ISSN 00360244, Russian Journal of Physical Chemistry A, 2010, Vol. 84, No. 10, pp. 1731–1744.

© Pleiades Publishing, Ltd., 2010.

Original Russian Text © P.I. Dem’yanov, P.M. Poleshchuk, I.P. Gloriozov, A.Yu. Vasil’kov, 2010, published in Zhurnal Fizicheskoi Khimii, 2010, Vol. 84, No. 10, pp. 1898–1912.

STRUCTURE OF SUBSTANCES
AND QUANTUM CHEMISTRY

Intramolecular Noncovalent Interactions:

Bis(toluene)chromium(0) Conformers
P. I. Dem’yanov, P. M. Poleshchuk, I. P. Gloriozov, and A. Yu. Vasil’kov
Department of Chemistry, Moscow State University, Moscow, 119991 Russia
Received November 10, 2009

Abstract—The structure of trans and cisconformers of bis(toluene)chromium(0) and the intramolecular

interactions in them are studied by means of MP2 and density functional theory along with topological and
NBO analyses. It was concluded for the first time that the locations of two hydrogen atoms of each methyl
group between the phenyl ring planes in the most stable cisconformer of bis(toluene)chromium(0) are
largely determined by the stabilizing interactions of methyl C–H bonds and their hydrogen atoms with the
metal atom and chromium–carbon bonds. It was concluded from the obtained data that the C–H···Cr con
tacts in the studied conformers should be considered as hydrogen bonds rather than agostic interactions.
Contrary to the existing conception of the quantum theory of atoms in molecules, repulsive interaction is
shown to occur between the pairs of hydrogen atoms of the two methyl groups in bis(toluene)chromium(0)
cisconformers rather than the stabilizing hydrogen–hydrogen interactions.
DOI: 10.1134/S0036024410100109

INTRODUCTION hedrane, and indacene [9]; in methyl and tertbutyl

According to IUPAC, “there is a chemical bond
between two atoms or groups of atoms in the case that
the forces acting between them are such as to lead to
the formation of an aggregate with sufficient stability
to make it convenient for the chemist to consider it as
an independent molecular species” [1]. Metallic,
covalent, ionic, coordination, hydrogen [2], agostic
[3–5], and other types of bonds can be distinguished.
The structure of a molecular system can be deter
mined not only by these rather strong bonds, however,
but also by weaker interactions, e.g., dispersion inter
action [6]. For example, dispersion interactions are
thus of great importance in the dimerization of both
saturated and unsaturated hydrocarbons and largely
determine the transformation of linear nalkanes into
folded ones [7]. In other authors’ opinion, hydrocar
bons are crystallized due to stabilizing intermolecular
H···H interactions [8].
It has recently been suggested that the H···H inter
action is a new type of stabilizing interaction between
two hydrogen atoms with similar or comparable
charges [9]. This type of interaction was entitled as
hydrogen–hydrogen bonding and, in the opinion of
the adherents of this type of interaction, it occurs
between orthohydrogen atoms in planar biphenyl [8–
10]; between H atoms located in the socalled bay
regions of angular aromatic hydrocarbons [9–11];
between hydrogen atoms of phenyl groups in crystals
of organoammonium tetraphenylborates [12], tet
raphenylphosphonium squarate [13], bianthrone [13],
and bis(benzophenone)azine [13]; between methyl H
atoms in tertbutyl substituted cyclobutadiene, tetra
cyclohexanes [14]; and between methyl and methyl
ene hydrogen atoms in Meldrum’s acid [15].
In all these cases, the presence of stabilizing H···H
interactions has been substantiated only by the pres
ence of (3, –1) critical points between each considered
pair of H atoms. These points are found by a topolog
ical analysis of electron density distribution ρ, either
obtained experimentally or calculated theoretically for
the corresponding molecular systems. This substanti
ation is based on the known statement of the quantum
theory of atoms in molecules (QTAIM) [16, 17]
according to which, for a molecular system in the sta
ble state, the presence of a (3, –1) type critical point
(CP) between two atoms and of the corresponding
atomic interaction line (AIL) in the distribution ρ is a
necessary and sufficient condition for these two atoms
to be bonded to each other in the usual chemical sense
[16, 18, 19]. For a system in the stable state, a (3, –1)
type CP is referred to as a bond critical point (BCP),
and the AIL is the bond path (BP).
The existence of bonding intermolecular H···H
interactions in the crystals of 1phenylocarborane
[20], [2,2]pcyclophane [21], and bis(benzene)chro
mium(0) [22] has also been grounded only by the pres
ence of BCP between certain pairs of H atoms. The
energies of intermolecular H···H contacts in the crys
tals of ocarborane, [2,2]pcyclophane, and bis(ben
zene)chromium(0) were estimated using the correla
tion found for 83 X–H···O hydrogen bonds (X=C, N,
O) [23]. Such an approach is unlikely to be justified,
since the correlations for H···H interactions and
hydrogen bonds can differ strongly. From the found

1731
1732 DEM’YANOV et al.
energies, the authors conclude that the energy of the
crystal lattice of 1phenylocarborane is nearly
completely determined by intermolecular H···H
interactions [20], or that these interactions are very
important in the formation of the crystal lattice of [2,
2]pcyclophane [21] and bis(benzene)chromium(0)
[22].
It should be noted, however, that as early as in 1992
[24], researchers came to the conclusion that (3, –1)
CPs and their associated AILs between the internal H
atoms in a Kekule hydrocarbon and between H atoms
in the bay regions of chrysene, phenanthrene, and
benz[a]anthracene, in fact correspond to nonbonding
repulsive interactions. Generally, therefore, in the
opinion of the authors of [24], the existence of AILs
does not necessarily mean the presence of bonding
between nuclei and should be considered as evidence
of either bonding or nonbonding, attractive or repul
sive interaction.
In recent years, the possibility of the existence of
stabilizing H···H interactions has been hardly criti
cized [25–29]. Moreover, the first experimental data
have recently been obtained [30] according to which
the short H···H distance (~2 Å) between hydrogen
atoms located in the socalled bay region of phenan
threne corresponds to repulsive interactions. This, in
the authors’ opinion [30], contradicts the QTAIM
concept of strongly interacting H atoms, but agrees
with the usual concept of repulsive van der Waals inter
action. It has therefore been suggested [30] to abandon
the use of the term “hydrogen–hydrogen interaction”
in cases where molecules or their fragments closely
approach one another and undergo the usual repulsive
van der Waals interactions. Negative position to the
presence of BCP and its associated BP has also been
expressed earlier [31, 32]. In Hoffmann’s opinion too
[33], the existence of BCP is not a criterion of bond
ing. All of the conclusions drawn in [30] were, how
ever, strongly criticized by Bader [19], who again pre
sented his views on BP as unambiguous evidence of
the existence of bonding interaction between the
atoms connected by BP.
The question of whether those who support the
existence of bonding H···H interactions or their oppo
nents are correct thus remains open. Additional stud
ies are required to clarify the nature of H···H contacts.
Convenient models for these studies could be the con
formers of bis(toluene)chromium(0) that belong to
the class of bisarene complexes of transition metals,
(arene)2М [34–36]. Due to the hindered rotation of
aromatic ligands around the metal–ligand axis, these
complexes can exist as different conformers. If the
molecules of aromatic ligands contain substituents,
then the number of conformers can increase consider
ably. The causes determining the relative stability of
conformers and the preferred orientation of substitu
ents in (arene)2M complexes have so far been poorly
studied. Analysis of data from the Cambridge Crystal
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
lographic Data Center [37] shows that in methyl sub
stituted bisarene complexes, two hydrogen atoms of
each methyl group are located in many cases between
the aromatic ligand planes and thus directed toward
the metal atom. Moreover, in the absence of specific
steric hindrances, two methyl groups of tertbutyl or
trimethylsilyl substituents also prefer to be located
between the aromatic (benzene) ligand planes.
A similar orientation of substituents of this type is
also observed in metallocenes [38]. It could be
assumed that the effects of crystal packing dictate this
orientation of substituent atoms and groups in bisare
nes and metallocenes. A recent theoretical study [39],
however, shows that the noted features are main
tained in the gas phase even for cisconformers of
bisarene complexes of chromium, in which the angle
ϕ(C7c1c2C7') (in the Scheme, c1 and c2 are the cen
ters of phenyl rings 1 and 2) between methyl, tertbutyl
or other alkyl substituents in the molecule of one arene
and the same substituents in the molecule of another
arene is 0°. It could be assumed that this orientation of
substituents in cisconformers is caused by stabilizing
H···H interactions.
The structure of trans and cisconformers of
bis(toluene)chromium(0) (Scheme, 1a–1d) and
intramolecular interactions in them were studied in
the present work with the use of density functional
theory [40–42] and second order Møller–Plesset per
turbation theory (MP2) [43]. Intramolecular interac
tions in the conformers were studied by topological
analysis within QTAIM [16, 17] and the natural bond
orbital (NBO) method [44, 45]. Special attention was
paid to the interactions of methyl groups in ciscon
formers.
CALCULATION METHODS
Calculations in the approximation of B971
hybrid exchangecorrelation GGA functional [46]
and within MP2 theory were performed using the
NWChem program [47] with a basis set composed of
the 6311++G(d, p) Pople basis set [48] for C and H
atoms and the allelectron quadruplezeta valence
def2QZVPP [49, 50] basis set for the Cr atom. This
basis set without the g functions is designated below as
PQZ. The g functions were removed from the def2
QZVPP basis set for Cr because the format of wave
functions required for the analysis within QTAIM
does not allow their presence. The absence of g func
tions has virtually no effect [49, 51] on the energies
and other properties of the molecular system under
study. The choice of the B971 functional was deter
mined (along with other functionals and MP2 calcula
tions) by its producing the best description of the bind
ing energies for complexes with charge transfer, weakly
bound complexes, and nonbonding interactions [52].
All of these interactions seem to substantially affect
the intramolecular interactions in bis(toluene)chro
Vol. 84 No. 10 2010
 INTRAMOLECULAR NONCOVALENT INTERACTIONS 1733

mium(0) conformers, and hence, their structure and
stability.
The interactions of methyl groups in a bis(2,6dim
ethylphenyl)cuprate anion are also best described by
the B971 functional [53] that yields results compara
ble to the data of MP2 calculations. Calculations in
the RIMP2 approximation [54–56] were carried out
using the PRIRODA04 software [57] and Hartree
Fock sets of basis functions developed for it: DZ (H {2,
1}/{6, 2}, C {3, 2, 1}/{10, 6, 2}, Cr {6, 4, 2, 1}/{19, 12,
7, 2}) and TZ (H {3, 2, 1}/{8, 3, 2}, C {4, 3, 2, 1}/{12,
8, 3, 2}, Cr {8, 6, 4, 2, 1}/{22, 14, 9, 3, 2}). Core elec
trons were not included in the correlation in the cal
culations in RIMP2 and MP2 approximations;
rather, RIMP2(FC) and MP2(FC) methods were
used. The B971/PQZ and B3PW91/6311G** meth
ods were employed in the calculations for benzene and
bis(benzene)chromium(0). It should be noted that the
considered molecular systems were optimized by
imposing a symmetry restriction (see below). The ener
gies of the molecular systems calculated by the B97
1/PQZ, MP2(FC)/PQZ (RIMP2(FC)/TZ) methods
were corrected for zeropoint vibrational energies
(ZPVEs).
The wave function files required for a topological
analysis [16, 17] of the electron density distribution in
the conformers under study and in other molecular
systems were obtained using the GAMESS program
package [58]. Molecular graphs were calculated using
the AIM2000 program [59, 60]. AIM2000 [59, 60],
AIMPAC [61], and PROAIMV [62–64] were
employed to search for CPs, calculate the delocaliza
tion indices δ(A, B), and integrate over the atomic
basins. The atomic Laplacian as an indicator of the
accuracy of numerical integration over atomic basins
for the H atoms of methyl groups did not exceed 2.1 ×
10–5 au. The energies of the atoms in conformers were
found so as to satisfy the atomic statement of the virial
theorem. NBO analysis [44, 45] was performed using
the NBO Version 3.1 program implemented in the
Gaussian 98 (Version 5.4) program package [65].
RESULTS AND DISCUSSION
Molecular Structure of Bis(toluene)chromium(0)
Conformers
The rotation potential of bis(toluene)chromium(0)
(1) in the range 0°–180° had been studied earlier [39].
In the present work, the conformers of 1 with eclipsed
benzene rings, in which the dihedral angle between
methyl groups is 180° (transeclipsed conformers) or
0° (ciseclipsed conformers) were studied only. The sta
tionary points corresponding to trans and ciseclipsed
conformers 1a (C2h symmetry) and 1b (C2v symmetry)
were found on the potential energy surface (PES) of
bis(toluene)chromium(0). In both conformers, the
hydrogen atoms of methyl groups Hα1, Hα1', Hα2,
and Hα2' are located between the phenyl ring planes,
or in other words, are directed toward the chromium
atom.

(1a) (1b)
5 6 α3 5 6 α3
4 4 1 7 4 4 1 7
3 2 α1 3 2 α1
α2 α2
Cr Cr
α1' α2'
R3 α2' 7' 2' 3' 5' 6' α1'
4' 4' 4' 4'
.c1 7 1' 7'
1'
R1 α3' 6' 5' 3' 2' α3'
R2
Cr
R2' (1c) (1d)
R1' α2 α2
.c2 7' 4
5 6
1 7
α1
4
5 6
1 7
α1
R3' 4 4
3 2 α3 3 2 α3
Cr Cr
α3' 2' 3' 5' 6' α3'
1' 4' 4' 4' 4' 1'
7' 7'
α1' 6' 5' 3' 2' α2' α1'
α2'
Scheme.

Stationary points corresponding to trans and groups in which Hα3 and Hα3' atoms are directed
ciseclipsed conformers 1c (C2h symmetry) and 1d (C2v towards the chromium atom) also found on the PES.
symmetry) with inverted methyl groups (i.e., methyl The B971 calculations show that the total energy E e

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 84 No. 10 2010

1734 DEM’YANOV et al.

Table 1. Relative electronic ( Eerel ) and corrected for ZPVE ( E0rel ) energies of bis(toluene)chromium(0) conformers as well as
dissociation energies ( Edis ) of transbis(toluene)chromium(0), kcal/mol
rel rel
Ee E0
No. Method Edis( 1a )
1a 1b 1c 1d 1a 1b 1c 1d
1 B971/PQZ//B971/PQZ 0.00 –0.02 3.14 3.59 0.00 0.30 2.61 3.20 142.3 (50.8)
2 MP2(FC)/PQZ//MP2(FC)/PQZ 0.00 0.32 4.26 5.35 0.00 0.84 4.32 6.63 207.0 (115.6)
3 RIMP2(FC)/TZ//RIMP2(FC)/TZ 0.00 0.22 4.38 5.22 0.00 0.74 4.44 6.49 218.9 (127.4)
4 MP2(FC)/QZ//RIMP2(FC)/TZ 0.00 –0.01 4.32 4.98 0.00 0.51 4.37 6.25 202.6 (111.2)
Note: Dissociation into two toluene molecules and the chromium atom in singlet or septet (in parentheses) states. Energies calculated by method 1
and methods 2–4 corrected for B971/PQZ and RIMP2/DZ calculated ZPVEs, respectively, are shown in Table. For 1b, the values
rel
E0 are 0.11 (PBEPBE/TZ [39]) and 0.30 kcal/mol (BPW91/TZVP [68]).

Table 2. Distances (d(A–B), Å) between the nuclei of some atoms of 1 optimized in B971/PQZ (I), MP2(FC)/PQZ (II),
and RIMP2(FC)/TZ (III) and experimentally measured in [Cr(η6–CH3C6H5)2]+[pcmcp]⎯ [69] conformers (IV)
1a 1b 1с 1d
A–B
I II III IV I II III IV I II III I II III
Cr–C1 2.176 2.109 2.100 2.168a 2.190 2.126 2.116 2.179a 2.192 2.123 2.116 2.223 2.156 2.146
Cr–C2 2.163 2.119 2.103 2.146b 2.166 2.122 2.106 2.145b 2.168 2.124 2.107 2.178 2.130 2.114
Cr–C3 2.163 2.122 2.106 2.147c 2.160 2.119 2.103 2.140c 2.160 2.119 2.105 2.155 2.114 2.100
Cr–C4 2.165 2.104 2.093 2.150d 2.159 2.107 2.093 2.136d 2.161 2.102 2.088 2.151 2.102 2.088
C1–C4′ 3.264 3.083 3.072 3.338e 3.178e 3.167e 3.281 3.100 3.086 3.469e 3.306e 3.300e
C2–C5′ 3.271 3.149 3.122 3.299f 3.185f 3.157f 3.273 3.154 3.128 3.352f 3.230f 3.205f
C3–C6′ 3.271 3.149 3.122 3.241g 3.115g 3.088g 3.273 3.154 3.128 3.205g 3.078g 3.051g
C4–C1′ 3.264 3.083 3.072 3.214h 3.048h 3.023h 3.281 3.099 3.086 3.148h 2.982h 2.954h
C7–C7′ 6.763 6.637 6.598 6.625 3.517 3.356 3.326 3.400 6.816 6.728 6.686 3.811 3.686 3.661
Hα1–H4′ 3.002 2.766 2.744 2.562i 2.393i 2.362i 2.444j 2.271j 2.252j 1.901k 1.801k 1.783k
Note: aAverage value from Cr–C1 and Cr–C1'. bAverage value from Cr–C2, Cr–C6, Cr–C1', and Cr–C6'. cAverage value from Cr–C3, Cr–C5,
Cr–C3', and Cr–C5'. dAverage value from Cr–C4 and Cr–C4'. ed(C1–C1'). fd(C2–C2'). gd(C3–C3'). hd(C4–C4'). id(Hα1Hα1').
jd(Hα3–H4'). kd(Hα3–Hα3').

of conformer 1b is lower by 0.02 kcal/mol than that
of transconformer 1a. Calculations in the
MP2(FC)/QZ//RIMP2(FC)/TZ approximation
lead to a similar conclusion (Table 1). These results are
unexpected, since maximum repulsion between
methyl groups must be observed in ciseclipsed con
former 1b [66–68]. The BP86/631G** [69] and
BPW91/TZVP [68] calculations predicting a some
what higher energy for 1b (0.09 and 0.30 kcal/mol
respectively) as compared to the energy of 1a do not
contradict the assumption of the repulsive interaction
between methyl groups in the ciseclipsed conformer.
According to an analysis of harmonic vibrational fre
quencies calculated using the B971/PQZ and RI
MP2/DZ methods, the minima on the PES corre
spond to conformers 1a and 1b, while the second
order saddle points correspond to 1c and 1d. Thus sta
tionary points on the PES correspond to all studied
conformers. It should be noted that the ZPVE cor
rected energies E 0rel of conformers increase in the
order 1a < 1b Ⰶ 1с < 1d.
The formation and structure of conformers 1с
and 1d have never been discussed in the literature.
Experimental data on the structure of neutral 1a and
1b are also absent. Single crystal Xray diffraction
analysis has been used to study only some bis(tolu
ene)chromium(I) salts. The structures of 1a and 1b
optimized by the B971 method and the trends in
changes in the complex geometry on transition from
1a to 1b (Table 2) are quite consistent with recent sin
gle crystal Xray diffraction data on the structure of
[Cr(η6CH3C6H5)2]+[pcmcp]– (pcmcp = penta(car
bomethoxy)cyclopentadienyl). The crystal unit cell
contains two independent structures of this complex
with angles ϕ between methyl groups of 151° and 0°
[69]. It is beleived [70] that the structures of Cr(0) and
Cr(I) bisarene complexes should not differ too
strongly, giving grounds to compare the structures of

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 84 No. 10 2010

 INTRAMOLECULAR NONCOVALENT INTERACTIONS
Table 3. Calculated angles between phenyl rings (α, deg) and some dihedral angles (θ, deg) in bis(toluene)chromium(0) con
formers
Angle 1a 1b 1с 1d 1a
B971/PQZ
α 0.0 2.3 0.0 5.9 0.0
θ(C5–C3–C2–C1) –0.3 0.2 0.1 1.0 –1.6
θ(C6–C2–C3–C4) 0.0 0.0 –0.2 –0.4 1.4
θ(C5–C3–C2–C7) 0.6 3.0 1.4 5.4 –2.4
Note: Positive (negative) θ values indicate a deviation of the C1, C4, and C7 atoms from the C2–C3–C5–C6 plane outward (inwards) of the
conformer molecule.
neutral 1a and 1b with the structures of [Cr(η6–
CH3C6H5)2]+[pcmcp]– conformers (Table 2).
On the other hand, upon the transition from
bis(benzene)titanium(0) [71] to cisbis(toluene)tita
nium(0), [71, 72] only a small increase in Ti–C dis
tances (not more than 0.05 Å) is observed in the crys
tal, whereas the C–C bond lengths in the benzene
rings of both complexes remain virtually unchanged
within the measurement error, indicating the negligi
ble effect of the methyl group’s introduction on the
structure of bis(benzene)titanium(0). We may there
fore expect that the introduction of a methyl group
into each ring of bis(benzene)chromium(0) should not
substantially change its geometry either. A comparison
of 1a and 1b structures calculated by the B971/PQZ
method with the structure of bis(benzene)chro
mium(0) in the gas phase [73] and in the crystal [22,
74, 75] also reveals only a short (~0.02–0.04 Å) elon
gation of Cr–Cbonds in 1a and 1b, as compared to
bis(benzene)chromium(0).
The presented data thus show that the calculations
in the B971/PQZ approximation yielded geometries
of bis(toluene)chromium(0) conformers close to those
determined experimentally for the related bisarene
complexes of chromium. On the other hand, as com
pared to the experimental data and B971/PQZcal
culations, the MP2 methods, and especially RIMP2,
produce noticeably shorter Cr–C distances in both 1a
and 1b. A similar picture is also observed in comparing
the data for 1c and 1d. From the presented data, it fol
lows that the MP2 and RIMP2 methods considerably
overestimate the interaction between toluene mole
cules and chromium in the considered conformers,
and MP2 calculations call for a more critical attitude
to be taken.
In compliance with the symmetry of calculated
conformers 1a–1d, the C2, C3, C5, and C6 atoms of
their phenyl rings lie in one plane. The same is also
true for C2', C3', C5', and C6' atoms. For the same
reason, the angle α between the mentioned planes is
0° in 1a and 1c; i.e., the phenyl rings are parallel to one
another in the molecules of these conformers. In 1b
and 1d, however, these rings form considerable angles
with one another (Table 3), with the distances between
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 84
1735
1b 1с 1d 1a 1b 1с 1d
МР2/PQZ RIMP2/TZ
2.8 0.0 6.2 0.0 2.8 0.0 6.2
–1.0 –1.6 –0.1 –1.2 –0.6 –0.8 0.4
0.7 1.0 0.4 1.1 0.7 1.1 0.4
1.4 0.0 5.1 –2.3 1.4 0.5 5.1
the paracarbon atoms d(С4–С4') becoming remark
ably shorter than the distances between the C ipso
atoms d(С1–С1') (Table 2).
According to the data of B971/PQZ calculations,
the C4 atom in 1a and 1b also lies in the C2–C3–C5–
C6 plane, and in 1c and 1d, it slightly deviates from
this plane towards the chromium atom. This is evi
denced by the value of dihedral angle θ(C6C2C3
C4) (Table 3). In 1a, the C1 atom (dihedral angle
θ(C5–C3–C2–C1)) deviates toward the chromium
atom relative to this plane, whereas in 1b–1d it devi
ates to the opposite direction, the deviation increasing
upon a transition from transconformer 1c to ciscon
former 1b and especially noticeably, to 1d. Judging by
the values of the dihedral angle θ(C5–C3–C2–C7),
the C7 methyl carbon atom deviates outwards from the
C2–C3–C5–C6 plane in all conformers, this devia
tion being appreciably larger in cisconformers and
reaching its maximum value (5.4°) in 1d.
The transition from trans to cisconformers is thus
accompanied not only by the formation of a consider
able angle between the phenyl rings of toluene mole
cules, but also by the methyl groups coming noticeably
out of the plane of these rings. These transformations
can be considered as evidence that cisconformers 1b
and 1d change their geometry (as compared to 1a and
1c) so as to provide the maximum possible distances
between the nearest hydrogen atoms of adjacent
methyl groups, maintaining the minimum possible
angle between the phenyl rings and ensuring most
strong interaction between the metal atom and both
toluene molecules. This compromise is reached in 1b
when the distances between the Hα1 and Hα1', Hα2
and Hα2' become comparable with the sum of the van
der Waals radii v(H) (1.20 [76], 1.1 [77], 1.06 [78],
1.10 ± 0.2 [79], 0.82–1.34 [80] Å) of the two H atoms,
or when in 1d the d(Hα3–Hα3') value (1.901, B971;
1.801, MP2; 1.783 Å, RIMP2) is considerably below
it (Table 2).
A structural feature of all bis(toluene)chromium(0)
conformers is that the hydrogen atoms of the phenyl
rings deviate from the plane of the C2, C3, C5, and C6
atoms toward the chromium atom. In 1а and 1b, the
angle of the H atoms’ deviation from this plane is
No. 10 2010
1736 DEM’YANOV et al.

(1a) α3 (1b) 3 α3
3 2 2
3 3 2 2
7 4 5 7
4 6
4 1 4 6 1
5 5 6 α2 α1
6 α1 5
α2 RCP1
Cr RCP2
Cr CP1
CP2
α1'
α2' 3' 5' 6' α2'
5'
7' 1' 4' 1'
2' 3' 4' 4'
4'
6' α1'
7'
2' 2'
α3' 6' 6' 5' 3' 3' α3'
5'

α2
(1c) α2 α1 (1d) α1
2 2 7
3 1 5 5 6
3 7 4 4
5 6 6 1
4 4 5 2 2
RCP2 3 α3
3 RCP1
RCP1 α3
RCP3
Cr Cr RCP1'
α3' RCP1'
5'
CP1
RCP2' 2' 6' 6'
3' 4' α3'
1' 4' 5'
7' 2' 3' 4'
4' 2'
α1' 1' α2'
7'
5' 3'
6' 3'
α2' 6' 5' α1'
2'

Fig. 1. Molecular graphs of 1a, 1b, 1c, and 1d, calculated by the B971/PQZ method. Black and gray spheres represent carbon
and hydrogen atoms, respectively; small black and gray spheres represent (3, –1) CPs and (3, +1) RCPs, respectively.

~2.2°. In 1с, this angle is smaller (~2.0°), and in 1d, and foremost to the chromium atomic basin [16]
the H2, H3, and H4 atoms deviate toward the metal by almost reaching the phenyl rings, while the carbon
1.3°, 2.1°, and 1.6° respectively. In the MP2 and atomic basins spread to the centers of the benzene
RIMP2 optimized conformers, the deviation of rings (Fig. 2). Electron densities in the internuclear
hydrogen atoms toward the metal reaches almost 4°. Cr–C areas that form the Cr–C BPs also increase ρ
inside the hexagonal pyramids. This results in an
increase in ρ, both inside the Cr–C6H5 pyramids and
Topological Analysis in the centers of the phenyl rings. The ρ value there
In order to understand the causes of structural fore monotonically decreases along the vectors start
changes upon the transition from trans to ciscon ing at the chromium atom and passing through the
formers, we analyzed within QTAIM [16, 17] the centers of the C2–C3–C5–C6 and C2'–C3'–C5'–
electron density distribution ρ and interatomic inter C6' planes of bis(toluene)chromium(0) (Fig. 3), pre
actions in the conformers under study. Figure 1 venting the presence of RCPs and CCPs along these vec
shows the molecular graphs [16] calculated in the tors. The same monotonous decrease in electron density,
B971/PQZ approximation for 1a–1с. It is seen in all starting from the chromium to the centers of the ben
the molecular graphs that the (3, +1) ring critical zene rings and farther along the sixfold axis, is observed
points (RCPs) [16] of phenyl rings and (3, +3) cage for bis(benzene)chromium(0) with D6h symmetry (as
critical points (CCPs) [16] are absent inside both hex calculated by both the B971/PQZ and B3PW91/6
agonal pyramids formed by a chromium atom with 311G** methods) (Fig. 4). The above reasons for the
each of phenyl rings. A similar picture is also observed absence of RCPs and CCPs in the molecular graphs of
in the molecular graphs calculated using the wave bis(toluene)chromium(0) and bis(benzene)chro
functions MP2/PQZ for these conformers. mium(0) differ substantially from those proposed ear
Topological analysis shows that the disappearance lier for bis(benzene)chromium(0) [22] and metal
of the abovementioned RCPs and CCPs is due first locenes [81].

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 84 No. 10 2010

 INTRAMOLECULAR NONCOVALENT INTERACTIONS 1737

(1a) (1b)

Ha3 Ha3

C4 C1 C4 C1
H4 H4 Ha1
Ha1
C7 C7
Ha2 Ha2
Cr Cr
Ha1'
C7 ' Ha1'
Ha2' C7 '
H4' H4' Ha2'
C1' C4' C4' C1'
Ha3'
Ha3'

Fig. 2. Electron density maps for conformers 1a and 1b in the C1–C4–C1'–C4' planes calculated by the B971/PQZ method.
Interatomic BPs and intersection curves of the above planes with the interatomic surfaces are superimposed on the maps. The
external countour corresponds to a value of 0.001 au; the other contours increase in the order 2 × 10n, 4 × 10n, and 8 × 10n, where
n increases with unit steps starting from –3. Crossed and light crosses denote atoms in and out of the plane, respectively. Small
triangles denote (3, –1) CP.

In the molecular graphs of 1c and 1d obtained in
the B971/PQZ approximation, there are also no
(3, –1) CPs and AILs between the chromium atoms
and some carbon atoms of the phenyl rings (Fig. 1). A
topological analysis based on MP2/PQZ calculations
reveals the absence of similar characteristics in the
molecular graphs of not only 1c and 1d, but also of 1a.
The molecular graphs of 1c and 1d demonstrate the
absence of other CPs as well, the presence of which is
dictated by the structures of these conformers. The
reasons for the absence of some CPs and AILs in the
molecular graphs of bis(toluene)chromium(0) con
formers are not discussed in the present work; only the
structural features and features of the molecular

ρ, au
ρ, au 1
䉭 2
0.04 䊊 3
0.04
4
1

0.02 0.02
2

0 0
1.0 1.5 2.0 2.5 1.0 1.5 2.0 2.5
d(Cr), Å d(Cr), Å

Fig. 3. Dependences of electron densities (ρ) in 1a (B97
1/PQZ calculations) on distance d(Cr) along a vector
directed from Cr to the center of the C2–C3–C5–C6
plane (1) and in the isolated toluene molecule along the
vector perpendicular to the phenyl ring in its RCP (2).
The RCP of toluene calculated by B971/PQZ coincides
with the center of the C2–C3–C5–C6 plane in bis(tolu
ene)chromium(0).
Fig. 4. Dependences of electron densities (ρ) in bis(ben
zene)chromium(0) on the distance (d(Cr)) along the vector
directed from Cr to the center of one of the benzene rings
(1, 3) and the electron density change in the isolated ben
zene molecule along its axis C6v (2, 4); 1, 2 B3PW91/6
311G** calculation, 3, 4, B971/PQZ. The RCPs of the
calculated benzene molecules coincide with the center of
the benzene ring of bis(benzene)chromium(0).

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 84 No. 10 2010

1738 DEM’YANOV et al.

Table 4. QTAIM data on the energy changes (in kcal/mol) and some other properties of Hα1, Hα2, Hα1', and Hα2' atoms
in 1b and Hα3 and Hα3' in 1d, as compared to similar values in 1a and 1c, respectively

Transition Δv(H), a.e. ΔN(H) ΔE(H)  (H)

ΔVne
ex
ΔVne (H)
net
ΔVne (H) ΔVr(H) Δ V (H)
B971/PQZ
1a 1b –0.68 0.0008 ± 0.0002 –0.36 –0.73 –374.29 –375.02 374.30 –0.72
1c 1d –3.11 0.0023 ± 0.0001 –1.95 –3.12 –329.46 –332.58 328.68 –3.90
MP2(FC)/PQZ
1a 1b –0.06 –0.0015 0.28 0.74 –189.71 –188.97 189.53 0.56
1c 1d –3.60 0.0001 –2.76 –2.98 –311.95 –314.93 309.40 –5.53
net
Note: The value ΔE(H) = ΔV(H)/2, ΔV(H) = ΔVne (H) + ΔVr(H); Δv(H) and ΔN(H) are the changes in the volume and the atomic pop
ulation of atom H, respectively.

graphs of bis(toluene)chromium(0) cisconformers Δ E ( Ω ) in the molecule in its equilibrium state can be

that relate to the interaction of methyl groups are con
sidered.
The molecular graphs of 1b calculated by the
B971/PQZ (Fig. 1) and MP2/PQZ methods show
(3, –1) CP1 and CP2 between Hα1 and Hα1' and
between Hα2 and Hα2' and the respective AIL(Hα1,
Hα1') and AIL(Hα2, Hα2'). The molecular graphs of
1d calculated by the same methods show (3, –1) CP1
between Hα3 and Hα3' and the respective AIL(Hα3,
Hα3') (Fig. 1). The CP properties and the lengths of
AILs in 1b and 1d are comparable to those found ear
lier for H···H contacts in biphenyl and other hydrocar
bons [9]. As noted above, the PES stationary points
correspond to conformers 1b and 1d. According to
QTAIM [16, 18, 19], therefore, the existence of (3,
–1) CPs and AILs between the methyl hydrogen
atoms in the molecular graphs of 1b and 1d is a neces
sary and sufficient condition to state that these H
atoms are chemically bonded to one another (nonco
valent interaction).
Hence, the (3, –1) CPs [16, 18, 19] between Hα1
and Hα1' and between Hα2 and Hα2' atoms in the
molecular graph of 1b and between Hα3 and Hα3' in
the molecular graph of 1d should be called BCPs and
the respective AIL(Hα1, Hα1'), AIL(Hα2, Hα2'), and
AIL(Hα3, Hα3') should be called BPs. In accordance
with the above QTAIM statement, it would therefore
be appropriate to speak about the existence of hydro
gen–hydrogen (H···H) stabilizing interactions [9, 10,
19] between both Hα1 and Hα1' (Hα1···Hα1' interac
tion) and between Hα2 and Hα2' (Hα2···Hα2' inter
action) in 1b, as well as between Hα3 and Hα3'
(Hα3···Hα3' interaction) in 1d. According to Matta
and coauthors [9, 82], one sign of the presence of
H···H bonding interactions between close H atoms is
the presence of BCPs, BPs, and a zero flux surface
between the atomic basins of two hydrogen atoms. All
of these are present for the Hα1···Hα1', Hα2···Hα2',
and Hα3···Hα3' contacts.
In compliance with the virial theorem for atom Ω
[16, 82–84], a change in the energy of the atom
expressed through a change in the potential energy
Δ V ( Ω ) of the atom: Δ E ( Ω ) = (1/2) Δ V ( Ω ) . Within
QTAIM [16, 82–84], the total change of Δ V ( Ω ) is
equated with the sum of changes in the energy of
attractive interactions between the electrons of the Ω
atom and all nuclei of the molecular system Δ V nenet( Ω ),
on the one hand, and changes in the energy of repul
sive interactions Δ V r ( Ω ) between the electrons of the
Ω atom and all the other electrons Δ V ee( Ω ) and
between the nucleus of the Ω atom and all the other
nuclei Δ V nn( Ω ), on the other hand:
Δ V ( Ω ) = Δ V nenet( Ω ) + Δ Vee( Ω ) + Δ V nn( Ω ). (1)
Based on the B971 and MP2 calculations, Table 4
lists QTAIM data on changes in the properties of Hα1,
Hα2, Hα1', and Hα2' atoms in 1b and Hα3 and Hα3'
atoms in 1d in comparison with their properties in 1a
and 1c, respectively. However, no definite conclusions
can be drawn from these data as to the presence or
absence of stabilizing interactions Hα1···Hα2,
Hα1'···Hα2' in 1b and Hα3···Hα3' in 1d. This is prima
rily due to the value Δ E ( Ω ) involving a change in the
atomic energy of the Ω atom not only because of its
interaction with all the other atoms of the molecular
system, but also because of a change in internal energy
Δ E int( Ω ) that can be represented [85] in the form of
the sum of changes in energy Δ V ne( Ω ) of its electron
density interaction with its own nucleus, the energy
Δ V ee( Ω ) of the interaction between Ω own electrons
(i.e., between electrons in the atomic basin of the Ω
atom), and changes in the kinetic energy Δ T ( Ω ) of
these electrons:
Δ E int( Ω ) = Δ V ne( Ω ) + Δ Vee( Ω ) + Δ T ( Ω ) . (2)
It is clear that in a quantitative estimation of changes
in the energy of the Ω atom caused by changes in its
interaction with other atoms of the molecular system,
the value Δ E int( Ω ) must be excluded from Δ E ( Ω ) ,

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 84 No. 10 2010

 INTRAMOLECULAR NONCOVALENT INTERACTIONS
since the binding energy (in the chemical sense of this
term) of H with H, or Ω with Ω' in a general case is
determined by the interaction energy of the nuclei of
the two atoms in question (H with H or Ω with Ω')
between themselves and with electrons confined in
their internuclear space, and of these electrons among
themselves. Alike, the energy of the interaction of the
nucleus and electron density of the Ω atom with nuclei
and electrons of atoms X ≠ Ω' does not relate directly
to the energy of the Ω···Ω' interaction.
In general, a change in the energy of the Ω atom
upon a transition from a molecule in which the Ω···Ω'
contact is absent to a molecule in which it appears
can be determined primarily by the change in the
interaction energy of Ω with other atoms X
( Δ E Χ( Ω )), rather than with Ω'. The total change in
energy Δ E ( Ω ) = (1 / 2) Δ V ( Ω ) found using the value
t
Δ V ( Ω ) calculated by Eq. (1) therefore cannot be
applied even to speculate whether the energy of the Ω
atom decreases or increases just because of the
emerged Ω···Ω' interaction (i.e., whether the interac
tion between two close Ω and Ω' atoms is stabilizing or
destabilizing). It is the nonsubtraction of Δ E int( Η ) and
Δ E Χ( Η ) from Δ E ( Η ) that is likely to result in a pre
t
dicted increase in the energy of the H atom (Δ E ( Η ) > 0)
t
in the formation of both weak [83, 86–88] and strong
[83] hydrogen bonds and a decrease in the H energy
( Δ E ( Η ) < 0) in H···H interactions (see Table 4 and
t
refs. [8–10, 14]). Excluding Δ E int( Ω ) from Δ E t( Ω )
can substantially reduce the predicted interaction
energies of helium and neon atoms (and some cations
with the adamantane cage), as compared to those cal
culated earlier [84] using (1).
NBO Analysis
NBO analysis shows the presence of secondary
orbital interactions of the Cr atom with Hα1, Hα2,
Hα3, Hα1', Hα2', Hα3' atoms and between Cr and
the respective C–H bonds. Here, the donation of the
electron density from the bonding σorbitals of C–H
bonds to the nonLewis lone pairs (LP*) of chromium
atom (σ(С–H) → LP*(Cr)) are either absent or the
stabilization energy Est for donations from LP and LP*
orbitals of the chromium atom to the Rydberg orbitals
of (RY*(H)) hydrogen atoms, LP(Cr) → RY*(H) and
LP*(Cr) → RY*(H) substantially exceeds Est for the
σ(С–H) → LP*(Cr) donations. Based on the crite
rion proposed in [51, 89] to differentiate between ago
stic interactions [3–5] and hydrogen bonds in transi
tion metal complexes [90–93], the interaction of
methyl C–H bonds with the Cr atom in bis(tolu
ene)chromium(0) should thus be considered as a
С⎯H···Cr hydrogen bond.
This interaction appears primarily due to the
LPs*(Cr) becoming partially populated owing to the
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
1739
donation of electron density from toluene molecules,
as a result of which the LP*(Cr) energies turn out to be
quite close to the energies of the RY*(H) orbitals. The
total stabilization energy of LP(Cr) → RY*(H) and
LP*(Cr) → RY*(H) donations for the Hα1 atom
(directed to the Cr atom) in 1a and 1b is ~3.4 and 13.3
and 3.3 kcal/mol for Hα3 (also directed to Cr) in 1с
and 1d, respectively. For reasons that are unclear, the
Est value is highly overestimated for 1с. Secondary
orbital interactions also exist between the H atoms of
methyl groups and Cr–C bonds. Here, the bonding
σ(Сr–C) and nonbonding σ*(Сr–C) orbitals serve as
electron density donors to the RY*(H)orbitals. The
total stabilization energy of σ(Сr–C) → RY*(H) and
σ*(Сr–C) → RY*(H) donations for Hα1 in 1a and 1b
is 5.4 and 3.7, while it is 2.6 and 4.5 kcal/mol for Hα3
in 1с and 1d, respectively.
In 1a and 1b, the total energy E stt ( α 1, α 2) of the
stabilizing interactions of the bis(toluene)chro
mium(0) core with the Hα1 and Hα2 atoms directed
to chromium (37.8 and 31.2 kcal/mol respectively) is
~2 times higher than E stt ( α 3) for the Hα3 atom
directed oppositely (17.8 and 14.6 kcal/mol, respec
tively). In 1с and 1d, on the other hand, the value of
E stt ( α 3) (26.9 and 30.8 kcal/mol respectively) is some
what lower than E stt ( α 1, α 2) in 1a and 1b. These data
allow us to understand why energies of 1с and 1d are
by ~3 kcal/mol higher than energies of 1a and 1b
(Table 1), and why the saddle points on the PES cor
respond to conformers 1с and 1d. Despite the quite
strong interaction of the chromium atom with Hα1
and Hα2 in 1a and 1b and with Hα3 in 1c and 1d there
are no BCPs as well as their associated BPs between
the Cr atom and Hα atoms. This is explained by
spreading the atomic basins of C1 and C7 atoms far
beyond the lines connecting the Cr atom with methyl
H atoms (Fig. 2). As a result, the ρ values in the regions
of potential BCPs are increased so that the ρ minima
between Cr and Hα atoms are disappeared, and BCPs
are not observed.
The absence of BCPs and CPs between Cr and Hα
atoms is thus due to the features of the ρ distribution in
the conformers in question, and the principal failure
of QTAIM to find all of the BCPs and CPs between the
noted atoms is due to the penetration of atomic basins
of the other atoms between them, rather than to the
absence of interaction between these atoms. The same
reasons are possible for the absence of BCPs and CPs,
e.g., between H atoms in H2O, and the geminal and
vicinal hydrogen atoms in the molecular graphs of
methane, ethane, and other hydrocarbons, even though
there are weak interactions between these atoms [94].
There are no BCPs and CPs between the oxygen atoms
in SO2 and SO3 despite the quite strong noncovalent
interaction between these atoms (δ(О, О) ≈ 0.3) [94].
For the same reason, there are no (3, –1) CPs and BPs
between the oxygen atoms in the nitro group of the
Vol. 84 No. 10 2010
1740 DEM’YANOV et al.
[C(NO2)3]– anion [95]. At the same time, these
QTAIM signs are present between the O atoms of the
different nitro groups of the anion, since the atomic
basins of the neighboring atoms do not prevent the
existence of ρ minima between these atoms [95].
The noted disadvantage inherent to QTAIM is also
distinctly manifested in its failure to find BCPs and CPs
between the transition metal atom and the H atom at
the Cα atom in titanium complexes [96] and one of the
conformers of the TpMe2NbCl(MeС≡CPh)(i–Pr)
complex [97]. It is strange that, based on the absence
of BCP and CP between the metal and the mentioned
H atom, the authors of [96, 97] reject the possibility of
αagostic interactions in these complexes despite the
many indications of their existence.
According to NBO analysis, the Hα1, Hα2, and
Hα3 atoms in 1a–1d also interact with the C1–C2
and C1–C6 bonds, i.e., with the nearest C–C bonds
of the aromatic ring. A noticeable contribution to the
stabilization of 1с and 1d is made by donations from
σ(С1–С7) to σ*(C7–Hα3) and from σ(С1'–С7') to
σ*(C7'–Hα3'). NBO analysis thus shows that the
transition from 1a to 1b and from 1с to 1d is accompa
nied not only by the approach of the corresponding H
atoms of methyl groups, but also by considerable
changes in the interaction of these atoms not only with
one another but also with other atoms and bonds. If
the changes in potential energies Δ V neex(H), ΔVee(H) ,
and ΔV nn(H) are not decomposed in the contributions
relating to each particular interaction, or if the total
energy change Δ E (H ) = Δ E (H) + Δ E (H) is not
int ex
decomposed even in the change in internal stabiliza
tion energy Δ E int(H) and the change in atomic energy
due to its interaction with all external atoms Δ E ex(H) ,
it is impossible to draw any definite conclusions about
how high the effect of H···H interactions on the
changes in these energies is in 1b and 1d (Table 4).
Consequently, based on the data from Table 4, it
cannot be concluded whether the H···H contacts in 1b
and 1d are stabilizing or destabilizing, or to which
interactions (stabilizing or destabilizing) correspond
(3, –1) CPs and the respective AILs between Hα
atoms in the molecular graphs of 1b and 1d. It is worth
noting that NBO analysis does not reveal any second
ary orbital interactions between the hydrogen atoms or
C–H bonds of the methyl groups in 1b.
The substantially larger values for the delocaliza
tion indices calculated in the B971 approximation for
1b (δ(Hα1, Hα1') = δ(Hα2, Hα2') = 0.011) and 1d
(δ(Hα3, Hα3') = 0.038), as compared to the similar
indices in 1a and 1c (1.8 × 10–5 and 1.7 × 10–4, respec
tively), show that, according to QTAIM, shared elec
trons appear between these pairs of H atoms. In accor
dance with the latest concepts of BPs as privileged
exchange channels [98], we may conclude that the
AILs between Hα1and Hα1' and between Hα2 and
Hα2' in the molecular graph for 1b and between Hα3
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
and Hα3' in the molecular graph for 1d (Fig. 1) repre
sent BPs. It remains unclear, however, whether the sta
bilization due to the appearance of exchange interac
tions [98] or the Pauli repulsion contributes more to
the total energy of the closedshell type interaction
between the mentioned pairs of atoms.
Comparison of Interactions
in Bis(toluene)chromium(0) Conformers
and Dimers of Toluene and Methane
A comparison of the E 0rel values calculated for 1a,
1b, 1с, and 1d (Table 1) shows that cisconformers 1b
and 1d are globally destabilized relative to 1a and 1c,
respectively. Neither a comparison of these energies
nor a topological analysis, however, provide an unam
biguous answer to the question of whether the H···H
contacts in 1b and 1d are locally destabilizing or stabi
lizing. Consideration of the energies of bonding and
repulsive interactions in toluene and methane dimers
would seem to be able to answer this question. It is
worth noting that the existence of toluene dimer
(PhMe)2 in the gas phase with a parallel arrangement
of toluene molecules like that in conformer 1b or 1d
has not been proved either experimentally or theoreti
cally [99–101]. In the present work, we also failed to
find such a dimer by the MP2/PQZ and RIMP2/TZ
methods. Only dimers 2a–2d were found on PES by
the RIMP2/TZ method (Fig. 5).
The model structure of dimer 2е, in which the phe
nyl rings are located exactly above one another and at
the same distance between their planes as between the
ring planes in 2а, was obtained from the dimer 2а
structure by shifting the rings in two mutually perpen
dicular directions without changing the geometries of
the toluene molecules. The dimer 2g structure, in
which methyl groups are oriented relative to one
another as in cisbis(toluene)chromium(0) 1b, was
obtained from 2d in the same manner. The dimer 2f
structure was obtained by rotating methyl groups in 2e
so that their orientation relative to the correspond
ing phenyl ring planes coincided with that in 1а. The
energy of 2f is higher by 0.05 kcal/mol than the
energy of 2е. This can be considered as the evidence
of quite free rotation of methyl groups in toluene
dimers. Dimers 2f and 2g are more weakly bonded
(the binding energy E b0 of toluene molecules is –3.88
and –2.43 kcal/mol, respectively) than dimers 2a
( E b0 = –6.76 kcal/mol) and 2d (E b0 = –5.96 kcal/mol).
The distances between the opposite carbon atoms of
the two phenyl rings in 2f and 2g (3.361–3.381 and
3.397–3.450 Å, respectively) are substantially longer
than the similar distances in 1a and 1b (Table 2).
On the other hand, a reduction in the distances R
between toluene molecules in its different dimers, as
compared to the optimal R values in these dimers,
results in a sharp increase in energies [100] due to the
rise in repulsive interactions. In conformers of 1,
Vol. 84 No. 10 2010
 INTRAMOLECULAR NONCOVALENT INTERACTIONS
(2a) (2b)
(2e)
Fig. 5. Toluene dimers calculated in the RIMP2/TZ approximation.
therefore, the interaction between these molecules
should be considered as repulsive. Indeed, for toluene
dimers 2h–2k (not shown in Fig. 5) in the geometries
of conformers 1a–1d, the E b0 values are already posi
tive (4.91, 5.66, 5.65, and 7.95 kcal/mol respectively)
and confirm the above assumption. In dimers 2f and
2g, the phenyl rings are parallel to one another, and
the carbon atoms of the methyl groups are in the ring
planes. The E b0 value for 2g with Hα1···Hα2 and
Hα1'···Hα2' contacts is higher by 1.45 kcal/mol than
that for 2f, this difference corresponding to repulsion
energy Erep of the methyl groups in 2g. On the other
hand, a comparison of E b0 values for 2i and 2h shows
that Erep between methyl groups in 2i (and, conse
quently, in 1b) is ~0.8 kcal/mol. The given estimates
show that an increase in the distance between the ipso
carbon atoms (i.e., the formation of angle α between
phenyl rings) and the outofplane position of methyl
groups relative to the rings can reduce the repulsion
energy between methyl hydrogen atoms in 1b from 1.4
to 0.8 kcal/mol, i.e., by 0.6 kcal/mol.
Let us try to clarify the character and energy of the
interaction between methyl groups in 1b and 1d also
from the analysis of data for methane dimers. Accord
ing to MP2/631++G** calculations [102], in an
eclipsed D2h methane dimer (3a) in which the pairs of
C–H bonds of methane molecules are oriented rela
tive to one another almost as methyl C–H bonds in 1b,
the equilibrium С···Сr and H···H distances are 3.942
and 3.122 Å, respectively, and the dissociation energy
De, CP (BSSE corrected) of this dimer is estimated as
0.2 kcal/mol. This virtually coincides with the data
from MP2/6311+G(2df, 2pd) calculations [103]. In
1b, optimized in the B971/PQZ approximation, the
d(С···С) and d(Н···Н) values are 3.517 and 2.562 Å,
respectively. At these distances, the interaction of
methane molecules in 3a is already repulsive with
repulsion energy Erep ~ 0.8 kcal/mol (see Fig. 3 in the
work [103]). This value coincides with the one above
obtained from the data for toluene dimers.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
1741
(2c) (2d)
(2f) (2g)
In an eclipsed D3h methane dimer (3b), one C–H
bond of each СН4 molecule is directed toward another
in almost the same way as a C–H bond of each methyl
group in 1d. In 3b, the equilibrium value
d(Н···Н)/d(С···С) is 2.667/4.849 and 2.692 Å, accord
ing to MP2/631++G** and MP2/6311++G**
[102] calculations, and the De, CP value of this dimer is
0.06 and 0.07 kcal/mol, respectively. The highest De, CP
value (0.11 kcal/mol) for 3b was obtained using
MP2/TZ(2d, 2p) [102] and MP2/6311+G(2df,
2pd) calculations [103]. In 1d, d(H···H) = 1.901 Å
was obtained by the B971/PQZ method. Accord
ing to MP2/6311G(2d, 2p) calculations, at this dis
tance the H···H repulsion energy Erep of two methane
molecules in 3b reaches ~0.4 kcal/mol. An analysis of
the interactions between methyl groups in bis(tolu
ene)chromium(0) cisconformers and methane mole
cules in its dimers thus allows us to conclude that there
is overall repulsive interaction between methyl hydrogen
atoms in 1b and 1d.
Chromium interacts very strongly with toluene
(Table 1), leading to the approach of toluene mole
cules in all conformers of 1 to distances substantially
shorter than those in toluene dimers. In 1b and 1d, the
distances between methyl H atoms become much
shorter than those between H atoms in methane
dimers 3a and 3b, respectively. This should necessarily
lead to considerable repulsive interactions between the
phenyl rings of toluene molecules in 1a–1d (see the
above) and methyl H atoms in 1b and 1d. One result of
repulsive interactions between methyl H atoms in cis
conformers 1b and 1d is not only the appearance of a
substantial angle between the phenyl ring planes, but
also the deviation of methyl groups from the ring
planes in the molecules of these conformers, as com
pared to those in molecules of transconformers
(Table 3), where there is no direct interaction between
methyl groups. High affinity of chromium to toluene,
however, is able to balance the energy of repulsive
interactions both between the methyl H atoms in 1b
and 1d and the phenyl rings in cis and transconform
Vol. 84 No. 10 2010
1742 DEM’YANOV et al.
ers of bis(toluene)chromium(0). In 1b and 1d, the
H···H repulsive forces are thus completely balanced by
“external force” such as the strong chromium–tolu
ene interaction. The resulting forces acting on each of
the Hα1, Hα2, Hα1', and Hα2' atoms in 1b and on
Hα3 and Hα3' in 1d are therefore zero, and the PES
stationary points correspond to conformers 1b and 1d.
From the above, it follows that (3, –1) CPs between
methyl hydrogen atoms in the molecular graphs of cis
conformers 1b and 1d and their associated AILs reflect
both globally and locally destabilizing interactions
between the pairs of H atoms, and hence between
methyl groups in general rather than the attractive
H···H interactions. This agrees with the negative atti
tude toward the possibility of the existence of stabiliz
ing H···H interactions [24–30], and that BCP exist
ence is not a criterion for bonding [30–33].
CONCLUSIONS
We studied the structure of bis(toluene)chro
mium(0) trans and cisconformers by means of the
density functional (B971 functional) and MP2 theo
ries. The location of the two hydrogen atoms of each
methyl group between the phenyl ring planes in the
most stable cisconformer of bis(toluene)chro
mium(0) was shown to be largely determined by the
stabilizing interactions of methyl C–H bonds and
their hydrogen atoms with the metal atom and chro
mium–carbon bonds. According to NBO analysis
data, the С–Н···Cr contacts should be considered as
hydrogen bonds rather than as agostic interactions.
NBO showed that the C–H bonds of methyl groups
also interact with Cr–C bonds, which can also
increase the deviation of these C–H bonds toward the
metal.
An analysis of the obtained and literature data
allowed us to conclude that, contrary to the existing
QTAIM concepts of stabilizing hydrogen–hydrogen
(H···H) interactions [8–15, 20–22], the interactions
between the pairs of hydrogen atoms of the two methyl
groups in cisconformers of bis(toluene)chromium(0)
are in fact both globally and locally destabilizing (i.e.,
repulsive). The (3, –1) CPs and their associated AILs
between the pairs of hydrogen atoms of the two methyl
groups in cisconformers of bis(toluene)chromium(0)
correspond to nonbonding interactions. Other disad
vantages of QTAIM were revealed, and the ΔE(H)
(ΔE(Ω)) value, i.e., the total change in the H (Ω) atom
energy that occurs during its interaction with another
H (Ω') atom, cannot be considered as the stabilization
energy of the H···H (Ω···Ω') interaction. Moreover,
ΔE(H) (ΔE(Ω)) cannot be applied even to draw qual
itative conclusions as to whether the interaction
between two close H atoms (Ω and Ω') is stabilizing or
destabilizing.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
ACKNOWLEDGMENTS
We are grateful to the Joint Supercomputer Center
of the Russian Academy of Sciences for allowing the
calculations, and to V.A. Chertkov (Department of
Chemistry, Moscow State University) for his help in
executing Gaussian 98 calculations.
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