containing compounds at low temperature (25 K) (Table S8)
atom in B12-cage while negatively charged for the whole
suggest that they are more likely to be synthesized at low
framework will be generated. The free positively charged boron
temperature conditions.
atom will change the direction of electric field [24] and exhibit high
Calculated NPA charge distribution and topological properties
reactivity towards weak nucleophiles,[58] which are the distinctive
based on QTAIM analysis confirm the charge-transfer character
features of superelectrophilic anion.
of [B12X11Ng]− (X = BO and OBO; Ng = He−Xe). According to
Ngs are the weakest nucleophiles in chemistry. Due to the
previous studies, heavier Ngs have higher tendency to form a
negative EAs of Ng atoms (Table S3), they have to shift their
covalent bond by σ donation, and our study agrees with this trend.
electron with partners to form chemical bonds. The binding
In Table 2, the electron density (ρbcp) and energy density (Hbcp) at
energies of Ngs to [B12(BO)11]− have been calculated using
the bond critical points (BCPs) from QTAIM analysis and the
different computational methods, including different functionals
delocalization index (δ) based on basin analysis are summarized.
and DLPNO-CCSD(T). The comparison (Tables S4–S6) allows to

Figure 2. Optimized structures of the ground state of [B12(BO)11Ng]– and [B12(OBO)11Ng]– (Ng = He – Xe). The structures were optimized at the B3LYP-D3BJ/def2-
TZVPPD level of theory.

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ChemPhysChem 10.1002/cphc.202100391

ARTICLE
Table 2. Calculated binding energies (ZPE corrected electronic energy), topological properties at the bond critical points and charge distribution at the B3LYP-
D3BJ/def2-TZVPPD level of theory.

B–Ng Bond NPA Charge

Species
Binding energy Free B in
Bond length (Å) ρbcp (e∙Å−3) Hbcp/ρbcp (Ha∙e−1) δ Bound Ng (e) Bound B (e)
(kJ∙mol−1) [B12X11]− (e)

[B12(BO)11He]− −2.8 2.51 0.04 0.18 0.04 0.040 0.918

[B12(BO)11Ne]− −5.5 2.51 0.07 0.10 0.07 0.043 0.870

−
[B12(BO)11Ar] −32.5 2.20 0.29 −0.48 0.34 0.314 0.587 0.803

[B12(BO)11Kr]− −51.2 2.26 0.35 −0.55 0.43 0.434 0.491

Accepted Manuscript
−
[B12(BO)11Xe] −77.2 2.37 0.41 −0.54 0.54 0.379 0.589

[B12(OBO)11He]− −2.8 1.50 0.31 −0.44 0.24 0.238 0.272

[B12(OBO)11Ne]− −8.8 2.11 0.15 −0.16 0.15 0.094 0.521

[B12(OBO)11Ar]− −66.2 2.01 0.42 −0.64 0.44 0.444 0.105 0.563

[B12(OBO)11Kr]− −94.7 2.12 0.46 −0.73 0.52 0.550 0.032

[B12(OBO)11Xe]− −134.0 2.28 0.50 −0.66 0.63 0.692 −0.056

Table 3. EDA results of all compounds using [B12X11]− (singlet, X = BO or OBO) and Ng (singlet) as interacting fragments at the B3LYP-D3BJ/TZ2P level of theory.
All values are in kJ∙mol−1.

Species ΔEorb ΔEelstat ΔEdisp ΔEPauli ΔEint %ΔEcov[a] %ΔEnon-cov[b]

[B12(BO)11He]− −3.9 −1.4 −3.1 5.8 −2.6 46.4% 53.6%

[B12(BO)11Ne]− −9.3 −5.3 −6.1 13.4 −7.3 44.9% 55.1%

−
[B12(BO)11Ar] −120.4 −57.2 −25.7 160.8 −42.5 59.2% 40.8%

[B12(BO)11Kr]− −166.7 −72.7 −34.2 205.4 −68.2 60.9% 39.1%

−
[B12(BO)11Xe] −226.8 −90.7 −45.9 261.2 −102.2 62.4% 37.6%

[B12(OBO)11He]− −109.0 −37.4 −6.0 142.8 −9.6 71.5% 28.5%

−
[B12(OBO)11Ne] −32.6 −18.1 −8.1 44.4 −14.4 55.4% 44.6%

[B12(OBO)11Ar]− −215.4 −88.0 −30.9 243.4 −90.9 64.4% 35.6%

−
[B12(OBO)11Kr] −260.2 −105.1 −41.2 282.3 −124.2 64.0% 36.0%

[B12(OBO)11Xe]− −318.1 −117.5 −56.2 319.5 −172.3 64.7% 35.3%

[a] %ΔEcov gives the percentage values of the covalent contribution (ΔEorb) to the total attractive interactions. [b] %ΔE non-cov gives the percentage values of the non-
covalent contribution (ΔEelstat + ΔEdisp) to the total attractive interactions.

Except for [B12(BO)11He]− and [B12(BO)11Ne]−, all values of Ng-
containing compounds in Hbcp/ρbcp are negative, implying a
covalent bonding character. That is consistent with the calculated
large value of ρbcp and δ. An interesting phenomenon is that even
lighter Ngs (He and Ne) binding with [B12(OBO)11]− also has
covalent character.
NPA results in Table 2 show that the atomic charge of the
binding-site boron atom in [B12(BO)11]− (+0.803 e) is much larger
than that in [B12(OBO)11]− (+0.563 e), demonstrating that
[B12(BO)11]− has stronger electrophilicity and may form a larger
charge gradient to exchange electron density with Ngs. However,
from the bond length, binding energy, and QTAIM results, He and
Ne may not be able to form stable covalent bonds with
[B12(BO)11]−. It can be found that in [B12(OBO)11He]− and
[B12(OBO)11Ne]−, He and Ne atoms are more positively charged
than those in [B12(BO)11He]− and [B12(BO)11Ne]−, which implies
that the binding-site boron atom in [B12(OBO)11]− abstracts more
electron density from the helium or neon atom. The heavier Ngs,
including Ar, Kr, and Xe, with larger atomic charge indicate a
considerable amount of charge redistribution, which can be
explained by strong covalent interactions between heavier Ngs
(Ar, Kr, and Xe) and B atoms. In addition, the Ngs located in a
“crater” among the five ligands, and some other interactions such
as dispersion and electrostatic interactions among surrounding
ligands should also exist.[23−25,61]
EDA was employed to partition the bonding interaction energy
between the two binding fragments into orbital interactions,
electrostatics, Pauli repulsion, and dispersion forces. Two

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ChemPhysChem
ARTICLE
Figure 3. The plane maps of ELF in [B12(BO)11Ng]− and [B12(OBO)11Ng]−. Red region represents large ELF value and black region small one.
different models have been considered for the EDA analysis. One
model uses the [B12X11]− (singlet, X = BO or OBO) and Ng (singlet),
indicating the donor-acceptor interaction between two fragments.
The other model uses [B12X11]2− (doublet, X = BO or OBO) and
Ng+ (doublet), which represents the electron-sharing single bond.
The numerical results of EDA analysis, including the ratio of
covalent (cov) and non-covalent (non-cov) interactions of two
fragments, are shown in Tables 3 and S9.
The smaller orbital interaction values in Table 3 for [B12X11]−
(singlet, X = BO or OBO) and Ng (singlet) reveal that the donor-
acceptor interaction model is more reasonable. The trends of
orbital interactions, electrostatics, Pauli repulsion, and dispersion
forces between fragments [B12X11]− (singlet) and Ngs (singlet) are
shown in Figure S3. The heavier Ngs (Ar, Kr, and Xe) all show
strong orbital interactions with boron atom in both [B 12(BO)11]− and
[B12(OBO)11]−, but the orbital interactions in [B12(OBO)11Ng]−
compounds are larger than those in the corresponding
[B12(BO)11Ng]− ones, as shown in Figure S3. This result indicates
that the covalent interaction between Ng and [B12(OBO)11]− is
stronger than that between Ng and [B12(BO)11]−, which is
consistent with the large binding energies in [B12(OBO)11Ng]−. The
large ratio of covalent interaction in these heavier Ng-containing
compounds in Table 3 demonstrates that all heavier Ngs can form
stable covalent bond with both [B12(BO)11]− and [B12(OBO)11]− and
the bonding strength between Ng and [B12(OBO)11]− is stronger.
However, when helium or neon atom binds with boron atom in
[B12(BO)11]−, covalent interactions contribute less than 50% to the
total attractive interactions between two fragments, which is in
agreement with their large B–Ng bond lengths. Nevertheless, if
He or Ne atom binds with [B12(OBO)11]−, the contribution from
covalent interactions is more than 55%. In particular, the orbital
interaction in [B12(OBO)11He]− contributes up to 71%, which is
even larger than that of heavier Ngs, indicating that He and B are
mainly bound by covalent bonding. Another interesting
phenomenon is that the ratio of covalent contribution in Table 3
increases from [B12X11He]− to [B12X11Xe]− (X = BO or OBO) except
for [B12(BO)11Ne]− or [B12(OBO)11Ne]−. The smaller ratio of
covalent interaction in the Ne−B bond probably suggests that
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10.1002/cphc.202100391
Accepted Manuscript
neon atom is more difficult to form a covalent bond than helium
atom.
The interaction between nucleophiles Ngs and
superelectrophiles [B12(BO)11]− or [B12(OBO)11]− is often regarded
as σ donor-acceptor interaction.[27] The deformation density is
used to visualize the charge transfer between two fragments.
Figure S4 shows the deformation density with the largest
contribution of dative bond and electron-sharing bond for
[B12(OBO)11]− and Ar. The deformation density shows that the B–
Ar σ dative bond is formed by σ donation from HOMO of Ar to the
unoccupied σ-type orbital at the binding-site boron atom.
In order to visualize the electronic behavior between B and
Ngs, the plane maps of ELF in [B12(BO)11Ng]− and
[B12(OBO)11Ng]− are presented in Figure 3. Except for
[B12(BO)11He]− and [B12(BO)11Ne]−, in which the electron localized
only around the B and He (or Ne) atoms, all the other Ng-
containing compounds show that the Ng atom does have certain
charge transfer with B atom. The stronger interactions with the
surrounding ligands (OBO) are due to the electrostatic
interactions caused by the buckling ligands which further stabilize
Ngs in the “crater”.
Conclusion
The superelectrophilic monoanions [B12(BO)11]− and
−
[B12(OBO)11] generated from their stable parent dianions
[B12(BO)12]2− and [B12(OBO)12]2− show strong binding ability
towards noble gases. Bonding analysis has revealed strong
covalent bonding between [B12(BO)11]− (or [B12(OBO)11]−) and
heavier noble gases (Ar, Kr, and Xe). These heavier Ng-
containing compounds can be experimentally synthesized
considering their large calculated binding energies. The
calculated binding energy of [B12(OBO)11Ne]− is close to that of
the reported [B12(CN)11Ne]−, suggesting that [B12(OBO)11Ne]−
could also be potentially synthesized. In contrast to
[B12(BO)11He]−, [B12(OBO)11He]− has larger extent of covalent
interaction between He and B atoms, but the small binding energy
ChemPhysChem 10.1002/cphc.202100391

ARTICLE
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Accepted Manuscript
Tonner, K. R. Asmis, J. Warneke, Chem. Eur. J. 2021, 27, DOI:
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Keywords: Stability • Noble gas element • Binding ability •
J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson,
Superelectrophilic • Covalent bond H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino,
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Accepted Manuscript

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Entry for the Table of Contents

Accepted Manuscript
Superelectrophilic anions [B12(BO)11]− and [B12(OBO)11]−,
generated from their stable dianions, show great binding ability
towards noble gas elements. Bonding analysis indicates that
B−Ng has covalent feature.

8
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