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The electronic structure and interatomic interactions in xenon hexafluoride

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Russian Journal of Coordination Chemistry, Vol. 31, No. 10, 2005, pp. 708–718. Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 10, 2005, pp. 746–756.
Original Russian Text Copyright © 2005 by Bobrov, Tsirelson.

Chemical Bonding in the Complexes XeF+5 X F –

6

(X = P, As, Sb, and Bi)

M. F. Bobrov and V. G. Tsirelson
Mendeleev University of Chemical Technology, Miusskaya pl. 9, Moscow, 125047 Russia
Received January 24, 2005

+ –
Abstract—Ab initio quantum-chemical calculations of the complexes XeF 5 XF 6 (X = P, As, Sb, and Bi) were
performed with the use of relativistic pseudopotentials for heavy atoms and full-electron basis sets. The chem-
ical bonds were characterized by the parameters of critical points (electron density, its Laplacian, total electron
+
energy, and its kinetic and potential components). It was demonstrated that the interaction between the XeF 5
– + –
cation and the XF 6 anion in XeF 5 XF 6 follows a key–lock scheme involving directed interactions of bridging
fluorine atoms Fb Xe and that the structuring function of the lone electron pair of the Xe atom is to com-
pensate the destabilizing electrostatic interaction between the Xe and X atoms bearing excess positive charges.

In complexes XeF6 · XFn – 1 (X is an element of the Earlier, we studied the geometrical and electronic
Periodic Table; n = 4, 5, or 6 [1–3]), the Xe atom is + –
structures of free molecules XeF 5 XF 6 (X = P, As, Sb,
bound to six, seven, or eight F atoms. An investigation or Bi) by quantum-chemical methods with large basis
of such complexes would make it possible to find out sets [10–14]. However, the roles of relativistic effects
how the parameters of the Xe–F bonds depend on their and electron correlation have not been discussed; nei-
mutual spatial arrangement and the type of the X atom. ther has a global search for all possible stationary points
However, the literature data on their quantum-chemical on the potential energy surface been performed.
calculations are unavailable. X-ray diffraction analysis In this study, we performed complete conforma-
of such complexes with X = P, As, Sb, and Bi in the + –
tional analysis of the complex fluorides XeF 5 XF 6 (X =
solid state [2, 4] and Raman and 19F NMR studies of
P, As, Sb, and Bi) and investigated the parameters of the
+ –
XeF 5 XF n in hydrofluoric acid solutions [2, 5–9] chemical bonds between the atoms of these complexes
+ in terms of Bader’s AIM theory [15, 16]. In addition, we
revealed that the XeF5 fragment exists as a XeF 5 cation estimated the reactivity characteristics (chemical hard-
with a symmetry close to C4ν. As for the XF 6 anion, its
– ness and nucleophilicity/electrophilicity) of these mol-
ecules.
structure is usually a distorted octahedron [4]. The unit
+ –
cell of XeF 5 AsF 6 crystal consists of four molecules
THEORETICAL CONCEPTS USED
+ – FOR ANALYSIS
linked in pairs into cyclic clusters ( XeF 5 AsF 6 )2 [4]; the
+ Quantum-chemical calculation with optimization of
XeF 5 cation forms three bridging fragments with two geometrical parameters allows one to find the coordi-
– nates of the nuclei of the molecule, which correspond
AsF 6 anions. Such a structure of the cluster
+ –
to the stationary point on the potential energy surface.
( XeF 5 AsF 6 )2 is due to peculiar interactions between To determine the type of this stationary point (mini-
– mum or saddle point), one should calculate a matrix of
Xe atoms and the F atoms of the octahedral AsF 6 ion: the second derivatives of energy with respect to the
two Xe–F–As bridges forms a dimer. Nevertheless, the coordinates (force constant matrix), which specifies the
bridging F atom can be regarded as belonging to the frequencies of normal nuclear vibrations. The type of
– the stationary point that matches a given molecular
AsF 6 anion since it is shifted only slightly to the Xe
structure is dictated by the number of imaginary fre-
atom. Raman spectroscopy has revealed that such a quencies. The conformation having no frequencies with
structure of molecular ions is retained in solutions of a negative wavenumber corresponds to an equilibrium
anhydrous HF [4]. geometry with a minimum energy [17].

1070-3284/05/3110-0708 © 2005 Pleiades Publishing, Inc.


CHEMICAL BONDING IN THE COMPLEXES Xe F 5 X F 6
The simplest reactivity indices of compounds are
effective atomic charges. We estimated them by using
the Mulliken analysis of orbital populations [18]
(although being sensitive to the size of the basis set, it
is useful for comparative analysis of compounds calcu-
lated in the same basis).
Another reactivity index was chemical hardness h.
In terms of the orbital concepts [19–22], η is defined by
the Koopmans theorem [23] as
η = (ELUMO – EHOMO)/2, (1)
where ELUMO and EHOMO are the energies of the lowest
unoccupied and highest occupied molecular orbitals,
respectively. The compound as a whole predominantly
exhibits nucleophilic properties at ELUMO > 0 and elec-
trophilic ones at ELUMO < 0 [24]. Of course, all these
parameters are orbital-dependent.
Orbital-independent information on atomic interac-
tions is provided by Bader’s theory [15, 16], which
describes chemical bonding in terms of topological
characteristics of electron density (ED) distribution.
Essential characteristics of this theory are the ED value
and its curvature at critical points (CPs), in which the
ED gradient is zero. The ED curvature along the mutu-
ally perpendicular directions at a critical point is deter-
mined by the eigenvalues of the ED Hessian λ1 ≤ λ2 ≤
λ3. The type of the critical point is determined by its
rank (number of nonzero values of the ED curvature
(li)) and sign (algebraic sum of the signs of λi). The
critical points of ED may be maxima, minima, and sad-
dle points. A saddle point with one positive and two
negative curvatures is most interesting for us. This CP
lies on a line connecting the neighboring nuclei, along
which the electron density is higher than at adjacent
side points (bond line) [16]. This point is named the
bond CP and has rank 3 and sign –1; so it is denoted CP
(3, –1). The electron density at the bond CP (rb) char-
acterizes the interatomic interaction.
The values of λi, the ED Laplacian ∇2ρb = λ1 + λ2 +
λ3, and the local densities of the kinetic (gb > 0) and
potential energies (νb < 0) at the bond CP characterize
the type of interatomic interaction. In [15, 16, 25–29], it
was shown that for covalent interactions between atoms,
the characteristic values are ρb > 0.15 au, |λ1|/λ3 > 1,
∇2ρb < 0, hb < 0, |νb|/gb > 2, and gb/ρb > 1 [15, 16] (hb =
gb + νb is the density of the total electron energy at the
bond CP). For ρb < 0.07 au, |λ1|/λ3 < 0.25, ∇2ρb > 0, hb > 0,
|νb|/gb < 1, and gb/ρb > 1, interatomic interactions are said
to be of the closed-shell type. For 0.07 < ρb < 0.15 au,
|λ1|/λ3 > 0.20, ∇2ρb > 0, hb < 0, 1 < |νb|/gb < 2, and
gb/ρb > 1, interatomic interactions are said to be of the
intermediate type [25–29].
Thus, the critical points and their parameters dis-
tinctly characterize the structure of a molecule and the
character of bonding between its atoms.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
+ – 709
The positions of electron pairs are localized empiri-
cally by identifying them as the maxima of the negative
Laplacian of the ED [16]. Unfortunately, this function
cannot discriminate between the valence electron shells
of atoms with Z > 20 [16]. For this reason, we used the
electron localization function (ELF) q [30–33]. It is
defined as
0
θ = 1/(1 + [Dσ(r)/ D σ (r)]2), (2)
0
where Dσ(r) and D σ (r) are the curvatures of paired
electron densities for electrons with identical spins at
point r of a system under study and for a uniform elec-
tron gas of equal density at the same point, respectively.
The ELF points to areas with reduced kinetic energy
densities, which arise from repulsion of electrons with
identical spins. The θ values are low in areas with a
high local density of the kinetic energy, in which,
according to the Pauli principle, the repulsion of elec-
trons with parallel spins is the greatest. In areas with a
decreasing kinetic energy, θ increases, approaching
unity [31, 32]. The areas with θ > 0.5 indicate localiza-
tion of electron pairs [31].
In the ELF topology, there are two types of basins
matching local maxima (attractors) [31]. Core basins Ci
are near nuclei i and provide information on the struc-
ture of core atomic shells. Valence basins appear along
internuclear vectors and in areas where lone electron
pairs are localized. Each valence basin of the ELF is
characterized by the synaptic order (i.e., the number of
cores with which the basin is linked). Monosynaptic
basins Vi are near nuclei i, while disynaptic basins Vi, j
are between nuclei i and j.
COMPUTATIONAL PROCEDURE
To find out how the level of a ab initio quantum-
chemical calculation affects the parameters of the com-
+ –
plexes XeF 5 XF 6 , we calculated the geometrical
+ –
parameters of the molecule of XeF 5 AsF 6 by the
restricted Hartree–Fock (RHF) method [34, 35] for dif-
ferent basis sets with the use of relativistic pseudopo-
tential for the Xe and X atoms [36–40]. Consideration
of the correlation in terms of the MP2/3-21G perturba-
tion theory did not change the structure appreciably. We
found it optimal, from the viewpoint of both accuracy
and time consumption, to calculate the geometry of the
+ –
complexes XeF 5 XF 6 by the RHF method [34] with the
6-311+G* basis set [35] for F atoms and relativistic
pseudopotentials for Xe and X atoms [36–40] (basis
set I). However, the use of pseudopotentials provides
neither the complete pattern of ED distribution nor its
accurate topology [41]. For this reason, geometry opti-
mization with basis I was followed by calculation of a
wavefunction with Gaussian full-electron basis sets
Vol. 31 No. 10 2005
710 BOBROV, TSIRELSON
F11
F10 F9
As
F7 F8
F6
F3
Xe
F5 F4
F2
F1
+ –
Fig. 1. Structure of the complex XeF 5 AsF 6 .
proposed by Tatewaki et al. [42] (basis set II); such a
wavefunction was used to calculate the ED. It should be
emphasized that the calculations with basis II gave the
same molecular geometry as the basis sets with relativ-
istic pseudopotentials, although the computation time
was substantially longer.
Computations were performed with the
GAMESS(US) program package [43, 44]. Topological
analysis of the electron density was carried out with the
AIMPAC program package [15] adapted for IBM PC
[45].
RESULTS AND DISCUSSION
Geometrical Structure
Let us consider the geometrical structure of the
+ – + –
complexes XeF 5 XF 6 with XeF 5 AsF 6 as an example.
Analysis of stationary points on the potential energy
surface, which were found by optimization of the
geometry of this molecule, showed that only conformer I
displayed in Fig. 1 corresponds to the energy minimum.
In the resulting structure, the Xe atom in the base of the
+ Our analysis of the frontier orbitals revealed that
square-pyramidal cation XeF 5 forms three bonds with
the bridging Fb atoms (b = 6, 7, and 8). The symmetry
+ complexes XeF 5 XF 6 ; i.e., these complexes are electro-
of the XeF 5 fragment is close to C4ν, which agrees with
experimental data for crystals and solutions [2, 4, 5–9].
The axial F1 atom is closer to the Xe atom than are
equatorial atoms, regardless of the basis set (Table 1).
The bond angle α1(F1XeF2) is virtually identical with
that obtained from X-ray diffraction data (Table 1).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
The calculation revealed that the symmetry of the
–
AsF 6 fragment is slightly different from octahedral,
which had been reported in [2, 4]; its symmetry remains
close to C3ν. This deviation is due to the nonsymmetri-
cal effects of the bridging fragments Xe–Fb–As, which
diminish the bond angle α3. The calculated As–Fj bond
lengths (j = 6–11) are very close to the X-ray diffraction
data, although the difference in the bond angles of the
–
AsF 6 fragment is ~10°. The dipole moment of the
+ –
XeF 5 AsF 6 molecule is 7.06 and 8.64 D in bases I and
II, respectively. The high polarity of the complex arises
from the fact that the interaction between XeF6 and
AsF5, which have low dipole moments, causes the
bridging F atoms to shift from the Xe atom to the As
+ –
atom, thus forming the ionic structure XeF 5 AsF 6 . Note
that this is characteristic of both the condensed phase
[4] and separate molecules.
Analysis of stationary points on the potential energy
+ –
surface for the other complexes XeF 5 XF 6 (X = P, Sb,
and Bi) showed that conformer I displayed in Fig. 1 has
a minimum energy.
The nature of the X atom affects the structure of the
+ –
complexes XeF 5 XF 6 (Table 2) as follows. The change
in the Xe–Fi bond lengths (i = 1–5) when passing from
+ – + –
XeF 5 PF 6 to XeF 5 BiF 6 does not exceed 0.006 Å. How-
ever, the lengths of the bridges r(Xe–Fb) (b = 6, 7, and
8) differ noticeably; in the series P–As–Sb–Bi, their
difference ∆r(Xe–Fb) decreases from 0.088 to 0.055 Å.
The positive charge on the Xe atom in all molecules is
virtually equal (2.48–2.49 e); the charge on the X atom
changes in the series X = P, As, Sb, and Bi as follows:
+1.93, +1.93, +2.52, and +2.76 e.
+
Thus, the structure of the XeF 5 cation is virtually
–
insensitive to the nature of the X atom in the XF 6
anion. The increase in the X–Fj distances (j = 6–11) in
–
the XF 6 anion is naturally associated with increasing
number of core shells in the X atom. Simultaneously,
the bridging fragment Xe–F–X becomes longer, while
the dipole moment of the molecule decreases from 7.59
to 4.05 D in the series X = P, As, Sb, and Bi.
ELUMO is negative for all the geometrically optimized
+ –
philes. They are slightly different in hardness: 0.268,
0.266, 0.267, and 0.261 au for X = P, As, Sb, and Bi,
respectively. All the molecules studied can be classified
among hard reagents and assumed to behave similarly
in orbital-controlled reactions. Obviously, favorable
conditions for an electrophilic attack are created by the
Vol. 31 No. 10 2005
 + – 711
CHEMICAL BONDING IN THE COMPLEXES Xe F 5 X F 6
negatively charged F atoms. Hypothetical reactive sites Table 1. Optimized equilibrium geometrical parameters
at the X and Xe atoms are surrounded by F atoms and (bond lengths (r (Å) and angles (α, (deg)) calculated with ba-
the probability of a nucleophilic attack on them, even sis sets I and II for conformer I and the corresponding param-
+ –
with consideration of thermal motion under real condi- eters for the fragment of the crystal structure of XeF 5 AsF 6
tions, is negligible. (X-ray diffraction data [4])
Method
Topological Analysis of the Electron Density Calculat- X-ray dif-
Calculated
ed with fraction
+
and Chemical Bonding in XeF 5 XF 6
–
Geometrical with basis I
basis II data [4]
parameter
+
Chemical Xe–F bonds in the XeF 5 cation. The r (Xe–F1) 1.839 1.853 1.79
ED values and other local ED characteristics at the crit- r (Xe–Fi), i = 2–5 1.860 1.867 1.82
ical points of equatorial Xe–Fi bonds (i = 2–5 in r (Xe–F6) 2.642 2.677 2.65
+ –
XeF 5 AsF 6 ) are close to those for the axial ï–F1 bond r (Xe–F7) 2.702 2.790 2.70
(Table 3). The ED Laplacian and the parameters |λ1|/λ3, r (Xe–F8) 2.710 2.789 2.81
hb, gb/ρb, and |νb|/gb characterize these bonds as polar, r (Xe–F6–As) 4.418 4.448 4.38
partially covalent bonds of the intermediate type with a r (Xe–F7–As) 4.474 4.552 4.46
negative electron energy. According to the ρb and hb
r (Xe–F8–As) 4.481 4.551 4.55
values, the bonds formed by equatorial atoms are
+ – Shift of Fb 19.6 20.4 21.0
weaker. This is also true for other complexes XeF 5 XF n to the As atom, % 20.8 22.6 21.1
(X = P, As, Sb, and Bi). 21.0 22.6 23.5
Bridging fragments Xe–Fb–X. The ρb and |λ1|/λ3 r (As–F6) 1.776 1.771 1.73
values characterizing the Xe–Fb bridging bonds in r (As–F7) 1.772 1.762 1.76
+ –
XeF 5 XF 6 are substantially lower than those for Xe–Fi r (As–F8) 1.771 1.762 1.74
bonds (i = 1–5) (Tables 3, 4), hb becomes slightly posi- r (As–F9) 1.678 1.684 1.65
tive (covalent component disappears), and usually r (As–F10) 1.678 1.684 1.69
gb/ρb > 1. Thus, these bonds represent typical interac- r (As–F11) 1.679 1.684 1.72
tions between closed shells [16].
α1 (F1XeF2) 79.7 79.8 79.7
–
Chemical X–F bonds in the XF 6 anion. The ï–Fb α2 (F6AsF7) 81.7 83.2 89.8
(b = 6, 7, and 8) and X–Fi bonds (i = 9, 10, and 11)
–
(Tables 5, 6) in the XF 6 anion are similar but slightly
pair of the Fb atom is directed toward the Xe atom. The
different in parameters: for the X–Fb bonds, ρb is lower
nonbonding EPLF maximum at the Xe atom (mono-
than for the X–Fj bond (j = 9–11), νb is less negative, –
and gb and gb/ρb are lower for longer internuclear dis- synaptic attractor) in the XF 6 anion is directed toward
tances. The high ρb values and the negative hb values the X atom: it indicates the area of localization of the
indicate a significant covalence of all these bonds. lone electron pair of Xe, the maximum is approxi-
Thus, the Xe–Fb and X–Fb bonds substantially differ mately equidistant from the lines of the Xe–Fb bonds.
in parameters: the Xe–Fb bonds approach idealized Such a pattern perfectly agrees with the quantitative
interactions between closed-shell atoms, while the + –
X−Fb bonds are largely covalent. It should be empha- characteristics of the chemical bonds in XeF 5 XF 6 con-
sized that the bridging F atoms are bound to the X atom sidered above and supplements it with important
much more strongly than to the Xe atom. +
details. For instance, the interaction between the XeF 5
Distribution of the electron localization function. –
+ – cation and the XF 6 anion can be said to follow the key–
The ELF cross sections in XeF 5 AsF 6 (Fig. 2) reveal the
following features characteristic of all the molecules lock scheme involving the directed Fb Xe interac-
studied. The partially covalent Xe–F1 and Xe–Fi bonds tions (bond lines form), while the lone electron pair of
(i = 2–5) show bonding maximums (disynaptic attrac- the Xe atom compensates the destabilizing electrostatic
tors) near the F atom, which are directed toward the Xe repulsion of the Xe and X atoms bearing excess positive
and X atoms. In the Xe–Fb bridging bonds with interac- charges (no bond line forms between the Xe and
tions of the closed-shell type, the maximum (also a X atoms). Note that the key–lock interactions involving
disynaptic attractor) corresponding to a lone electron the lone electron pairs of the Cl atom were also identi-

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 31 No. 10 2005

712 BOBROV, TSIRELSON

Table 2. Geometrical parameters (bond lengths r (Å), bond angles α (deg), and dipole moments µ (D)) calculated with basis
+ –
set I for conformer I of the complexes XeF 5 XF 6 (X = P, As, Sb, and Bi)

X atom P As Sb Bi
µ 7.59 7.06 7.03 4.05
r (F1–Xe) 1.838 1.839 1.840 1.844
r (Fi–Xe), i = 2–5 1.860 1.860 1.859 1.862
r (Xe–F6) 2.655 2.643 2.673 2.636
r (Xe–F7) 2.655 2.701 2.717 2.672
r (Xe–F8) 2.743 2.709 2.735 2.691
∆r (Xe–FÏ) 0.088 0.066 0.062 0.055
r (Xe–F6–X) 4.314 4.420 4.610 4.855
r (Xe–F7–X) 4.314 4.473 4.652 4.891
r (Xe–F8–X) 4.392 4.480 4.669 4.908
Shift of Fb 23.1 19.6 16.0 9.2
to the X atom, %
23.1 20.8 16.8 9.3
24.9 20.9 17.2 9.7
r (X–F6) 1.659 1.777 1.937 2.219
r (X–F7) 1.659 1.772 1.935 2.219
r (X–F8) 1.649 1.771 1.934 2.217
r (X–F9) 1.559 1.678 1.857 2.119
r (X–F10) 1.559 1.678 1.857 2.119
r (X–F11) 1.559 1.679 1.857 2.119
α1 (F1XeF2) 79.6 79.7 79.6 79.0
α2 (XeFbX) 100.4 100.9 100.2 100.7
α3 (F6XF7) 84.3 81.7 79.8 74.0

fied in the study of spatial arrangement of chlorine mol-
ecules in the crystalline state [46].
The results obtained can be summarized as follows.
+ –
The geometrical parameters of XeF 5 XF 6
molecules
(X = P, As, Sb, and Bi), which were calculated by the
Hartree–Fock method with full-electron basis sets [42],
approximate to those obtained with the use of relativis-
tic pseudopotentials for the Xe and As atoms (in this
case, less time was required for computations). There-
fore, the latter method can be recommended for calcu-
lation of the molecular geometries of complexes con-
taining heavy atoms, while full-electron basis sets
should be used for topological analysis of the electron
density.
On the whole, all the molecules studied exhibit elec-
trophilic properties and are approximately equal in
chemical hardness. The parameters of the chemical
bonds suggest that the equatorial F atoms in the XeF 5
+
cation are most weakly bound and hence most reactive.
The calculated numerical characteristics of the crit-
ical points of the chemical bonds (electron density, its
Laplacian, total electron energy, and its kinetic and
potential components) allowed us to define interactions
of the xenon atom with the axial and equatorial fluorine
+
atoms in the XeF 5 cation as polar, partially covalent
bonds of the intermediate type with a negative electron
energy; the bonds formed by the equatorial atoms are
weaker. The electron energy at the critical points of the
Xe–Fb bridging bonds is slightly positive (covalent
component disappears). Thus, these bonds are close to
the idealized interactions between atoms with closed
–
electron shells. In the XF 6 anion, all the X–F bonds are
of the intermediate type with a considerable covalence.
The bridging F atoms are bound to the X atom substan-
tially more strongly than to the Xe atom.

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 31 No. 10 2005

 + – 713
CHEMICAL BONDING IN THE COMPLEXES Xe F 5 X F 6

+ –
Table 3. Parameters of the critical points of the bonds in XeF 5 AsF 6 *

Bond Xe–F1 Xe–Fi (i = 2–5) Xe–Fb (i = 6–8) X–Fb (i = 6–8) X–Fj (j = 9–11)
r, Å 1.839 1.860 2.643 1.777 1.678
2.701 1.772 1.678
2.709 1.771 1.679
ρb 0.172 0.161 0.030 0.129 0.169
0.028 0.131 0.169
0.027 0.132 0.169
∇2ρb 0.302 0.321 0.130 0.602 0.849
0.124 0.609 0.849
0.122 0.610 0.848
λ1 –0.238 –0.222 –0.034 –0.206 –0.297
–0.030 –0.210 –0.297
–0.030 –0.210 –0.296
λ2 –0.238 –0.210 –0.033 –0.205 –0.296
–0.030 –0.209 –0.296
–0.030 –0.209 –0.296
λ3 0.778 0.752 0.197 1.012 1.441
0.184 1.027 1.442
0.182 1.030 1.434
|λ1|/λ3 0.306 0.295 0.170 0.203 0.206
0.165 0.204 0.206
0.165 0.204 0.206
νb –0.306 –0.283 –0.028 –0.258 –0.384
–0.025 –0.263 –0.385
–0.025 –0.264 –0.384
gb 0.190 0.182 0.031 0.204 0.298
0.028 0.208 0.298
0.028 0.208 0.298
|νb|/gb 1.604 1.560 0.931 1.263 1.289
0.903 1.267 1.289
0.903 1.267 1.289
hb –0.115 –0.102 0.002 –0.054 –0.086
0.003 –0.055 –0.086
0.003 –0.056 –0.086
hb /ρb –0.668 –0.632 0.070 –0.416 –0.510
0.099 –0.422 –0.510
0.099 –0.423 –0.510
gb /ρb 1.106 1.130 1.003 1.580 1.765
1.019 1.583 1.765
1.019 1.584 1.765
* All the parameters but the bond lengths are quoted in au.

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 31 No. 10 2005

714 BOBROV, TSIRELSON

+ –
Table 4. Parameters of the critical points of the Xe–Fb bond in XeF 5 XF 6 (X = P, As, Sb, and Bi)*

+ – + – + – + –
Molecule XeF 5 PF 6 XeF 5 AsF 6 XeF 5 SbF 6 XeF 5 BiF 6

r (Xe–F6), Å 2.655 2.643 2.673 2.636

7),
r (Xe–F Å 2.655 2.701 2.717 2.672
8),
r (Xe–F Å 2.743 2.709 2.735 2.691
ρb 0.030 0.030 0.029 0.030
0.030 0.028 0.027 0.029
0.026 0.027 0.026 0.028
∇2rb 0.133 0.130 0.122 0.127
0.133 0.124 0.118 0.126
0.120 0.122 0.115 0.124
λ1 –0.034 –0.034 –0.031 –0.033
–0.034 –0.030 –0.029 –0.031
–0.028 –0.030 –0.027 –0.030
λ2 –0.033 –0.033 –0.030 –0.032
–0.033 –0.030 –0.028 –0.031
–0.028 –0.030 –0.027 –0.030
λ3 0.200 0.197 0.183 0.192
0.200 0.184 0.175 0.188
0.175 0.182 0.170 0.184
|λ1|/λ3 0.168 0.170 0.168 0.170
0.168 0.165 0.163 0.166
0.160 0.165 0.161 0.164
νb –0.029 –0.028 –0.026 –0.028
–0.029 –0.025 –0.024 –0.027
–0.024 –0.025 –0.023 –0.026
gb 0.031 0.031 0.028 0.030
0.031 0.028 0.027 0.029
0.027 0.028 0.026 0.028
|νb|/gb 0.929 0.931 0.919 0.935
0.930 0.903 0.898 0.916
0.891 0.903 0.891 0.908
hb 0.002 0.002 0.002 0.002
0.002 0.003 0.003 0.003
0.003 0.003 0.003 0.003
hb /ρb 0.073 0.067 0.081 0.064
0.072 0.099 0.103 0.084
0.114 0.099 0.110 0.093
gb /ρb 1.028 1.003 0.992 0.985
1.028 1.019 1.007 1.002
1.042 1.019 1.007 1.006
* All the parameters but the bond lengths are quoted in au.

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 + – 715
CHEMICAL BONDING IN THE COMPLEXES Xe F 5 X F 6
+ –
Table 5. Parameters of the critical points of the Fb–X bond in XeF 5 XF 6 (X = P, As, Sb, and Bi)*

+ – + – + – + –
Molecule XeF 5 PF 6 XeF 5 AsF 6 XeF 5 SbF 6 XeF 5 BiF 6

r (X–F6), Å 1.659 1.777 1.937 2.219

7),
r (X–F Å 1.659 1.772 1.935 2.219
8),
r (X–F Å 1.649 1.771 1.934 2.217
ρb 0.122 0.129 0.107 0.059
0.122 0.131 0.108 0.060
0.125 0.132 0.108 0.060
∇2rb 0.636 0.602 0.632 0.339
0.635 0.609 0.636 0.338
0.670 0.610 0.638 0.341
λ1 –0.174 –0.206 –0.160 –0.065
–0.174 –0.210 –0.161 –0.065
–0.183 –0.210 –0.162 –0.066
λ2 –0.174 –0.205 –0.159 –0.065
–0.174 –0.209 –0.160 –0.065
–0.182 –0.209 –0.161 –0.065
λ3 0.984 1.012 0.951 0.468
0.982 1.027 0.957 0.469
1.036 1.030 0.960 0.472
|λ1|/λ3 0.177 0.203 0.168 0.139
0.177 0.204 0.168 0.140
0.176 0.204 0.169 0.140
νb –0.265 –0.258 –0.204 –0.123
–0.265 –0.263 –0.207 –0.122
–0.276 –0.264 –0.207 –0.124
gb 0.212 0.204 0.181 0.104
0.212 0.208 0.183 0.104
0.222 0.208 0.183 0.105
|νb|/gb 1.251 1.263 1.127 1.184
1.251 1.267 1.130 1.183
1.244 1.267 1.131 1.185
hb –0.053 –0.054 –0.023 –0.019
–0.053 –0.055 –0.024 –0.019
–0.054 –0.056 –0.024 –0.019
hb /ρb –0.435 –0.416 –0.216 –0.320
–0.436 –0.422 –0.220 –0.319
–0.432 –0.423 –0.221 –0.323
gb /ρb 1.739 1.580 1.694 1.741
1.736 1.584 1.695 1.750
1.771 1.583 1.695 1.747
* All the parameters but the bond lengths are quoted in au.

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 31 No. 10 2005

716 BOBROV, TSIRELSON

+ –
Table 6. Parameters of the critical points of the Fi–X bond (i = 9–11) in XeF 5 XF 6 (X = P, As, Sb, and Bi)*

+ – + – + – + –
Molecule XeF 5 PF 6 XeF 5 AsF 6 XeF 5 SbF 6 XeF 5 BiF 6

r (X–F9), Å 1.559 1.678 1.857 2.119

10),
r (X–F Å 1.559 1.678 1.857 2.119
11),
r (X–F Å 1.559 1.679 1.857 2.120
ρb 0.154 0.169 0.133 0.076
0.154 0.169 0.133 0.076
0.154 0.169 0.133 0.077
∇2rb 1.082 0.849 0.809 0.476
1.077 0.849 0.809 0.478
1.082 0.848 0.809 0.476
λ1 –0.269 –0.297 –0.208 –0.084
–0.269 –0.297 –0.208 –0.084
–0.269 –0.296 –0.208 –0.084
λ2 –0.269 –0.296 –0.207 –0.084
–0.268 –0.296 –0.207 –0.084
–0.269 –0.296 –0.207 –0.085
λ3 1.620 1.441 1.224 0.644
1.615 1.442 1.224 0.646
1.619 1.434 1.223 0.644
|λ1|/λ3 0.166 0.206 0.170 0.130
0.167 0.206 0.170 0.130
0.166 0.206 0.170 0.131
νb –0.389 –0.384 –0.280 –0.181
–0.389 –0.385 –0.280 –0.181
–0.390 –0.384 –0.379 –0.180
gb 0.330 0.298 0.241 0.150
0.329 0.298 0.241 0.150
0.330 0.298 0.241 0.150
|νb|/gb 1.179 1.289 1.162 1.207
1.182 1.289 1.162 1.207
1.179 1.289 1.161 1.207
hb –0.059 –0.086 –0.039 –0.031
–0.060 –0.086 –0.039 –0.031
–0.059 –0.086 –0.038 –0.030
hb /ρb –0.383 –0.510 –0.293 –0.405
–0.390 –0.510 –0.293 –0.405
–0.383 –0.510 –0.294 –0.404
gb /ρb 2.143 1.765 1.812 1.974
2.134 1.765 1.812 1.974
2.140 1.765 1.812 1.974
* All the parameters but the bond lengths are quoted in au.

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 31 No. 10 2005

 + – 717
CHEMICAL BONDING IN THE COMPLEXES Xe F 5 X F 6
ACKNOWLEDGMENTS
We are grateful to A.V. Tsvetkov for his assistance
F11 during the initial step of this study.
As This work was supported by the Ministry of Educa-
tion of the Russian Foundation (grant no. E 02-5.0-161)
and the Grant “Leading Scientific and Pedagogical
Organizations” (GRNTI code 31.25.17).

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