A Journal of

Accepted Article

Title: Theoretical and crystallographic study on Pb(IV) tetrel bonding

interactions Antonio Franconetti[a] and Antonio Frontera*[a]

Authors: Antonio Franconetti and Antonio Frontera

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To be cited as: Chem. Eur. J. 10.1002/chem.201900447

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Theoretical and crystallographic study on Pb(IV) tetrel bonding
interactions
Antonio Franconetti[a] and Antonio Frontera*[a]
Dedication ((optional))
Abstract: In this manuscript the ability of tetrahedral Pb(IV) to
establish noncovalent σ-hole tetrel bonding interactions with electron
rich atoms (ElR, anions and Lewis bases) has been studied at the
PBE0-D3/def2-TZVPD level of theory. We have analysed the
Cambridge Crystallographic Database (CSD), which is a convenient
storehouse of geometrical information, to investigate the existence of
tetrel bonding interactions involving tetrahedral Pb(IV) derivatives.
We have found several examples of tetrel bonding interactions that
are crucial in their crystal packing, ranging from monodimensional
(0D) to bidimensional (2D) assemblies. In addition to the energetic
and theoretical study of several XPb(CH3)3···ElR complexes (X = F,
CN, CF3 and CH3), we have also used Bader’s theory of “atoms in
molecules” to further analyse and characterize the noncovalent
interactions described herein.
Introduction
Supramolecular chemists mostly design and study assemblies
that are of greater complexity than individual molecules. [1,2] It is a
multidisciplinary field that grows very fast due to the ability of
synthetic chemists to build complicated structures. By combining
covalent chemistry and coordination chemistry, nowadays, it is
possible to reach fine-tuned structures with the adequate size,
shape and functionality. Supramolecular Chemistry and
molecular recognition are concepts intimately related.[ 3 ] The
well-designed molecules spontaneously form assemblies in a
controlled way through intermolecular forces (non-covalent
interactions).
A profound understanding of non-covalent interactions is
required to control assembly and self-assembly processes since
they are often orchestrated by an intricate combination of
forces.[4,5] Therefore, an accurate description of the non-covalent
interaction that are established between molecules is essential
for the continuous development of the field. The most reliable
and utilized directional interactions are hydrogen [6] and halogen
bonding[7] sometimes combined with less directional but stronger
forces like ion pairing. Non-covalent interactions involving
aromatic rings like π-stacking, anion–π and cation–π are also
very important in this field. [8]
[a] Dr. Antonio Franconetti and Prof. Dr. Antonio Frontera
Departament de Química
Universitat de les Illes Balears
Crta de Valldemossa km 7.7, 07122 Palma de Mallorca (Baleares),
SPAIN
E-mail: toni.frontera@uib.es
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/chem.201900447
Other types of interactions are also exploited to design
supramolecular structures and catalysts. [ 9 ] Indeed, there is a
growing recognition that σ-hole[10] and π-hole interactions[11] are
useful in supramolecular chemistry and crystal engineering. In
Accepted Manuscript
particular tetrel,[ 12 ] pnictogen,[ 13 ] chalcogen,[ 14 ] aerogen
bonding[ 15 ] and even regium bonding[ 16 ] are becoming new
players in this field.[17] They follow a bonding scheme that is
analogous to hydrogen bonding: X–D···A, where X is any atom,
D is the donor atom (Lewis acid) from the main group of
elements, and A is any electron rich atom (anion or lone pair
donor). The σ-hole becomes more positive (stronger interaction)
when D is more polarizable and when the X atom is more
electron withdrawing. The atomic polarizability increases on
going down the group, particularly for the group of tetrels (group
14): C = 11.5 au, Si = 38.1 au, Ge = 40.3 au, and Sn = 55.6 au
(au = atomic units); thus a stronger interaction should occur
when descending the group, and, consequently, lead is
expected to form the strongest σ-hole interactions.[18]
There are several examples in the literature of experimental[19]
and theoretical[20] investigations devoted to tetrel bonding, which
was named as such in 2013. [21] A quite differential feature of
tetrel bonding compared to halogen, chalcogen or pnicogen
bonding is that the charge distribution on the tetrel atom is not
anisotropic (absence of negative belts or lone pairs). More
importantly, the four σ-holes are located in the middle of three
sp3-hybridized bonds, drastically reducing the accessibility to the
σ-hole. Moreover, the heavier tetrel atoms are not equally suited
for noncovalent σ-hole bonding because some easily expand
their valence, thus engaging in more traditional chemistry. In fact
the heavier tetrels (tin and lead) have rich coordination
chemistry[22,23,24,25] and are commonly seen as metals. Moreover,
hypervalent species with Ge and Si (also considered metalloids)
are also well-known.[26] Still, the heavier tetrel atoms can engage
in noncovalent σ-hole interactions when placed in a chemical
environment that prevents hypervalency.[27]
There are several examples in the literature where tetrel bonding
interactions involving Pb(II) have been used in crystal
engineering and supramolecular chemistry. However, σ-hole
interactions involving Pb(IV) have been scarcely reported in the
literature.[28] In these previous reports, the theoretical studies are
basically devoted to Tin(IV) with little attention to Pb(IV) or
focused to the hypervalency. In addition, in the previous works
the CSD is either not analyzed or focused to penta and
hexavalent derivatives. In this manuscript we provide a survey of
crystal structures retrieved from the CSD to evidence the ability
of tetrahedral Pb(IV) to establish tetrel bonding interactions with
lone pair donor atoms (O, S, N and Br). We provide examples of
0D, 1D and 2D assemblies in their X-ray solid state structure
governed by tetrel bonding interactions. Moreover, we have
investigated the ability of XPb(CH3)3, (X = F, CN, CF3 and CH3)
to establish σ‒hole noncovalent interactions with electron rich
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atoms (NH3, CO, HCN, Cl–, Br–, I–, see Fig. 1) by means of DFT
calculations (PBE0-D3/def2-TZVPD). In a series of complexes
(X = F), we have also analyzed the effect on changing Pb by Sn
on the energetic and geometric features of the complexes.
Finally, we have also used the Bader’s theory of “atoms in
molecules” to further describe and rationalize the interactions
described above.
tetracoordinated Pb(IV) atom is acting as Lewis acid has not
been previously studied in the literature as a sub-class of σ-hole
interactions. The sum of van der Waals and covalent radii of Pb
combined with several elements are given in Table 1.
Table 1. Data of ΣRvdW and ΣRcov values in Å for Pb combined with lone pair
donor atoms (Y).

Pb···Y ΣRvdW ΣRcov

Y=O 3.54 2.12

Y=N 3.57 2.17

Y=S 3.82 2.51

Accepted Manuscript
Y=F 3.49 2.03

Y = Cl 3.77 2.48

Y = Br 3.87 2.66

Y=I 4.00 2.85

We have found 20 organo-lead(IV) structures in the CSD

Figure 1 Compounds 1‒4 and complexes 5‒34 used in this study.
Results and discussion
CSD study
We have examined the CSD in order to provide experimental
evidence of the importance of σ-hole tetrel bonding interactions
in the solid state of Pb(IV) organic derivatives. In contrast to
Pb(II) coordination compounds, tetrel bonding interaction where
exhibiting tetrel bonding interactions (see Fig. 2 for some
selected examples). In particular, the 0D assemblies are
diphenyl-(2,2'-sulfanediyldibenzenethiolato-S,S')-lead
(QORWUQ, [ 29 ] Fig. 2a) and (μ3-sulfido)-(μ2-sulfido)-trimethyl-
tetrakis(triphenylphosphine)-lead-di-platinum hexafluoro-
phosphate salt (CIMDUY, [30] Fig 2b). The QORWUQ structure
forms self-assembled dimers in the solid state governed by the
formation of two symmetrically equivalent Pb···S interactions
that are slightly shorter than ΣRvdW (see Table 1). In the X-ray
structure of CIMDUY the trimethyl-lead group is bonded to the
μ3-sulfido S-atom. The σ-hole opposite to the Pb–S bond
interacts with the [PF6]– anion establishing a bifurcated tetrel
bonding with two fluorine atoms of the anion. One of the Pb···F

Figure 2 Ball and stick representations of refcodes QORWUC (a) CIMDUY (b), MEPBAZ (c), QASGOH (d), BRPHPB (e), and SNSCRD (f). Tetrel bonds are
represented as black dashed lines; hydrogens have been omitted for clarity. Distances (in Å) are shown close to the respective interactions. Color code: gray
carbon, blue nitrogen, red oxygen, brown bromine, orange phosphorous, yellow sulfur, pale grey platinum, dark gray lead.

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Chemistry - A European Journal 10.1002/chem.201900447

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tetrel bond distances is shorter than ΣR vdW and the other one is
0.2 Å longer. In both compounds (CIMDUY and QORWUQ) the
tetrel bond is established opposite to the most polarized Pb–S
bond, as expected in σ-hole interactions.

As examples of 1D supramolecular assemblies with Pb···O and

Pb···S tetrel bonding interactions we have selected the X-ray
structures of trimethyl-lead-diazo-ethylacetate (MEPBAZ, Fig.2c)
[ 31
and trimethyl-methylthiolato-lead (QASGOH, [ 32 ] Fig. 2d),
respectively.

In MEPBAZ structure the lead atom of a molecule and the

carbonyl oxygen atom of the adjacent molecule are connected

by a directional tetrel bonding interaction (C–Pb···O angle is
175⁰) thus explaining the formation of the infinite 1D
supramolecular assembly. The Pb···O distance is significantly
longer than ΣRcov and 0.5 A shorter than ΣRvdW suggesting a
strong noncovalent interaction. In the X-ray solid state structure
of QASGOH the infinite 1D assembly is clearly dominated by the
directional Pb···S noncovalent interactions (C–Pb···S angle
174⁰). It is worth mentioning that the lone pair of the S atom
approaches the tetrel atom along the extension of the C–Pb
bond, where the most positive σ-hole is located. An additional
example of 1D assembly is shown in Fig. 2e where the X-ray
structure of triphenyl-(2-bromophenyl-thiolato)-lead (refcode
BRPHPB)33 is represented. In this case the electron donor is a
Br atom and the Pb···Br tetrel bonding interaction is quite
directional (S–Pb···Br angle 169⁰). It can be observed that the
orientation of the bromophenyl ring facilitates the interaction of
the negative belt of the Br atom with σ-hole opposite to the S–Pb
bond. Finally, as example of 2D assembly, we have selected the
pentacarbonyl-(bis(trimethyl-lead)-sulfido)-tungsten structure
(SNSCRD).34 ] Two different Pb···O tetrel bonding interaction are
formed, thus generating the 2D supramolecular sheet. In both
contacts, O atoms belonging to the tungsten carbonyl ligands
approach to the Pb metal centers (3.549 and 3.785 Å) and form
the tetrel bonding interactions opposite to the most polarized S–
Pb bond. One of the Pb···O tetrel bond distances is
approximately equal to ΣRvdW and the other one is 0.2 Å longer
(see Table 1).
MEP Surface study
As a preliminary study, we have computed the molecular
electrostatic potential (MEP) surface of compounds 1 to 4 (see
Fig. 3). As it can be observed, for compounds 1 to 4 the MEP
surface showed the presence of a positive potential area located
at the outermost region of the Pb atom, opposite to the C‒Pb
bond (σ‒hole). Consequently, an attractive interaction with
electron rich atoms can be anticipated. In addition, the MEP
value at the σ‒hole decreases on going from 1 to 4, in line with
the electron-withdrawing ability of the substituent. The MEP is
also positive at the H-atoms of the methyl groups, which is +21
kcal/mol in compounds 1–3 and only +10 in compound 4. In the
latter the difference of MEP value at the Pb atom and H atom is
significantly reduced to 3 kcal/mol. Therefore, in compound 4 the
C–H···ElR H-bond could be competitive with the tetrel bond.
Accepted Manuscript
Figure 3 MEP (Molecular Electrostatic Potential) surfaces for compounds 1 to
4. Energy values in kcal/mol. MEP values at selected points of the surface are
indicated. For compounds 1 (a), 2 (b) and 3 (c) the energetic range is –50 to +
45 kcal/mol. For compound 4 (c) the MEP scale is ±15 kcal/mol.
Energetic study
The interaction energies and equilibrium distances obtained for
Pb(CH3)3X complexes 5 to 28 (see Fig. 1) studied herein are
summarized in Table 2. The examination of the results indicates
that the interaction energy values are strong for the anions
interacting with compounds 1–3 (ranging from ‒32.4 to ‒17.6
kcal/mol) and moderately strong for the same tetrel donor
molecules interacting with ammonia (ranging from ‒6.3 to ‒4.3
kcal/mol). The complexes with Pb(CH3)4 as tetrel donor are
weaker, in line with the MEP values commented above (see Fig.
2).
The anion complexes 11–13 present stronger interaction
energies than 5–7, conversely to the MEP analysis that shows
more positive values at the σ-hole of Pb(CH3)F. This is likely
due to the fact the CN substituent is a better leaving group. In
fact, complex 11 shows, a significant elongation of the Pb–CN
bond (from 2.229 Å in 2 to 2.456 Å in 11). On the contrary, for
the neutral electron donors, the interaction energies are slightly
stronger for Pb(CH3)F than for Pb(CH3)CN, in agreement with
the MEP values at the σ-hole. The tetrahedral environment of
the Pb atom changes to trigonal bipyramidal in the Cl–
complexes (see complexes 5 and 11 in Fig. 4). As expected, the
strongest complexes present the shorter equilibrium distances
that in all cases are longer than the sum of covalent radii (ΣRcov,
see Table 1) and shorter than the van der Waals radii (ΣR vdw,
see Table 1). It is worth mentioning that the energies of

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complexes 23 to 28, where the Pb–CH3 is not polarized, are not

negligible, ranging from –7.7 for the chloride complex to –1.3 for
the CO complex, thus revealing a strong ability of tetrahedral Pb
to establish tetrel bonding interactions even if it is not bonded to
electron withdrawing groups.

Table 2. BSSE-corrected Interaction energies (ΔE, kcal/mol), equilibrium

distances (R, Å) and the density at the bond CP that characterizes the tetrel
bond (ρ, a.u.) at the PBE0-D3/def2-TZVPD level of theory for complexes 6 to
28.

Complex ΔE R ρ (a.u.)

Accepted Manuscript
5 [Pb(CH3)3F:Cl–] –28.3 2.804 0.0329

6 [Pb(CH3)3F:Br–] –23.9 3.007 0.0319

7 [Pb(CH3)3F:I–] –19.7 3.319 0.0234

8 [Pb(CH3)3F:NH3] –6.3 3.010 0.0182

9 [Pb(CH3)3F:CO] –2.0 3.646 0.0053

10 [Pb(CH3)3F:HCN] –4.6 3.242 0.0095

11 [Pb(CH3)3CN:Cl–] –32.4 2.787 0.0408

12 [Pb(CH3)3CN:Br–] –28.0 3.000 0.0326

13 [Pb(CH3)3CN:I–] –24.6 3.320 0.0263

14 [Pb(CH3)3CN:NH3] –5.5 3.160 0.0129

15 [Pb(CH3)3CN:CO] –1.9 3.777 0.0042

16 [Pb(CH3)3CN:HCN] –4.5 3.376 0.0074

17 [Pb(CH3)3CF3:Cl–] –25.9 2.862 0.0355

18 [Pb(CH3)3CF3:Br–] –21.6 3.086 0.0280

Figure 4 Optimized geometries of some representative complexes at the
19 [Pb(CH3)3CF3:I–] –17.6 3.454 0.0188 PBE0-D3/def2-TZVPD level of theory. Distances in Å. ΔR values in complexes
5 and 10 correspond to the elongation of the Pb–X bond upon complexation.
20 [Pb(CH3)3CF3:NH3] –4.3 3.346 0.0100

21 [Pb(CH3)3CF3:CO] –1.6 3.867 0.0037

22 [Pb(CH3)3CF3:HCN] –3.6 3.489 0.0061

Table 3. BSSE-corrected Interaction energies (ΔE, kcal/mol), equilibrium
– distances (R, Å) and the density at the bond CP that characterizes the tetrel
23 [Pb(CH3)3CH3:Cl ] –7.7 3.386 0.0133
bond (ρ, a.u.) at the PBE0-D3/def2-TZVPD level of theory for complexes 29 to
34.
24 [Pb(CH3)3CH3:Br–] –3.4 3.715 0.0091
Complex ΔE R ρ (a.u.)
25 [Pb(CH3)3CH3:I–] –2.7 4.085 0.0065
29 [Sn(CH3)3F:Cl–] –26.9 2.678 0.0439
26 [Pb(CH3)3CH3:NH3] –2.5 3.844 0.0043
30 [Sn(CH3)3F:Br–] –21.3 2.906 0.0345
27 [Pb(CH3)3CH3:CO] –1.3 4.121 0.0025
31 [Sn(CH3)3F:I–] –15.9 3.248 0.0243
28 [Pb(CH3)3CH3:HCN] –2.2 3.803 0.0035
32 [Sn(CH3)3F:NH3] –6.1 2.825 0.0225

33 [Sn(CH3)3F:CO] –1.8 3.739 0.0040

34 [Sn(CH3)3F:HCN] –4.0 3.290 0.0077

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Chemistry - A European Journal
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For the Pb(CH3)3F series of complexes, we have also studied
the effect of changing Pb by Sn and the results are gathered in
Table 3. As described for other σ-hole interactions, the
interaction energies of complexes 29–34 weaken with respect to
the Pb complexes 5–10. In fact, the MEP value at the σ-hole
opposite to the F–Sn bond is 39 kcal/mol, 5 kcal/mol weaker
than that opposite to the F–Pb bond (see Fig. 3a).
AIM analysis
We have used the Bader’s theory of “atoms in molecules” to
characterize the noncovalent tetrel bond complexes described
above. The density values at the bond CP that connects the Pb
atom to the electron rich atom are included in Table 2. Moreover,
the distributions of critical points (CPs) and bond paths for
complexes 5–11, as a representative set are shown in Fig. 5. It
can be noticed in all cases the presence of a bond CP (green
sphere) and bond path interconnecting the Pb atom to the
electron rich atom.
Figure 5 Distribution of bond critical points and bond paths in complexes 5–10
and 33. Bond critical points are represented by green spheres. The bond
paths connecting bond critical points are also represented. The value of the
density at the bond critical point (ρ, a.u.) is also indicated in italics.
This article is protected by copyright. All rights reserved.
10.1002/chem.201900447
Remarkably, the AIM analysis also shows that the H-atoms of
the methyl groups are not involved in the interaction. For the Sn
complexes 29-34 the distribution of bond critical points and bond
paths is identical to the Pb series apart from the CO complex 33.
In this particular system, the distribution shows the existence of
three additional bond CPs and bond paths symmetrically
distributed that connect the C atom to the H-atoms of the methyl
group. This is likely due to the longer Sn···C distance and
shorter C···H distance observed in complex 33 compared to 9.
Interestingly, the comparison of the BSSE-corrected interaction
energies of complexes 5-28 with the electron charge density at
the bond CP that connects the Pb to the electron rich atom
reveals a remarkable trend. There is a strong correlation r2 =
Accepted Manuscript
0.966 between the interaction energy and the values of the
density (see Figure 6) at the bond CP. This result evidences that
the value of ρ(r) at the cage CP can be used as a measure of
bond order in tetrel bonding interactions. It should be
emphasized the importance of this correlation, since anionic and
neutral electron donors are included in the same representation.
Figure 6 Plot of the regression between the electron density at the bond CP
and the interaction energy for complexes 5–28.
NCIplot analysis
We also carried out the NCIplot index calculation of Pb(IV) tetrel
bonding complexes 5–28 to further explore the nature of the
tetrel bonding interaction. The NCIplot is an intuitive index that
enables the visualization of noncovalent interactions easily and
the extent to which molecular regions interact. It essentially
provides qualitative information using a red–yellow–green–blue
scale with red for repulsive and blue for attractive. Green and
yellow surfaces represent weak attractive and weak repulsive
interactions, respectively. The representations of the NCIplots
computed for one series of complexes are shown in Figure 7
and the rest in the ESI (Figure S1). As noted, for complex 17 the
NCI plot shows a dark blue isosurface between the anion the
Pb(IV) that progressively changes from dark blue to light blue on
going from complex 17 to 19, in line with the interaction energies
and the values or ρ(r) at the bond CPs gathered in Table 2.
Moreover, the isosurface that characterizes the tetrel bond is
green in the neutral complexes 20–22, also in agreement with
the energetic and geometric features of these complexes. This
behavior is also observed in the series of compounds 1 and 3
(see Figure S1). In the series of compound 4, the isosurfaces
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are green for all complexes thus indicating weaker interactions.
It should be highlighted that there is a significant difference
between the AIM and the NCIplot analyses. That is, the NCIplot
reveals a weak interaction between the electron rich atom and
the H-atoms of the methyl groups, as revealed by the shape of
the NCIplot surface. In all cases the isosurface located between
the H-atoms and the electron donor is green thus indicating a
small contribution to the overall interaction energy.
Figure 7. NCI plots of complexes 17–22 at the PBE0-D3/def2-TZVP level of
theory. The gradient cutoff is s=0.35 au, and the color scale is in the range
−0.04<ρ<0.04 a.u.
Conclusions
The results reported in this manuscript highlight the ability of
organolead(IV) compounds to establish noncovalent tetrel
bonding interactions with several anions and NH3, CO, and HCN
molecules. The results presented herein also provide
experimental evidence retrieved from the CSD of the ability of
tetrahedral Pb(IV) atom to interact with electron rich atoms that
can be important in the field of crystal engineering. We have
successfully characterized the interactions using the NCI plot
and the Bader’s theory of “atoms in molecules” that reveals the
existence of a unique bond critical point and bond path
connecting the tetrahedral Pb atom to the electron donor.
Computational Methods
The energies of all complexes included in this study were computed at
the PBE0[ 35 ]-D3[ 36 ]/def2-TZVPD[ 37 ] level of theory by means of the
program TURBOMOLE version 7.0. [38] For tin and lead, the basis set
includes scalar-relativistic calculations with effective core potentials
(ECPs), [39] relativity is taken into account using the Dirac-Hartree-Fock
ECPs. [40] Moreover, for a set of complexes (X = F, Y = Cl, Br, I, NH3, CO
and HCN) we have also taken into consideration spin-orbit effects using
the def2-TZVP-2c basis set for lead. This uses the “exact two
component” (X2C) [41] method for treating relativistic effects and spin-orbit
coupling effects.[42 ] We have corrected the basis set superposition error
using the counterpoise methodology.[ 43 ] The MEP (Molecular
Electrostatic Potential) calculations have been performed at the PBE0-
D3/def2-TZVP level of theory by means of the Gaussian-16 calculation
This article is protected by copyright. All rights reserved.
10.1002/chem.201900447
package. [44] The Bader’s "Atoms in molecules" theory[45] has been used
to study the interactions discussed herein by means of the AIMall
calculation package. [46] The calculations for wavefunction analyses were
carried out at the PBE0-D3/def2-TZVP level of theory. Moreover, the
NCIplot[47] isosurfaces have been computed at the same level using the
density cube files (fine grid) obtained from Gaussian-16. The isosurfaces
correspond to both favorable and unfavorable interactions, which
depends on the sign of the second density Hessian eigenvalue and
represented by the isosurface color. The standard color scheme has
been used that is: red–yellow–green–blue scale with red for repulsive
(ρ+cut) and blue for attractive (ρ+cut) NCI interaction density. Green and
yellow surfaces represent weak attractive and weak repulsive
noncovalent contacts, respectively.
Accepted Manuscript
Acknowledgements
We thank the DGICYT of Spain (project CTQ2017-85821-R
FEDER funds). We thank the CTI (UIB) for computational
facilities. A. F. thanks MINECO/AEI from SPAIN for a “Juan de la
Cierva” contract. We also thank F. Listorti and N. Crespí (UIB)
for helpful discussions.
Keywords: tetrel bonding • CSD analysis • σ-hole interactions •
Supramolecular Chemistry • DFT caculations
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In this manuscript the ability of Antonio Franconetti and Antonio
organolead(IV) compounds and Frontera*
several electron rich molecules to
establish noncovalent tetrel bonding Page No. – Page No.

Accepted Manuscript
interactions has been studied at the
Theoretical and crystallographic
PBE0-D3/def2-TZVPD level of
study on Pb(IV) tetrel bonding
theory. Experimental evidence has
interactions
been obtained from the Cambridge
Structural Database.

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