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Unsupported Donor−Acceptor Complexes of Noble Gases with

Group 13 Elements
Lakhya J. Mazumder, Amlan J. Kalita, Shahnaz S. Rohman, Chayanika Kashyap, Sabnam S. Ullah,
Indrani Baruah, Ashapurna Boro, Ankur K. Guha,* and Pankaz K. Sharma*
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ABSTRACT: Unsupported donor−acceptor complexes of noble gases (Ng) with group 13

elements have been theoretically studied using density functional theory. Calculations reveal that
heavier noble gases form thermodynamically stable compounds. The present study reveals that no
rigid framework is necessary to stabilize the donor−acceptor complexes. Rather, prepyramidaliza-
Downloaded via 42.108.33.154 on October 3, 2021 at 16:25:46 (UTC).

tion at the Lewis acid center may be an interesting alternative to stabilize these complexes.
Detailed bonding analyses reveal the formation of two-center−two-electron dative bonding, where
Ng atoms act as a donor.

■ INTRODUCTION
Noble gases (Ng) having a complete outer electronic shell exist
actions without the use of steric protection? Is it possible for
the noble gases to form a usual two-center−two-electron
bond? To answer these questions, we have carried out
as individual atoms. They are not likely to be involved in
quantum chemical calculations on donor−acceptor complexes
chemical bonding. Extreme conditions such as strong oxidizing
between noble gases and group 13 elements (Scheme 1). The
agents, such as F2, or extreme activation by laser irradiation,
electric discharge, etc. are required, and the products are
trapped in low-temperature matrices. After the first synthesis of Scheme 1. Pyramidal Lewis Acidic Boron Centers
Considered in This Study
xenon compounds by Bartlett1 and Hoppe2 in 1962, many
compounds featuring Ng−X (X = halogen, oxygen, sulfur,
nitrogen, and carbon) bonds have been isolated and
characterized.3 The chemistry of krypton and other noble
gases has been thoroughly reviewed.4−6
Noble-gas compounds are generally metastable and readily
dissociate into their atomic form. The bonding situation in the
stable compound, NgF2, is described as three-center−four-
electron bonds,7 where terminal fluorine atoms also participate
in the bond formation. Similar bonding situation has also been
described in Au+−Ng−F−.8 The other possibility of three-
center−four-electron bond formation is through donor−
acceptor interaction, as pointed by Mück et al.9 Such a
bonding situation can describe the experimentally synthesized bond dissociation energies (BDEs) of BH3−Ng complexes are
very low, which might be due to the requirement of large
compounds such as HArF10 and HKrF,11 which were prepared
preparation energy by planar boron acceptors to achieve
by the photolysis of HF in argon and krypton matrices.
pyramidal conformation upon complexation with noble gases.
However, calculations reveal that both HArF and HKrF
We, therefore, envisioned that prepyramidalized boron center
molecules are metastable due to exothermic dissociation into
(B1−B8, Scheme 1) will be effective to stabilize such donor−
free Ng and HF.12 To overcome the problem of dissociation,
acceptor complexes. It should be noted that Mück et al. have
Mück et al. have theoretically proposed the use of a rigid cage,
also used a prepyramidalized acceptor center in their study.9
such as a push−pull cryptand ligand, which contains both
donor (D) and acceptor (A) sites.9 Their calculations reveal
that the dissociation process, A−Ng−D = Ng + AD (A = Received: January 29, 2021
acceptor and D = donor), is endergonic (ΔG > 0), indicating Accepted: March 5, 2021
that the cryptand-encapsulated noble-gas compounds are Published: March 16, 2021
thermodynamically stable.
Is there a possibility of formation of thermodynamically
stable noble-gas compounds featuring donor−acceptor inter-
© 2021 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsomega.1c00543
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Figure 1. BP86-D3(BJ)/def2-TZVPP optimized geometries of the donor−acceptor complexes. Bond lengths are in Å. Values in italics refer to the
BP86/def2-TZVPP level.

Table 1. Wiberg Bond Index (WBI), Force Constant (k in mDyne Å−1), Difference in Pyramidalization Angle at B (ΔθB, in
Degrees), and Bond Dissociation Energies (kJ mol−1) of the Donor−Acceptor Complexesa
molecule bond wib force constant (k) difference (ΔθB) BDE
B1−X B−Ar 0.071 0.0281 0.6 5.8
B−Kr 0.134 0.0234 1.5 9.6
B−Xe 0.240 0.0312 3.3 16.7
B2−X B−Ar 0.078 0.0172 0.9 6.2
B−Kr 0.134 0.0257 1.5 10.4
B−Xe 0.253 0.0230 2.7 18.4
B3−X B−Ar 0.071 0.0262 0.6 6.7
B−Kr 0.134 0.0177 1.2 10.4
B−Xe 0.221 0.0107 2.4 18.0
B4−X B−Ar 0.086 0.0350 0.6 7.5
B−Kr 0.145 0.0238 1.2 11.7
B−Xe 0.284 0.0343 2.9 20.0
B5−X B−Ar 0.053 0.0251 0.6 4.4
B−Kr 0.083 0.0189 0.9 6.2
B−Xe 0.137 0.0194 1.5 10.0
B6−X B−Ar 0.049 0.0322 0.1 5.8
B−Kr 0.085 0.0247 0.2 9.2
B−Xe 0.167 0.0242 1.2 15.9
B7−X B−Ar 0.395 (0.381) 0.314 (0.237) 9.9 (9.9) 20.0 (8.3)
B−Kr 0.536 (0.516) 0.445 (0.362) 12.9 (12.9) 35.9 (21.0)
B−Xe 0.667 (0.650) 0.512 (0.443) 15.9 (15.9) 61.5 (40.9)
B8−X B−Ar 0.226 (0.125) 0.099 (0.025) 6.0 (3.3) 9.6 (0.5)
B−Kr 0.397 (0.362) 0.206 (0.162) 10.5 (9.9) 21.7 (6.5)
B−Xe 0.591 (0.566) 0.557 (0.454) 15.3 (15.3) 44.3 (22.8)
a
Values within parentheses refer to the BP86/def2-TZVPP level.

The strategy of using prepyramidalized boron center has been metal boron donor−acceptor complexes.13 Recently, our group
utilized by Borthakur et al. in stabilizing unsupported transition has reported pyramidal tricoordinate boron centers (B7−B8,
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Scheme 1) stabilized by pnictogens.14 Our calculation revealed

that P3B and As3B molecules are global minima with extreme
pyramidalization at the boron center with enhanced Lewis
acidity.15 Therefore, these prepyramidalized boron centers are
quite likely to form stable Ng−B donor−acceptor complexes.
Herein, we have carried out density functional calculations to
investigate the possibility of formation of donor−acceptor
complexes between experimentally known prepyramidalized
boron centers (B1−B6)13 and our previously proposed
molecules B7−B8.14

■ COMPUTATIONAL DETAILS
All of the structures were fully optimized without any
symmetry constraints at the BP86-D3(BJ)/def2-TZVPP
level.16 This theory includes third generation of Grimme’s
Figure 3. (a) Bonding molecular orbital of the complexes featuring
empirical dispersion with the Becke−Johnson damping Ng → B dative bond and (b) density difference plot of the donor−
function.17 This method is known to produce very good acceptor adducts (red = density increment, blue = density depletion).
geometries, and the dispersion correction produces bond
dissociation energies with least mean deviation.18 Harmonic Table 2. Charge Decomposition Analysis (CDA) Results of
frequency calculations were also performed to understand the the Adductsa
nature of the stationary state. All structures were found to be at
their local minima with all real values of the Hessian matrix. All molecules donation (d) repulsion (r) residue (Δ) |q|
of these calculations were performed using the GAUSSIAN 16 B1−Ar 0.032 −0.304 −0.020 0.043
suite of program.19 All energies are zero-point- and thermal- B1−Kr 0.021 −0.301 −0.021 0.083
corrected. Basis set superposition error (BSSE) is not B1−Xe 0.011 −0.307 −0.023 0.154
considered as it is reported that while using DFT-D methods B2−Ar 0.042 −0.303 −0.019 0.049
with triple zeta quality basis set, BSSE correction can be B2−Kr 0.016 −0.311 −0.021 0.084
avoided.20 The electronic structures of these molecules were B2−Xe 0.021 −0.308 −0.021 0.166
analyzed using natural bond orbital (NBO) analyses,21 B−Ar 0.039 −0.309 −0.020 0.044
quantum theory of atoms in molecules (QTAIM),22 and B3−Kr 0.034 −0.301 −0.023 0.078
electron localization function (ELF)23 at the BP86-D3(BJ)/ B3−Xe 0.012 −0.302 −0.018 0.143
def2-TZVPP level. QTAIM and ELF analyses were performed B4−Ar 0.043 −0.303 −0.019 0.054
using Multiwfn program code.24 Charge decomposition B4−Kr 0.039 −0.313 −0.021 0.091
analysis (CDA)25 was performed using Multiwfn program B4−Xe 0.023 −0.304 −0.024 0.187
code. The force constant k was calculated using the compliance B5−Ar 0.029 −0.306 −0.020 0.033
program code.26 B5−Kr 0.024 −0.307 −0.022 0.053
To investigate the effect of dispersion on the molecular B5−Xe 0.017 −0.303 −0.021 0.089
geometry, bond dissociation energy, and electronic structure, B6−Ar 0.022 −0.304 −0.018 0.033
some of the molecules were optimized at BP86 functional B6−Kr 0.015 −0.301 −0.019 0.058
without D3 correction. B6−Xe 0.020 −0.310 −0.020 0.117

■
B7−Ar 0.147 −0.300 −0.002 0.273
RESULTS AND DISCUSSION B7−Kr 0.175 −0.311 −0.001 0.387
B7−Xe 0.210 −0.301 −0.002 0.507
Figure 1 shows the optimized geometries of the donor− B8−Ar 0.094 −0.310 −0.013 0.158
acceptor complexes. Lighter noble gases He and Ne form very B8−Kr 0.136 −0.305 −0.011 0.285
B8−Xe 0.186 −0.306 −0.010 0.446
a
Here, donation means donation from Ng to empty orbital of B. The
magnitude of charge transfer |q| is also tabulated. Back-donation from
BR3 fragment to Ng gases is zero in all cases.

weak complexes, and hence are not discussed in the text.

However, heavier noble gases Ar, Kr, and Xe form stronger
complexes, and hence are emphasized throughout the text.
With noble gases Ar, Kr, and Xe, B−Ng bond lengths are
slightly longer than single bonds in comparison to the self-
consistent radii of Pyykkö,27 which might be due to the dative
nature of these bonds. The shortest B−Ng distances are found
for the B7 adducts, while the longest ones are found for the B6
adduct. B8 also forms a stronger B−Ng interaction as revealed
by their bond distances, bond dissociation energies, and force
Figure 2. Correlation plot between change in pyramidalization angle constant values (Table 1). However, the B−Ng bonds of the
(ΔθB) and BDE values for the complexes with xenon. B8−Ng adducts are slightly weaker than that of B7 but
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Figure 4. (a) Laplacian plot of electron density (red = charge concentration, blue = charge depletion) and (b) electron localization function in the
P−B−Xe plane of the B7−Xe molecule.

Table 3. Calculated Electron Density ρ, Laplacian of Electron Density ∇2ρ, Local Electronic Energy Density H(r), and ELF
Values at the B−Ng Bond Critical Pointa
molecule bond ρ ∇2ρ H(r) ELF
B1−X B−Ar 0.010 0.029 −0.001 0.051
B−Kr 0.015 0.030 −0.002 0.101
B−Xe 0.021 0.028 −0.002 0.198
B2−X B−Ar 0.011 0.031 −0.001 0.052
B−Kr 0.015 0.031 −0.002 0.095
B−Xe 0.022 0.029 −0.002 0.197
B3−X B−Ar 0.010 0.030 −0.001 0.048
B−Kr 0.014 0.031 −0.000 0.088
B−Xe 0.019 0.028 −0.001 0.172
B4−X B−Ar 0.012 0.032 −0.003 0.058
B−Kr 0.016 0.032 −0.003 0.103
B−Xe 0.024 0.029 −0.003 0.225
B5−X B−Ar 0.009 0.024 −0.002 0.043
B−Kr 0.011 0.024 −0.001 0.075
B−Xe 0.014 0.021 −0.002 0.144
B6−X B−Ar 0.007 0.021 −0.002 0.035
B−Kr 0.010 0.023 −0.003 0.064
B−Xe 0.014 0.024 −0.003 0.139
B7−X B−Ar 0.047 (0.045) 0.029 (0.028) −0.022 (−0.019) 0.262 (0.268)
B−Kr 0.057 (0.054) 0.004 (0.004) −0.032 (−0.028) 0.342 (0.358)
B−Xe 0.065 (0.062) −0.030 (−0.026) −0.037 (−0.033) 0.516 (0.526)
B8−X B−Ar 0.029 (0.017) 0.040 (0.035) −0.005 (−0.000) 0.218 (0.107)
B−Kr 0.043 (0.039) 0.018 (0.023) −0.014 (−0.011) 0.385 (0.361)
B−Xe 0.058 (0.054) −0.014 (−0.007) −0.026 (−0.022) 0.552 (0.545)
a
All bond critical point values are in au. Values within parentheses refer to the BP86/def2-TZVPP level.

stronger than the rest. Dispersion plays a major role in these donor−acceptor complexes. The WBI values as well as the
molecules as evident from Figure 1 and Table 1. Pure BP86/ force constant values increase from Ar to Xe. Similarly, the
def2-TZVPP without D3 correction resulted in longer B−Ng bond dissociation energy (BDE) values also increase from Ar
bonds with lower bond dissociation energies for B7 and B8 to Xe. The lowest BDE value is found for the B5−Ar complex,
molecules. while the highest value is found for the B7−Xe complex,
The bond strengths are measured in terms of their Wiberg reaching a maximum value of 61.5 kJ mol−1. There is a
bond indices (WBI) as well as their force constant, k, values. dramatic increase in WIB, k, and BDE for the complexes with
Table 1 contains some important numerical data of the B7 and B8. The increase in all of these parameters with B7 and
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■
http://pubs.acs.org/journal/acsodf Article

B8 can be rationalized by the fact that both these acceptor CONCLUSIONS

molecules feature a highly pyramidalized boron center.14 The Quantum chemical calculations have been carried out to
high degree of pyramidalization imparts higher Lewis acidity to propose a design strategy to realize the formation of
the boron center,14 which in turn helps in stronger dative bond unsupported donor−acceptor complexes between noble gases
formation with the noble gases. The change in pyramidaliza- with group 13 Lewis acids. The bonding feature shows the
tion angle at B (ΔθB), measured as the difference in hitherto unexplored two-center−two-electron-type interaction.
pyramidalization angle at B in the free acid and in the Calculations reveal that heavier noble gases form stable
donor−acceptor complex, is maximum with B7 and B8, for donor−acceptor complexes with sizable bond dissociation
which higher BDE values were found. This implies that B7 and energies. This study also highlights the fact that prepyramid-
B8 are more flexible to form stronger donor−acceptor alization of the Lewis acidic center is an interesting strategy to
complexes. A good correlation has been found between the realize stable donor−acceptor complexes of noble gases.
change in pyramidalization angle (ΔθB) and BDE values Detailed bonding analyses reveal the donor−acceptor inter-
(Figure 2). action in these molecules, where noble gases act as electron
We then turned our attention to investigate the electronic pair donors. Topological analyses within the realm of QTAIM
structure of the complexes. Figure 3 shows the frontier Kohn− and ELF reveal that these bonds have significant covalent
Sham molecular orbital as well as the density difference plot of character and are polar. The results presented in this study will
the complexes. The Ng−B bonding molecular orbitals are shed light on the possibility of realizing unsupported donor−
located at either HOMO-10 or HOMO-11 with a larger acceptor complexes of noble gases in future, and experimental
contribution from the Ng (80−83%) p orbital, indicating the realization is yet to be achieved.
Ng → B donor−acceptor two-center−two-electron bond. The
density difference plot also reveals the same phenomenon. The
density increment zone (red) is located at the B center, while
■ ASSOCIATED CONTENT
* Supporting Information
sı
the depletion zone (blue) is located at Ng gases. Thus, the The Supporting Information is available free of charge at
bonding situation is exactly of donor−acceptor type as https://pubs.acs.org/doi/10.1021/acsomega.1c00543.
expected. To quantify the donor−acceptor interaction, we
have carried out charge decomposition analyses25 of the Cartesian coordinates of all of the molecules along with
adducts. As the fragments are closed-shell species, the their total energies in au (PDF)
application of CDA to quantify charge donation/back-
donation will be appropriate. Table 2 contains the numerical
data. The CDA results clearly quantify that there is significant
■ AUTHOR INFORMATION
Corresponding Authors
donation from the Ng fragment to the empty orbitals on B. Ankur K. Guha − Advanced Computational Chemistry Centre,
The amount of donation increases for B7 and B8 complexes Cotton University, Guwahati 781001, Assam, India;
compared to others. This indicates that the boron atoms in B7 orcid.org/0000-0003-4370-8108;
and B8 are better acceptors. The repulsive terms are all Email: [email protected]
negative, indicating reduced closed-shell repulsion.25 Table 2 Pankaz K. Sharma − Advanced Computational Chemistry
also contains the magnitude of charge transfer |q| from Ng to Centre, Cotton University, Guwahati 781001, Assam, India;
the Lewis acidic boron centers. The values of |q| are found to Email: [email protected]
be higher, with B7 and B8 indicating their stronger accepting
ability. Authors
The bonding in these adducts is further analyzed using Lakhya J. Mazumder − Advanced Computational Chemistry
quantum theory of atoms in molecules (QTAIM)22 and Centre, Cotton University, Guwahati 781001, Assam, India
electron localization function (ELF).23 Figure 4 shows the Amlan J. Kalita − Advanced Computational Chemistry Centre,
Laplacian plot of electron density and electron localization Cotton University, Guwahati 781001, Assam, India
function in the P−B−Xe plane for the B7−Xe molecule as a Shahnaz S. Rohman − Advanced Computational Chemistry
representative case. QTAIM reveals a bond path (Figure 4a) Centre, Cotton University, Guwahati 781001, Assam, India
and an associated (3, −1) bond critical point22 between B−Xe Chayanika Kashyap − Advanced Computational Chemistry
atoms, which indicates the bonding interaction between the Centre, Cotton University, Guwahati 781001, Assam, India
pair of atoms. ELF analyses (Figure 4b) also reveals Sabnam S. Ullah − Advanced Computational Chemistry
localization of a significant amount of electron density between Centre, Cotton University, Guwahati 781001, Assam, India
the B and Xe atomic basins. Indrani Baruah − Advanced Computational Chemistry Centre,
Cotton University, Guwahati 781001, Assam, India
Table 3 contains the topological parameters of electron
Ashapurna Boro − Advanced Computational Chemistry
density for the B−Ng bond. There is a significant electron
Centre, Cotton University, Guwahati 781001, Assam, India
density, ρ, at the B−Ng bond critical points, which increases
with heavier noble gases. The B7−Xe adduct has the highest Complete contact information is available at:
electron density (0.065 au) at the B−Xe bond critical point https://pubs.acs.org/10.1021/acsomega.1c00543
among all of the studied compounds. It should be noted that
the calculated BDE for this adduct was also found to be highest Notes
(Table 1). The Laplacian of electron density, ∇2ρ, is positive in The authors declare no competing financial interest.
all cases, and the total electronic energy density, H(r), is
negative, suggesting that these bonds should be described as
polar with significant covalency.28 Significant values of electron
■ ACKNOWLEDGMENTS
A.K.G. thanks the Science and Engineering Research Board
localization function (ELF) are also observed. (SERB), Government of India, for providing financial
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■
38, 3098−3100. (b) Perdew, J. P. Density-functional approximation
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ACS Omega 2021, 6, 8656−8661