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OBCN isomerization and noble gas insertion

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2019, 21, 26311
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compounds of identical valence electron number
species: stability and bonding†
Mei Wen,a Zhuo Zhe Lib and An Yong Li *c

Received 8th September 2019,
Accepted 13th November 2019
DOI: 10.1039/c9cp04980k
rsc.li/pccp
A series of new noble gas (Ng) insertion compounds of the general type XNgX, XNgY and XNgY+ has
been theoretically studied using ab initio and DFT methods herein. We first studied the isomerization
process of the OBCN compound, and then investigated the bonding properties and stability of the
compounds formed by inserting Ng into the single bond of the three low energy isomers by high-level
ab initio calculations. The OBNgCN compounds are thermochemically stable with respect to all
dissociation channels except for the processes of releasing OBCN/OBNC and free Ng. Furthermore, the
two dissociation processes OBNgCN - Ng + OBNC and OBNgNC - Ng + OBCN are kinetically
prohibited by the relatively high free energy barrier ranging from 22.7 to 31.7 kcal mol1 except for the
OBKrCN and OBKrNC analogues. And the adaptive natural density partitioning (AdNDP) analysis
indicated that chemical bonding in OBNgCN compounds is realized via a delocalized 3-center
2-electron (3c-2e) s-bond in the B–Ng–C moiety and a totally delocalized 5-center 2-electron (5c-2e)
s-bond in the whole O–B–Ng–C–N. Natural bond orbital (NBO) theory, atoms-in-molecules (AIM) and
energy decomposition analysis (EDA) based on the molecular wavefunction revealed that the B–Ng
bond and Ng–C bond have some covalent character in OBNgCN. In addition, the calculation and
detailed bonding analysis on a large number of neutral and monocationic compounds with identical
valence electron numbers to OBNgCN demonstrate that the two bonds directly linked to the Ng atoms
have covalent properties in neutral compounds, whereas Ng forms one typical covalent bond and one
partial covalent and partial ionic bond with the neighboring atoms in the monocationic compounds.

Introduction or pseudo-halogen and Y is an electronegative atom or group).

The first noble gas (Ng) compound, XePtF6,1 was synthesized
experimentally in 1962 by Bartlett. After this pioneering work, a
large number of species containing chemically bound noble gas
(Ng) atoms have been analyzed and prepared in recent decades.2–19
Among the confirmed Ng-containing compounds, the Ng-insertion
compounds20–32 are one of the frontier areas of research in the
chemical sciences and have received extensive attention.
The Ng-insertion compounds have the general formula of
XNgY (where Ng is a noble gas atom, X is a hydrogen or halogen
a
School of Chemistry and Chemical Engineering, Southwest University,
Chongqing 400715, P. R. China. E-mail: 13042325719@163.com
b
School of Chemistry and Chemical Engineering, Southwest University,
Chongqing 400715, P. R. China. E-mail: syjzdxlzz@126.com
c
School of Chemistry and Chemical Engineering, Southwest University,
Chongqing 400715, P. R. China. E-mail: ayli001@swu.edu.cn, aylifnsy@swu.edu.cn
† Electronic supplementary information (ESI) available: IRC plot for the conver-
sion of OBCN isomers calculated at the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP level,
the molecular geometry of monovalent cationic isoelectronic compounds, etc. See
DOI: 10.1039/c9cp04980k
It is worth noting that the first argon-stabilizing compound,
HArF,7 possessing a barrier of 0.35 eV (8.07 kcal mol1), was
successfully prepared in 2000 and HKrF was identified in 2002 by
the same group.33 This work prompted researchers to predict and
prepare a variety of new ionic and neutral noble gas insertion
compounds. And a great many Ng-insertion compounds char-
acterized by Ng–carbon, –oxygen, –nitrogen, and –halogen bonds
have been isolated and characterized, such as HNgCCH (Ng = Kr,
Xe),34–36 HXeCC,34,35 HNgCN20 (Ng = Kr, Xe), MCCNgH,37
HNgCCX,38,39 HNgC3N40 (Ng = Kr, Xe), HNgC4H (Ng = Kr, Xe),41
FNgEF (E = Sn, Pb; Ng = Kr, Xe, Rn),43 H3SiNgNSi (Ng = Xe, Rn),44
FXeN (SO2F)2,45 XXeCN (X = Cl, Br),42 and FXe(N3).46
NCNgNSi (Ng = Xe, Rn)47 compounds, formed by inserting
Ng atoms into silaisocyanogen (NCNSi), have been theoretically
predicted to be stable and may exist in bound form at ambient
temperature. Silaisocyanogen, NCNSi, was identified spectro-
scopically in 2015.48 OBCN has the same number of valence
electrons as NCNSi. Herein, we mainly calculated the isomerization
process in the OBCN compound, and then inserted the Ng atom
into the three low-energy isomerization structures. The most stable

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Ng inserting compound, OBNgCN, is thermochemically stable
with respect to all possible dissociation channels except the one
producing Ng and OBCN. Moreover, there is a series of groups
that have an identical valence electron number of 9, including
the neutral groups OB, CN, NSi and HCC, and monovalent
cation groups OSi+, CS+, NN+ and CO+. The former neutral and
the latter ionic species are herein collectively referred to as X
and Y+, respectively. They are combined with each other to form
XX and XY+ compounds with the same valence electron number
of 18, including NCCN, SiNNSi, BOOB, HCCCCH, OBNSi,
OBCCH, HCCNSi, HCCCN, OBCO+, OBOSi+, OBCS+, CONSi+,
SiONSi+, SCNSi+, NRNNSi+, NCCO+, NCOSi+, NCCS+,
NCNRN+, COCCH+, OSiCCH+, SCCCH+ and NRNCCH+. Then,
by inserting a Ng atom into these compounds, we obtain a series
Published on 18 November 2019. Downloaded on 1/3/2020 5:52:18 AM.
of Ng-containing compounds, namely NCNgCN, SiNNgNSi,
BONgOB, HCCNgCCH, OBNgNSi, OBNgCCH, HCCNgNSi,
CNNgCCH, OBNgCO+, OBNgOSi+, OBNgCS+, CONgNSi+,
SiONgNSi+, SCNgNSi+, NRNNgNSi+, NCNgCO+, NCNgOSi+,
NCNgCS+, NCNgNRN+, CONgCCH+, OSiNgCCH+, SCNgCCH+
and NRNNgCCH+, all of which have also been calculated to
explore their stability. Interestingly, the HCCXeCCH and
HCCKrCCH compounds were predicted to be metastable in
2006.49 In this article, all of the neutral and monocationic
compounds can be expressed by the formula XNgX and XNgY+,
respectively.
Computational details
The molecular structures and vibrational frequencies for the
present compounds were calculated by means of the hybrid
density functionals plus the dispersion correction B3LYP-D350,51
and the second-order Møller–Plesset perturbation MP252–56
along with the aug-cc-pVTZ basis sets.57–59 All calculations were
performed with the Gaussian 09 package.60 The aug-cc-pVTZ
basis set was used for Kr and aug-cc-pVTZ-PP with relativistic
effective core pseudopotentials (ECP) was used for Xe and
Rn.61,62 The energies of these compounds were refined by a
single energy calculation at the CCSD(T)63/aug-cc-pVTZ/aug-cc-
pVTZ-PP level based on the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP
optimized structures. Moreover, transition structures (TSs) were
evaluated at the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP level and the
intrinsic reaction coordinates (IRCs) were calculated to ensure
that these TSs are connected with the desired minima along the
energy path. Then, using the GenNBO5.0 program64,65 based on
natural bond orbital (NBO) theory, the natural population
analysis (NPA) of these molecules, including natural atomic
charge and Wiberg bond order (WBI), was carried out at the
MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP level. The electron density
topological properties, including electron density r, Laplacian
r2r, and electron local energy density H at the bond critical
points (BCPs), were also calculated at the MP2/aug-cc-pVTZ/aug-
cc-pVTZ-PP level using AIM66,67 theory and Multiwfn software.68
The energy decomposition analysis (EDA) and deformation
density calculation were carried out using the ETS-NOCV (the
extended transition state method with the natural orbitals for
26312 | Phys. Chem. Chem. Phys., 2019, 21, 26311--26323
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chemical valence theory) charge and energy decomposition
scheme at the revPBE-D3/TZ2P//CCSD(T)/aug-cc-pVTZ/aug-cc-
pVTZ-PP69,70 level using the ADF (2013.01) program package.71
The scalar relativistic effect of heavy elements is considered by
the method of zero-order regular approximation.72 In the ETS-
NOCV scheme, the total interaction energy DEint between the
two interacting fragments is decomposed into four types of
energy terms: classical attractive electrostatic interaction energy
DEelstat, the Pauli repulsive interaction energy DEPauli between
the occupied orbitals of the two fragments, the attractive orbital
interaction energy DEorb arising from the charge transfer and
mixing of the occupied and unoccupied orbitals on the frag-
ments and the polarization effect and the dispersion energy
DEdisp, which is an important contribution for heavier elements.
Therefore, DEint can be written as: DEint = DEelstat + DEPauli +
DEorb + DEdisp. Besides, the total deformation density Dr caused
by the formation of a chemical bond was also calculated.
Moreover, we analyzed the pair-wise orbital interactions such
that DEorb can be decomposed into the pair-wise orbital inter-
action energies, mainly including DE(s1), DE(s2), DE(p1) and
DE(p2), which represent the characteristics of the formed bond
and also show the s-donation and p-back donation between the
two interacting fragments.
The properties of chemical bonding within OBNgCN com-
pounds were further examined using the AdNDP (Adaptive
Natural Density Partitioning)73 method, which is rooted in the
concept of the electron pair as the prime component of chemical
bonding models. And it represents the electronic structures of
molecules with n-center-two-electron (nc–2e) bonds. With n
varying from one to the total amount of atoms in the studied
system, AdNDP recovers both Lewis bonding elements and
delocalized bonding elements.
Results and discussion
Isomerization processes and geometric structures
The isomerization processes in the OBCN system have been
calculated at the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP level and
the reaction pathways for the isomerization are depicted in
Fig. 1. Furthermore, we have also calculated the equilibrium
structures at the CCSD/aug-cc-pVTZ/aug-cc-pVTZ-PP level in
order to validate the stability of these isomers, and the data
in parentheses indicate the bond distances. It can be concluded
that OBCN is the most stable structure among the five studied
isomers. The processes of OBCN converting to OBNC and
BCNO are kinetically hindered by 43.3 and 180.7 kcal mol1,
respectively, indicating that the transformations cannot be
realized even at some high temperatures. And the isomeriza-
tion process of OBCN converting to CNOB (nonlinear structure)
is a two-step process in which OBCN can be indirectly converted
to BONC through the intermediate OBNC. The second step needs
an additional 150.0 kcal mol1 DG‡ to cross the activation free
energy barrier. Therefore, it is difficult to have an isomeric
transformation starting from the most stable OBCN compound.
In contrast, the higher energy isomer NCOB (nonlinear structure)
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Fig. 1 The isomerization processes in the BOCN system calculated at the MP2/aug-cc-pVTZ level. The bond distances within parentheses are
calculated at the CCSD/aug-cc-pVTZ level. Bond distances and relative free energy (DG) are in units of Å and kcal mol1.
can be prepared under low temperature conditions considering
the fact that the conversion to the lowest energy isomer OBCN is
restricted by an appreciable DG‡ value (15.5 kcal mol1). All the
corresponding Intrinsic Reaction Coordinate (IRC) paths are
depicted in Fig. S1–S4 in the ESI.†
Then, we tried to insert noble gas Ng (Ng = Kr, Xe, Rn) into
OBCN to form its Ng inserted analogues. The calculated results
prove that inserting Ng atoms into the central C–B bond is the
only way to obtain inserted compounds. Furthermore, inserting
Ng atoms into the central B–N bond and central O–B bond
of the lower energy isomers OBNC and NCOB (nonlinear
structure) respectively is also possible. The computation of
the associated transition states (TSs) has been performed for
the OBNgNC - OBCN + Ng and OBNgCN - OBNC + Ng
transformation processes. The molecular geometry of OBNgCN
and OBNgNC compounds calculated by CCSD(T)/aug-cc-pVTZ/
aug-cc-pVTZ-PP and the transition states (TSs) calculated by
MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP are shown in Fig. 2. Fig. 3
depicts the IRC plots for the conversion OBKrNC - OBCN + Kr
and OBKrCN - OBNC + Kr, and the conversion for Xe and Rn
analogs are shown in Fig. S5 and S6 in the ESI.† In addition,
other neutral and monovalent cationic isoelectronic species
have also been calculated, and the optimized geometries of the
minimum energy structures are shown in Fig. 4 and Fig. S7 (see
ESI†), respectively. Fig. 4 shows that all these Ng inserting
neutral compounds are linear except for one isomer, BONgCN.
Bond energies and thermodynamic stability
The stability of the Ng inserting compounds OBNgCN can be
evaluated by the energy change DE, enthalpy change DH and
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Gibbs free energy change DG with respect to all possible
dissociation channels (see Table 1). For these OBNgCN com-
pounds, we also further optimize the minimum energy structures
using the CCSD(T)/aug-cc-pVTZ/aug-cc-pVTZ-PP method. The
results calculated using the CCSD(T)/aug-cc-pVTZ/aug-cc-pVTZ-PP
and MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP methods are shown in
Table 1 and Table S1 (see ESI†), respectively. Comparing these
results in Table 1 and Table S1 (ESI†), it is obvious that the
difference between the values of the two methods does not
exceed 5 kcal mol1, except for OBNgCN - OB + Ng + CN. In
this article, we have considered three possible three-body (3-B)
and four 2-B dissociation channels for the OBNgCN com-
pounds. It can be observed from Table 1 that all these three-
body (3-B) dissociation channels are endergonic, endothermic,
and nonspontaneous in nature, except for the OBKrCN - OB +
Kr + CN dissociation pathway, which is slightly spontaneous by
a small negative DG (13.1 kcal mol1) at 298 K. It is distinct
that the OBNgCN - OB + Ng + CN dissociation process can be
hindered under a lower temperature condition owing to the
positive entropy changes. Actually, at some elevated tem-
peratures, this channel may somehow become executable as
the free energy change DG at 298 K is 11.0 and 26.7 kcal mol1
for Xe and Rn inserted analogues, respectively. However, the
3-B ionic dissociation channels are not feasible owing to
the high endergonicity ranging from 197.1 kcal mol1 to
305.7 kcal mol1.
The four 2-body dissociation channels can be divided into
two neutral and two ionic fragment schemes. The ionic chan-
nels show considerable positive energy values, which indicates
that the predicted compounds are more stable than the respective
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Fig. 2 The molecular geometry of OBNgCN and OBNgNC (Ng = Kr, Xe, Rn) calculated by CCSD(T)/aug-cc-pVTZ/aug-cc-pVTZ-PP and transition state
structures (corresponding to the dissociation processes OBNgCN - OBNC + Ng and OBNgNC - OBCN + Ng) calculated by MP2/aug-cc-pVTZ/aug-
cc-pVTZ-PP. The bond lengths are in units of Å.

Fig. 3 IRC plots for the conversion of OBKrNC - OBCN + Kr and OBKrCN - OBNC + Kr calculated at the B3LYP-D3/aug-cc-pVTZ/aug-cc-pVTZ-PP
level.

dissociated products. Nevertheless, the two neutral dissociation rate constant k for the OBNgNC - OBCN + Ng and OBNgCN -
channels, OBNgCN - OBCN + Ng and OBNgCN - OBNC + Ng, OBNC + Ng transformation processes computed at 298 K using the
are exergonic, exothermic and spontaneous with high negative Eyring equation,74,75
energetic changes at 298 K. These resulting fragments are opti-  
kkB T DGa
mized to have minimum energy structures at the MP2 level. k¼ exp 
h RT
Now, it is worth evaluating the kinetic stability of the predicted
OBNgCN compounds, which are thermodynamically unstable with where k is the transmission coefficient, kB is Boltzmann’s constant,
respect to the global minimum products (OBNgNC - OBCN + Ng h is Planck’s constant, and DG‡ is the Gibbs free energy of
and OBNgCN - OBNC + Ng). Hence, we have also provided the activation. k is often assumed to be equal to one as it reflects

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Fig. 4 The molecular geometry of the neutral isoelectronic compounds XNgY (Ng = Kr, Xe, Rn), and the bond lengths (in units of Å) calculated by MP2/
aug-cc-pVTZ/aug-cc-pVTZ-PP.

Table 1 Energy change DE calculated by CCSD(T)/aug-cc-pVTZ/aug-cc-pVTZ-PP, the corrections to enthalpy change DH and Gibbs free energy
change DG from MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP calculations added to the CCSD(T)/aug-cc-pVTZ/aug-cc-pVTZ-PP results for different dissocia-
tion channels of OBNgCN (Ng = Kr, Xe, Rn). All these quantities are in units of kcal mol1

DE DH DG
Processes Kr Xe Rn Kr Xe Rn Kr Xe Rn
OBNgCN - +
OB + Ng + CN 
218.9 242.9 257.3 217.0 241.0 255.4 197.1 221.2 236.9
OBNgCN - OB + Ng + CN+ 267.4 291.3 305.7 266.0 290.0 304.4 246.0 270.1 285.9
OBNgCN - OB + Ng + CN 9.0 32.9 47.3 7.7 31.7 46.1 13.1 11.0 26.7
OBNgCN - OBNg+ + CN 132.1 139.1 144.7 131.5 138.4 144.0 119.2 126.1 132.0
OBNgCN - OB + CNNg+ 190.8 188.3 190.6 189.9 187.2 189.6 177.5 174.9 178.5
OBNgCN - OBCN + Ng 126.5 102.6 88.1 125.6 101.7 87.3 135.3 111.3 95.5
OBNgCN - OBNC + Ng 120.0 96.1 81.7 119.1 95.1 80.7 128.9 104.9 89.1

what fraction of the flux through the transition state proceeds to temperature is needed to make the latter species stable against
the product without recrossing the transition state, so a transmis- these dissociations.
sion coefficient equal to one means that the fundamental no-
recrossing assumption of transition state theory holds perfectly. In NBO and AIM analyses
the case of the Xe and Rn species, very small k values indicate that The bonding nature of the neutral Ng-inserting compounds
OBXeNC, OBXeCN, OBRnNC and OBRnCN would be stable even at was investigated by using natural atomic charges, Wiberg bond
room temperature; however, for Kr species, the corresponding k indices (WBIs) and the HOMO–LUMO energy gap, which were
values at 298 K are substantial (see Table 2). Therefore, a lower calculated by the NBO method; the results for these compounds
are listed in Table 3. For the OBCN compound, the NBO
analysis represents its Lewis structure as OQB–CRN, so
Table 2 The rate constant (k, s1) for the dissociation processes OBNgNC - inserting Ng atoms into the triple bond and double bond is
OBCN + Ng and OBNgCN - OBNC + Ng computed at the MP2/aug-cc- not a viable choice, which is consistent with the above-
pVTZ/cc-pVTZ-PP level mentioned calculation that inserting Ng atoms into the central
Transition DGa Rate C–B bond is the only way to obtain Ng insertion compounds.
Process states (kcal mol1) constants Values (s1) Similarly, low-energy isomers and other species with identical
OBKrNC - OBCN + Kr TS1 10.0 k1 2.4  105 valence electron numbers also conform to this rule. The natural
OBKrCN - OBNC + Kr TS2 15.9 k2 1.1  101 charge on Ng atoms of the neutral compounds shows that they
OBXeNC - OBCN + Xe TS1 22.7 k1 1.1  104 carry a high positive charge ranging from 0.458 to 1.269e with
OBXeCN - OBNC + Xe TS2 25.5 k2 11.1  107
OBRnNC - OBCN + Rn TS1 27.2 k1 5.6  108 a gradual increase from Kr to Rn. It can be observed from
OBRnCN - OBNC + Rn TS2 31.7 k2 2.5  1011 Table 3 that the WBIs for B/C/N/–Ng bonds have quite high values

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Table 3 Natural atom charges (a.u.) on the Ng atom and X and Y groups, WBIs of the X–Ng and Ng–Y bonds, and the HOMO–LUMO gap calculated at
the MP2/aug-cc-pVTZ/cc-pVTZ-PP level for the neutral Ng-inserting compounds XNgY

qNg qOB qCN/NSi WBIO–B WBIC–N/N–Si WBIB–Ng WBIC/N–Ng DEH–L

OBCN — 0.298 0.298 1.830 2.941 — — 15.003
OBKrCN 0.631 0.072 0.703 1.814 2.944 0.746 0.256 11.217
OBXeCN 0.793 0.090 0.703 1.797 2.951 0.810 0.316 12.039
OBRnCN 0.869 0.159 0.710 1.782 2.952 0.803 0.315 12.069
OBKrNSi 0.665 0.017 0.682 1.776 1.577 0.768 0.266 9.792
OBXeNSi 0.854 0.148 0.706 1.758 1.506 0.833 0.310 10.436
OBRnNSi 0.934 0.206 0.728 1.746 1.510 0.824 0.292 10.464

qNg qOB/CN/SiN WBIO–B/C–N/Si–N WBIB–Ng/C–Ng/N–Ng DEH–L

OBKrBO 0.458 0.229 1.722 0.410 9.317
OBXeBO 0.621 0.311 1.734 0.507 10.647
OBRnBO 0.701 0.351 1.731 0.514 10.808
NCKrCN 0.834 0.417 2.957 0.558 12.729
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NCXeCN 1.030 0.515 2.955 0.581 13.652

NCRnCN 1.112 0.556 2.954 0.557 13.390
SiNKrNSi 0.940 0.470 1.478 0.545 10.355
SiNXeNSi 1.184 0.592 1.448 0.534 10.640
SiNRnNSi 1.269 0.635 1.462 0.496 10.522

qNg qOB/CN/SiN qCCH WBIO–B/C–N/Si–N WBIC–C WBIB–Ng/C–Ng/N–Ng WBIC–Ng DEH–L

OBKrCCH 0.617 0.049 0.568 1.774 2.986 0.661 0.347 10.650
OBXeCCH 0.790 0.196 0.594 1.759 2.981 0.719 0.417 11.050
OBRnCCH 0.871 0.249 0.622 1.748 2.982 0.715 0.402 10.970
NCKrCCH 0.833 0.544 0.289 2.946 2.962 0.467 0.676 12.314
NCXeCCH 1.030 0.606 0.424 2.947 2.954 0.493 0.686 12.011
NCRnCCH 1.112 0.632 0.481 2.947 2.958 0.476 0.652 11.791
SiNKrCCH 0.882 0.552 0.330 1.500 2.961 0.448 0.699 10.647
SiNXeCCH 1.093 0.633 0.460 1.465 2.957 0.445 0.698 10.702
SiNRnCCH 1.175 0.665 0.510 1.476 2.963 0.415 0.660 10.595

ranging from 0.256 to 0.810 for these neutral compounds,
indicating the possible covalent interaction in these cases. Taking
OBCN as an example, we compare the WBI values and partial
atomic group charges in the parent OBCN with those in the
predicted OBNgCN. The double bond property of OQB and the
triple bond nature of CRN remain unchanged even after the Ng
insertion. The partial atomic group charges in the parent OBCN
were q(OB) = 0.298 and q(CN) = 0.298, respectively. Based on the
reported partial atomic charges on the constituent atoms, it is
apparent that upon insertion of a noble gas atom into OBCN, an
extensive redistribution of electron density takes place that
interferes with the bonding of the involved atoms. For the
OBKrCN, OBXeCN and OBRnCN compounds, the partial atomic
charges acquired by CN were 0.703, 0.703, and 0.710,
respectively. In addition, the energy difference (DEH–L) between
HOMO and LUMO, a measure of chemical hardness,76,77 also
measures the high stability of the Ng inserted systems where
DEH–L is noted to be quite high (9.317–13.652 eV), as shown in
Table 3.
Then, we further investigated the nature of B/C/N–Ng bonds
in these neutral compounds XNgX and XNgY using the electron
density topological analysis technique. Generally, at the bond
critical point (BCP) of a chemical bond, a high electron density
r(r) (40.1e) and a negative Laplacian r2r(r) of the electron
density denote a covalent bond, and the reverse situation
represents a noncovalent interaction (ionic and van der Waals
interactions). Although the above criterion can explain the
bonding situation in many cases, it fails to describe the bonds
involving the 3d orbital and heavier atoms. Other descriptors
like the energy density H(r) and the ratio of local kinetic energy
density G(r) and electron density r(r) have also been put
forward. H(r), defined as the sum of local kinetic energy density
G(r) and local potential energy density V(r) at the BCP, is an
important index for characterizing the nature of a chemical bond.
Covalent bonds possess values of H(r) o 0 and G(r)/r(r) o 1,
whereas a bond with H(r) 4 0 and G(r)/r(r) 4 1 has a closed-
shell interaction. The detailed BCP QTAIM information, i.e.,
electron density topological properties including electron density
r(r), electron density Laplacian r2r(r), local electron energy
density H(r) and the ratio of local kinetic energy density G(r)
and electron density r(r) at the BCPs, for the B/C/N–Ng bonds of
the neutral compounds is listed in Table 4. In these calculated
neutral compounds, all B/C/N–Ng bonds are pigeonholed as
covalent bonds based on the fact that all H(r) values are
negative and G(r)/r(r) is less than one. In addition, the electron
localization function ELF values at the BCPs of these neutral
compounds were also calculated and are listed in Table 4. ELF
values are in the range of 0–1. A large ELF value means that the
electrons are strongly localized, indicating a covalent bond, a
lone pair or the inner shell of an atom. Here, the ELF values of
the B/C/N–Ng bonds are between 0.321 and 0.941, which means
that the B/C/N–Ng bonds are typical covalent bonds, corres-
ponding to the above analysis. Thus, the detailed bonding
analyses demonstrate the covalent nature of the two bonds

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Table 4 Electron density r, Laplacian r2r, electron local energy density H, the ratio of local kinetic energy density G(r) and electron density r(r) and
electron localization function (ELF) at the bond critical points (BCPs) of the B/C/N–Ng bonds in the Ng insertion compounds calculated by the MP2/aug-
cc-pVTZ/cc-pVTZ-PP method

B–Ng Ng–C/N
r(r) r2r(r) H(r) G(r)/r(r) ELF r(r) r2r(r) H(r) G(r)/r(r) ELF
OBKrCN 0.113 0.141 0.068 0.289 0.941 0.080 0.087 0.023 0.557 0.468
OBXeCN 0.105 0.089 0.054 0.304 0.901 0.079 0.063 0.027 0.541 0.471
OBRnCN 0.095 0.033 0.044 0.374 0.795 0.075 0.086 0.025 0.614 0.382
OBKrNSi 0.101 0.071 0.051 0.324 0.918 0.096 0.137 0.032 0.686 0.453
OBXeNSi 0.102 0.070 0.050 0.320 0.871 0.094 0.103 0.039 0.686 0.413
OBRnNSi 0.092 0.021 0.041 0.387 0.753 0.089 0.142 0.033 0.777 0.321

B/C/N–Ng
r(r) r2r(r) H(r) G(r)/r(r) ELF
OBKrBO 0.072 0.072 0.023 0.375 0.797
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OBXeBO 0.077 0.077 0.028 0.342 0.795

OBRnBO 0.074 0.074 0.026 0.391 0.689
NCKrCN 0.111 0.055 0.044 0.515 0.723
NCXeCN 0.105 0.031 0.048 0.533 0.597
NCRnCN 0.096 0.082 0.040 0.627 0.466
SiNKrNSi 0.109 0.128 0.040 0.660 0.613
SiNXeNSi 0.111 0.081 0.055 0.679 0.476
SiNRnNSi 0.102 0.143 0.044 0.782 0.364

B/C/N–Ng Ng–C
r(r) r2r(r) H(r) G(r)/r(r) ELF r(r) r2r(r) H(r) G(r)/r(r) ELF
OBKrCCH 0.093 0.038 0.041 0.336 0.894 0.094 0.079 0.031 0.537 0.619
OBXeCCH 0.093 0.042 0.041 0.329 0.849 0.093 0.048 0.037 0.527 0.571
OBRnCCH 0.085 0.005 0.035 0.393 0.731 0.087 0.080 0.033 0.606 0.453
NCKrCCH 0.102 0.068 0.037 0.527 0.625 0.126 0.027 0.056 0.501 0.807
NCXeCCH 0.094 0.048 0.039 0.540 0.532 0.118 0.008 0.061 0.531 0.667
NCRnCCH 0.086 0.087 0.033 0.628 0.415 0.107 0.074 0.048 0.624 0.531
SiNKrCCH 0.109 0.125 0.041 0.665 0.561 0.122 0.039 0.052 0.509 0.780
SiNXeCCH 0.104 0.092 0.049 0.687 0.449 0.116 0.013 0.058 0.532 0.634
SiNRnCCH 0.096 0.146 0.039 0.789 0.343 0.104 0.075 0.046 0.622 0.502

that are directly attached to the Ng atoms in these neutral
compounds.
Then, the NBO and AIM analyses were also carried to
investigate the bonding properties of the two bonds that are
directly attached to the Ng atom in the monovalent cationic
compounds XNgY+, and the results are provided in Tables S2
and S3 in the ESI.† There are 5 types of monovalent cationic
compounds, namely CONgCN+, OBNgOSi+/CS+/NN+/CO+, SiNNg-
SiO+/SC+/NN+, NCNgOSi+/CS+/NN+, and HCCNgOSi+/CS+/NN+/
CO+. Among these monovalent cationic compounds, there are
two direct bonds to the Ng atom, and the WBIs of the bond that
connects to the X group vary within 0.799–1.036, which means
significant covalent properties. Meanwhile, the bonds possess
values of H(r) o 0 and G(r)/r(r) o 1 except for OBKrNN+, which
further confirms their covalent nature. On the other hand, the
WBIs of the other bond that connects to the Y group are quite
low, ranging within 0.009–0.222, which corroborates with the
partial electrostatic description and partial covalent description
of these bonds based on the charge distribution and the fact
that G(r)/r(r) o 1 (see Tables S2 and S3, ESI†).
The bonding situation of the OBNgCN compounds was also
elucidated using the AdNDP (adaptive natural density partitioning)
analysis, which is an extension of the popular natural bond
orbital (NBO) analysis, and the results are depicted in Fig. 5.
This approach shows us both the localized and/or delocalized
(i.e., localized on several atoms) bonding elements involved in
the system. It reveals three lone pairs (LPs) on the Ng atom and
two pairs on the O and N atoms with occupation numbers above
1.98|e|. Fig. 5 further indicates the fact that the insertion of the
Ng atom has no effect on the double bond nature of the OB
fragment consisting of one s- and two p-bonds and the triple
bond nature of the CN fragment consisting of one s- and two
p-bonds. The OBNgCN system consists of a 3c-2e s-bond involving a
B–Ng–C moiety and a totally delocalized 5c-2e s-bond involving the
O–B–Ng–C–N moiety with occupation numbers close to the ideal
value of 2.00|e|. A similar situation can also be observed from the
color-scale plot of the electron localization function (ELF) in Fig. 6.
In addition, the color-scale plot of the electron localization function
(ELF) for OBNgCN shown in Fig. 6 reveals the formation of 2c-2e
bonds in the CN group, which was found to have one 2c-2e
s-bond and two 2c-2e p-bonds in AdNDP analyses. Therefore,
the delocalized bonding holds Ng and the remaining fragments
together in the OBNgCN compounds.
Furthermore, the ELF isosurfaces were drawn to more intuitively
show the bonding situation of the OBNgCN compounds. An
isovalue of ELF = 0.800 was demonstrated to be an effective
standard for the classical valence compounds.78 Fig. 7 shows the
0.800 isosurfaces for linear OBNgCN compounds (Ng = Kr, Xe, Rn).

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Fig. 5 The bonding elements recovered by the AdNDP analysis for OBNgCN (Ng = Kr–Rn).
Fig. 6 Color-scale plots of electron localization function (ELF) for
OBNgCN at the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP level, with Ng = Kr,
Xe, Rn from left to right. From top to bottom are O, B, Ng, C, and N atoms,
respectively.
Single bond basins and lone pair basins generally tend to be more
spherical in shape, whereas that characterized by a s–p double
bond shows more of an ellipsoidal shape,79 and the triple bond
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Fig. 7 ELF isosurfaces (ELF = 0.800) for OBKrCN (a), OBXeCN (b), and
OBRnCN (c).
basins represent a ring shape. The ELF isosurface clearly high-
lights the lone electron pair regions of the noble gas atoms.
Fig. 7 not only further reveals the partial covalent nature of the
two bonds that are directly attached to the Ng atoms for the
OBNgCN compounds (Ng = Kr, Xe, Rn), but also demonstrates
the triple bond and the double bond properties for the OB group
and the CN group, respectively.
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Energy decomposition analysis
The EDA (energy decomposition analysis) calculations with the
ETS-NOCV scheme for the neutral compounds have been
performed using ionic and neutral fragment schemes to affirm
the covalent nature of the B/C/N–Ng bonds, and the results of
ionic fragment schemes and neutral fragment schemes are
collected in Table 5 and Table S4 (see ESI†), respectively. When
there are multiple partitioning schemes, the scheme that
generates the lowest DEorb value should be considered as the
optimal way to describe the bonding situation.80,81 For the B/C/
N–Ng bonds in our cases, the ionic scheme produces a smaller
DEorb value in terms of the neutral scheme, except for the B–Kr
bond. It can be concluded that the ionic scheme is more
reasonable compared to the neutral one, certainly, excluding
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covalent characteristics of these bonds in the neutral compounds.
In the neutral scheme, the orbital interaction DEorb provides
the predominant contribution towards the B/C/N–Ng bond
stabilization, it ranges from 64.31% to 81.19%, whereas the
electrostatic interaction energy DEelstat is responsible for only
18.38–34.78% of the total attraction. In all cases, the dispersion
energy DEdis (o1.13%) has a very insignificant impact in
stabilizing these bonds.
The plots of the deformation density Dr obviously reveal
charge transfer in the pair-wise orbital interaction between the
interacting fragments. Herein, we have drawn the plots of the
deformation densities of the B–Ng and Ng–C bonds for the
OBNgCN compound, including the corresponding pairwise orbi-
tal interaction energies DE(s1), DE(s2), DE(p1) and DE(p2), as

the B–Kr bond. In the ionic segmentation, the electrostatic
interaction energy DEelstat plays the most dominant role in the
total attraction (ca. 56.05–69.54%); meanwhile, the orbital
interaction DEorb also makes a considerable contribution
(ca. 30.12–43.16% of the total attraction), which justifies the
shown in Fig. S8 (see ESI†). Note that the red color indicates
Dr o 0, and the blue color represents Dr 4 0; according to the
current color coding, electron density flows from the red region
to the blue region. For the B–Ng bond, the energy DE(s1)
provides the major contribution towards DEorb for OBNgCN.

Table 5 EDA results with the ETS-NOCV scheme at the level of revPBE-D3/TZ2P//CCSD(T)/aug-cc-pVTZ/aug-cc-pVTZ-PP. All energy termsa are in
units of kcal mol1

Fragments DEPauli DEelstat DEorb DEdis DEint DE(s1) DE(s2) DE(p1) DE(p2)
 +
OBKrCN OB + KrCN 276.93 292.79(59.00) 202.66(40.84) 0.83(0.17) 219.35 182.39(90.00) 5.98 4.45 4.45
OBXeCN OB + XeCN+ 284.25 311.89(63.66) 177.08(36.14) 0.97(0.20) 205.68 157.73(89.07) 5.62 4.54 4.54
OBRnCN OB + RnCN+ 286.19 323.37(66.71) 160.40(33.09) 0.99(0.20) 198.57 141.85(88.43) 5.65 4.51 4.51
OBKrCN OBKr+ + CN 107.21 174.76(67.36) 83.90(32.34) 0.79(0.30) 152.24 70.09(83.54) 1.87 3.80 3.80
OBXeCN OBXe+ + CN 125.13 189.33(68.86) 84.65(30.79) 0.95(0.35) 149.80 70.28(83.03) 2.06 3.91 3.91
OBRnCN OBRn+ + CN 141.00 200.93(69.92) 84.29 (29.33) 2.15(0.75) 146.37 68.65(81.44) 2.33 4.32 4.32
OBKrNSi OB + KrNSi+ 249.15 249.67(58.71) 173.69(40.85) 1.87(0.44) 176.08 157.17(90.49) 5.74 2.58 2.58
OBXeNSi OB + XeNSi+ 254.81 268.17(63.13) 154.49(36.37) 2.15(0.51) 169.99 138.00(89.32) 5.69 3.31 3.10
OBRnNSi OB + RnNSi+ 251.57 275.44(65.68) 141.82(33.82) 2.12(0.51) 167.81 126.39(89.12) 5.71 3.10 3.10
OBKrNSi OBKr+ + NSi 119.82 179.94(62.88) 103.79(36.27) 2.45(0.86) 166.35 78.36(75.50) 1.54 9.15 9.15
OBXeNSi OBXe+ + NSi 149.04 202.64(64.39) 109.12(34.67) 2.94(0.93) 165.66 81.25(74.46) 1.97 9.53 9.53
OBRnNSi OBRn+ + NSi 152.13 209.16(65.83) 105.64(33.25) 2.95(0.93) 165.61 76.59(72.50) 2.28 10.03 10.03
OBKrOB OBKr+ + OB 154.25 208.60(62.43) 123.83(37.06) 1.71(0.51) 179.90 113.37(91.55) 2.37 2.21 2.21
OBXeOB OBXe+ + OB 192.89 241.30(66.58) 119.09(32.86) 2.04(0.56) 169.54 107.77(90.49) 2.87 2.64 2.64
OBRnOB OBRn+ + OB 212.19 260.75(69.14) 114.35(30.32) 2.05(0.54) 164.96 102.48(89.62) 3.31 2.82 2.82
NCKrCN NCKr+ + CN 175.93 216.79(60.48) 139.78(38.99) 1.89(0.53) 182.54 119.74(85.66) 3.43 5.96 5.96
NCXeCN NCXe+ + CN 192.60 236.86(64.40) 128.68(34.99) 2.24(0.61) 175.17 106.72(82.93) 3.94 6.39 6.39
NCRnCN NCRn+ + CN 195.43 245.14(66.80) 119.60(32.59) 2.25(0.61) 171.56 97.24(81.31) 4.36 6.71 6.71
SiNKrNSi SiNKr+ + NSi 154.74 178.27(56.05) 137.26(43.16) 2.50(0.79) 163.29 110.85(80.76) 3.36 8.45 8.45
SiNXeNSi SiNXe+ + NSi 195.23 215.37(60.38) 138.29(38.77) 3.04(0.85) 161.47 105.20(76.07) 5.18 10.58 10.58
SiNRnNSi SiNRn+ + NSi 196.45 223.50(62.59) 130.53(36.56) 3.04(0.85) 160.61 96.44(73.89) 5.24 11.21 11.21
OBKrCCH OB + KrCCH+ 221.67 252.90(60.32) 164.54(39.25) 1.82(0.43) 197.59 147.55(89.67) 2.66 2.27 2.27
OBXeCCH OB + XeCCH+ 228.19 267.42(64.88) 142.63(34.61) 2.10(0.51) 183.96 126.84(88.93) 2.02 2.84 2.84
OBRnCCH OB + RnCCH+ 231.03 276.73(67.52) 131.05(31.97) 2.08(0.51) 178.82 116.13(88.61) 1.69 3.07 3.07
OBKrCCH OBKr+ + CCH 256.78 267.48(62.29) 160.27(37.33) 1.63(0.38) 172.60 143.56(89.57) 5.23 5.45 5.45
OBXeCCH OBXe+ + CCH 262.34 276.78(60.58) 178.04(38.97) 2.09(0.46) 194.57 138.90(78.02) 6.01 6.23 6.23
OBRnCCH OBRn+ + CCH 269.08 287.56(61.36) 179.03(38.20) 2.05(0.44) 199.56 122.79(68.59) 6.01 6.23 6.23
NCKrCCH NC + KrCCH+ 152.72 197.63(62.81) 115.15(36.60) 1.87(0.59) 161.93 96.15(83.50) 1.44 4.79 4.79
NCXeCCH NC + XeCCH+ 162.84 211.14(66.13) 105.96(33.19) 2.20(0.69) 156.46 86.52(81.65) 1.32 5.02 5.02
NCRnCCH NC + RnCCH+ 168.06 219.37(69.13) 100.39(31.18) 2.21(0.69) 153.91 80.57(80.26) 1.27 5.33 5.33
NCKrCCH NCKr+ + CCH 241.71 267.45(60.01) 176.22(39.54) 1.97(0.44) 203.93 148.44(84.23) 5.37 9.19 9.19
NCXeCCH NCXe+ + CCH 268.60 297.20(63.77) 166.53(35.73) 2.35(0.50) 197.48 137.01(82.27) 6.13 9.58 9.58
NCRnCCH NCRn+ + CCH 270.25 307.90(66.44) 153.19(33.05) 2.35(0.51) 193.20 123.39(80.55) 6.33 9.75 9.75
SiNKrCCH SiN + KrCCH+ 151.91 196.85(59.69) 130.38(39.54) 2.53(0.77) 177.84 99.34(76.19) 1.58 10.38 10.38
SiNXeCCH SiN + XeCCH+ 170.67 216.56(62.71) 125.76(36.42) 3.00(0.87) 174.65 92.80(73.79) 1.44 10.91 10.91
SiNRnCCH SiN + RnCCH+ 168.98 215.45(63.31) 121.88(35.81) 2.99(0.88) 179.88 94.61(77.63) 1.67 10.85 10.85
SiNKrCCH SiNKr+ + CCH 229.47 235.16(59.22) 159.96(40.28) 1.98(0.50) 167.63 136.98(85.64) 5.83 6.38 6.38
SiNXeCCH SiNXe+ + CCH 243.58 258.54(62.90) 150.15(36.53) 2.34(0.57) 167.44 125.91(83.86) 6.55 6.88 6.88
SiNRnCCH SiNRn+ + CCH 236.54 263.19(65.28) 137.69(34.15) 2.32(0.58) 166.67 114.12(82.88) 6.34 6.88 6.88
a
The percentages within the parentheses show the contributions towards the total attractive energy DEelstat + DEorb + DEdis, and those within the
square brackets for DE(s1) show the contributions towards the total orbital interaction energy DEorb.

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Fig. 8 Plots of the deformation density Dr(r), and shape of the most important interacting orbitals of the pairwise orbital interactions between OB and
KrCN+ in OBKrCN.
The s-back donation DE(s2) is the second-most important
pairwise orbital interaction, which transfers electron density
from the HOMO of the OB group to a vacant p orbital on Ng.
The p-back donations DE(p1) and DE(p2) are small contribu-
tions towards DEorb, which originate from the charge transfers
from the HOMO1 of OB to one vacant d orbital of Ng and
from HOMO2 of OB to another vacant d orbital of Ng,
respectively. Fig. 8 depicts the plots of the deformation densities
and shape of the most important interacting orbitals of the pairwise
orbital interactions between OB and KrCN+ in OBKrCN.
On the other hand, for the monovalent cationic compounds
XNgY+, the results for the X–Ng bonds and the Y–Ng bonds of
the EDA calculations with the ETS-NOCV scheme are shown in
Tables S5 and S6 in the ESI,† respectively. The term DEorb (ca.
59.33–81.00%) is found to be more dominant over the DEelstat
term (ca. 18.67–40.17%), as shown in Table S5 (ESI†), which
indicates that the X–Ng bonds have typical covalent properties.
Nevertheless, the contribution of the DEelstat term ranges from
33.90 to 60.53% and the DEorb term varies from 35.86 to 57.21%
for the Ng–Y bonds in the EDA results in Table S6 (ESI†).
Hence, the Y–Ng bonds may be considered partly as of covalent
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type and partly as of electrostatic type. Note that the interaction
energy DEint of the Y–Ng bonds is much smaller than those of
the X–Ng bonds, which demonstrates the weak interaction of
the Y–Ng bonds.
Vibrational frequencies
For these linear molecules, the main modes of vibration are
bending vibration and stretching vibration. The harmonic
frequencies and infrared intensity (in parentheses) for these
neutral compounds calculated at the MP2/aug-cc-pVTZ/aug-cc-
pVTZ-PP level of theory are listed in Table 6, and the mono-
valent cationic compounds are listed in Table S7 in the ESI.† n1
and n2 are respectively the in-plane bending vibration (planar
rocking vibration) and out-of-plane bending vibration (twisting
vibration). n3, n4, and n5 all represent the stretching vibration.
For OBNgCN compounds, the strongest infrared-active vibrational
mode is the asymmetric B–Ng–C bond stretch n3(B–Ng–C), which
decreases from Kr to Rn. The n4(O–B) and n5(C–N) respectively
represent the O–B bond and C–N bond symmetric stretch vibration
modes. We can see that the insertion of Ng reduces the bending
vibration frequency and the stretching vibration frequency.
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Table 6 Frequencies (cm1) and infrared intensity (in parentheses) of some vibrational modes for the Ng-insertion compounds of OBNgCN and
OBNgNC calculated at the MP2/aug-cc-pVTZ/aug-cc-pVTZ-PP level of theory

n1 n2 n3(B–Ng–C) — n4(O–B) n5(C–N)

OBCN 211.7(33) 496.1(18) 728.8(4) 1943.7(45) 2188.4(114)
OBKrCN 60.3(14) 350.6(16) 259.4(336) — 1891.0(4) 2033.2(120)
OBXeCN 58.6(13) 357.6(6) 278.4(253) — 1893.0(2) 2035.3(120)
OBRnCN 57.3(12) 336.9(6) 272.9(202) — 1891.7(6) 2043.1(109)
n1 n2 n3(N–Ng) n4(B–Ng) n5(O–B) n6(N–Si)
OBKrNSi 109.9(29) 333.1(0) 227.4(70) 307.2(254) 1869.6(3) 1167.6(141)
OBXeNSi 140.6(30) 343.2(0) 270.2(74) 300.5(164) 1881.9(8) 1180.5(244)
OBRnNSi 127.6(25) 320.9(0) 265.2(137) 298.2(56) 1882.4(13) 1188.5(222)
n1 n2 n3(B–Ng–B) n4(O–B)
OBKrOB 44.7(14) 303.2(12) 281.4(119) 1850.5(17) — —
OBXeOB 51.2(13) 332.7(10) 240.3(192) 1857.3(11) — —
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OBRnOB 53.6(12) 323.4(10) 237.1(162) 1861.2(16) — —

n1 n2 n3(C–Ng–C) n4(C–N)
NCKrCN 65.0(13) 357.5(0) 361.1(277) 2024.1(346) — —
NCXeCN 68.8(13) 353.2(0) 324.7(277) 2041.2(273) — —
NCRnCN 65.2(13) 328.1(0) 316.1(233) 2050.1(235) — —
n1 n2 n3(N–Ng–N) n4(N–Si)
SiNKrNSi 38.6(3) 263.2(46) 374.7(82) 1206.9(143) — —
SiNXeNSi 44.2(1) 275.9(44) 314.5(265) 1206.5(526) — —
SiNRnNSi 42.3(1) 252.6(40) 291.4(223) 1208.3(491) — —
n1 n2 n3(C–Ng) n4(B–Ng) n5(O–B) n6(C–C)
OBKrCCH 54.2(1) 342.8(7) 340.7(178) 258.7(86) 1864.8(0) 1959.5(5)
OBXeCCH 57.5(1) 349.5(0) 330.7(88) 275.5(185) 1872.9(6) 1957.3(19)
OBRnCCH 58.9(2) 326.7(0) 339.3(57) 270.2(173) 1873.8(11) 1960.2(15)
n1 n2 n3(C–Ng) n4(C–Ng) n5(N–C) n6(C–C)
NCKrCCH 60.3(1) 348.7(6) 338.7(74) 344.9(291) 344.9(291) 1997.6(48)
NCXeCCH 64.3(2) 336.9(8) 377.4(62) 315.6(249) 315.6(249) 2000.5(39)
NCRnCCH 62.8(2) 311.6(8) 384.1(32) 309.3(226) 309.3(226) 1999.1(28)
n1 n2 n3(N–Ng) n4(C–Ng) n5(N–Si) n6(C–C)
SiNKrCCH 47.4(2) 308.4(30) 265.1(2) 376.6(314) 1187.8(113) 1988.8(34)
SiNXeCCH 53.0(1) 307.8(33) 284.1(84) 365.9(243) 1199.3(213) 1993.9(26)
SiNRnCCH 51.7(1) 283.8(31) 278.0(112) 363.1(166) 1205.3(192) 1991.7(19)

Conclusions compounds were calculated. The nature of the B/C/N–Ng bonds

In our work, a novel series of noble gas-inserted species with
XNgY and XNgY+ formulas have been investigated with respect
to the structures, stability and bonding nature. The OBNgCN
(Ng = Kr, Xe, Rn) compounds are found to be thermochemically
stable with respect to all dissociation channels, except for the
processes producing OBCN/OBNC and the free Ng atom. In all
cases, the dissociations of OBNgCN - OBNC + Ng and
OBNgNC - OBCN + Ng are kinetically limited by a certain
number of free energy barriers, and the free energy barrier
ranges from 10.037 to 31.747 kcal mol1, and increases with Kr,
Xe, and Rn. The OBNgCN compounds show many similarities
with NCNgNSi in physical properties, molecular symmetry,
structure and chemical reactivity, which satisfies the principle
of isoelectronics.82 According to the AdNDP analysis, the OBNgCN
compounds, similar to NCNgNSi, possess a 3c-2e s-bond and a
totally delocalized 5c-2e s-bond. Then, a variety of compounds
with the identical valence electron number to that of OBNgCN
in these compounds was further analyzed by the NBO, AIM, ELF
and EDA methods. And all the results demonstrate that the neutral
groups X (X = OB, CN, NSi and HCC) form typical covalent bonds
with Ng atoms, whereas the Y–Ng bonds (Y = OSi+, CS+, NN+ and
CO+) exhibit partial covalent properties and partial ionic bond
properties. Therefore, these findings have theoretically greatly
expanded and enriched the inert gas insertion compounds.
Conflicts of interest
The authors declare no competing financial interests.
Acknowledgements
This study was supported by the Quantum Chemistry Laboratory
of the College of Chemistry and Chemical Engineering, South-
west University.

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