Aryl–Aryl Interactions in (Aryl-Perhalogenated) 1,2-Diaryldisilanes

Article abstract of DOI:10.1002/chem.201905727

Three 1,2-diaryltetramethyldisilanes X₅C₆-(SiMe₂)₂-C₆X₅ with two C₆H₅, C₆F₅, or C₆Cl₅ groups were studied concerning the im

Full text of DOI:10.1002/chem.201905727

A Journal of
Accepted Article
Title: Aryl-Aryl Interactions in (aryl-perhalogenated) 1,2-Diaryldisilanes
Authors: Norbert Werner Mitzel, Marvin Linnemannstöns, Jan
Schwabedissen, Beate Neumann, Georg Stammler, and
Raphael Berger
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To be cited as: Chem. Eur. J. 10.1002/chem.201905727
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Aryl-Aryl Interactions in (aryl-perhalogenated) 1,2-Diaryldisilanes
Marvin Linnemannstöns,[a] Jan Schwabedissen,[b] Beate Neumann,[a] Hans-Georg Stammler,[a] Raphael
J. F. Berger[b] and Norbert W. Mitzel*[a]
Dedicated to Professor Carlos Omar Della Védova on the occasion of his 65th birthday
Three 1,2-diaryltetramethyldisilanes X5C6-(SiMe2)2-C6X5 with two
C6H5, C6F5 or C6Cl5 groups were studied concerning the impor-
tance of London dispersion driven interactions between their aryl
groups. They were prepared from 1,2-dichlorotetramethyldisilane
by salt elimination. Their structures were determined in the solid
state by X-ray diffraction and for free molecules by gas electron-
diffraction. The solid-state structures of the fluorinated and chlo-
rinated derivatives are dominated by aryl-aryl interactions. Unex-
pectedly, Cl5C6-(SiMe2)2-C6Cl5 exists exclusively as eclipsed syn-
conformer in the gas phase with strongly distorted Si-C6Cl5 units
due to strong intramolecular interactions. In contrast, F5C6-
(SiMe2)2-C6F5 reveals weaker interactions. The contributions to
the total interaction energy was analyzed by SAPT calculations.
interaction in proteins,[10] intercalation of drugs into DNA,[11] crystal
engineering[12] and in many host-guest recognition processes.[13]
In the history of QC calculations, the C6H6 (1) dimer was repea-
tedly studied. In contrast to the herringbone-like arrangement in
the crystal structure of pure 1,[14–16] the isolated benzene dimer
exists in two equilibrium structures: a tilted T-shaped one and a
parallel-displaced one. The complex dynamics and small differen-
ce in binding energies has caught the interest of experimentalists
and theoreticians.[17] Analogous to 1, Varadwaj et al. found twelve
different structures for the dimer of hexafluorobenzene (C6F6, 2)
by QC methods,[18] the parallel displaced structure of the dimer
being the most stable one. In contrast to the herringbone-like ar-
rangements in solid 1 and 2,[14,15] the 1:1 co-crystal reveals colum-
nar stacks of alternating C6H6 and C6F6 units.[19] First attempts of
explanation quoted interacting quadrupoles with their moments
being of equal magnitude but of opposite sign (1: −29.0·10−40; 2:
31.7·10−40 C m2).[20] Later studies indicated that electrostatics
alone cannot explain the intermolecular arrangement and that LD
contributes at least as much to the total interaction energy.[21]
Pure hexachlorobenzene (C6Cl6, 3) behaves differently than 1 or
2. Its crystal structure comprises molecular stacks similar to the
columnar structures of the 1:1 C6H6∙C6F6 co-crystal.[22] Several
pentachlorophenyl compounds show a related behavior.[23]
Recently, we investigated the effects of stacking interactions of
three compounds with phenyl and perfluorophenyl rings bridged
by (sila)propyl chains.[24] In the solid state, these molecules recei-
ve stabilization by intermolecular aryl-aryl stacking interactions,
whereas free molecules, determined by gas electron diffraction
(GED), find their energetic minima as conformers bearing intra-
molecular aryl-aryl interactions.
We turn now to the interactions between symmetric pairs of per-
chlorinated, perfluorinated and parental phenyl groups, both in the
solid and in the gas phase. Gases contain free molecules, inde-
pendent of intermolecular forces omnipresent in both crystal and
solution phases, and thus they are ideally suited for evaluating the
results of QC methods. We chose the disilane backbone as a spa-
cer linking the aryl groups due to its conformational flexibility
observed in earlier investigations.[25] Three symmetrically substi-
tuted 1,2-diaryl-1,1,2,2-tetramethyldisilanes X5C6-(SiMe2)2-C6X5
[X = H(5), F(6), Cl(7)] were generated by salt elimination from 1,2-
dichlorodisilane 4 with the corresponding lithium phenyl species
C6X5Li in good yields after purification by column chromatography
and recrystallisation (5 84%, 6 79%, 7 67%). Silanes 5–7 are
insensitive towards water and can be stored under air for at least
several months without decomposition.
London dispersion (LD) forces are basically the attractive part of
van-der-Waals interactions[1] and are generally regarded as weak
compared to other types of molecular interactions. Accordingly,
their importance for chemical reactivity and stability as well as
their impact on molecular structure seem to have been underesti-
mated in the past. Single pairs of C–H∙∙∙H–C fragments indeed
interact weakly but for larger systems with multiple interaction
partners, the contribution of dispersion increases rapidly.[2] Exam-
ples include the diverse phenomena such as the variation in boi-
ling points along the homologous series of n-alkanes, the greater
stability of branched vs. linear isomers as well as the folded hair-
pin structure of gaseous n-alkanes longer than heptadecane.[3]
Wagner and Schreiner recently underlined the importance of LD[4]
and suggested to revise the established understanding of the
influence of steric effects on the stability of molecules in general.
For instance, steric repulsion between phenyl groups in hexaphe-
nylethane (HPE) is held accountable for its thermodynamic insta-
bility,[5] whereas the introduction of even more sterically deman-
ding substituents (like tBu, Ad) in all twelve meta-positions leads
to isolable HPE derivatives, obviously due to stabilization by LD.[6]
A delicate balance between Pauli repulsion and LD attraction
leads to unusually long C–C bonds observed in several diamond-
oid dimers;[7] they were studied to evaluate a range of quantum-
chemical (QC) methods that take LD into account.[8]
Non-covalent intermolecular interactions between aromatic sys-
tems are of great importance for many supramolecular organiza-
tion and recognition processes,[9] for example for the side-chain
[a]
M. Sc. M. Linnemannstöns, B. Neumann, Dr. H.-G. Stammler and
Prof. Dr. N. W. Mitzel
Lehrstuhl für Anorganische Chemie und Strukturchemie
Fakultät für Chemie, Universität Bielefeld,
Universitätsstraße 25, 33615 Bielefeld (Germany)
E-mail: mitzel@uni-bielefeld.de
The structures of 5–7 in the solid state were determined by X-
ray diffraction on single crystals obtained by slow evaporation of
the solvent from saturated solutions.[26] The twinning in crystals of
5 and 7 could be satisfactorily modelled. Figure 1 illustrates 1,2-
diphenyl-disilane 5 to reveal a anti-conformation with a torsion
angle φ(CSiSiC) at 177.2(1)°. Substantial π-stacking to neighbo-
ring molecules is not observed, but the tilted T-like arrangement
[b]
Dr. J. Schwabedissen and PD Dr. R. J. F. Berger
Chemie und Physik der Materialien
Paris-Lodron-Universität Salzburg
Jakob-Haringer-Straße 2a, 5020 Salzburg (Austria)
Supporting information for this article is given via a link at the end of
the document. CCDC 1965241–1965243
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10.1002/chem.201905727
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COMMUNICATION
of phenyl groups of neighboring molecules resembles the crystal
packing of benzene. The coordination geometry at the silicon
atoms is almost tetrahedral and the Si–Si bond length [2.342(1) Å]
lies within the typical range[25] for 1,1,2,2-tetramethyldisilanes.
There are also slightly longer intermolecular aryl-aryl-interactions
with a distance dcentroids at 3.93(1) Å. The columnar stacks found
in crystalline 7 resemble those in solid C6Cl6.[22] The mean planes
of the C6Cl5 units in 7 enclose angle of 63.9(2) and 65.5(2)° rela-
tive to the vector connecting the ring centroids. The corresponding
[22]
tilt angle for solid C6Cl6 was given as 63°. In addition to the
stacking interactions, several other intermolecular Cl∙∙∙Cl contacts
below the sum of the vdW radii [3.347(1)–3.716(1) Å] are found.
Table 1. Selected experimental structures parameters for 5–7 in the crystalline
state (XRD) and in the gas phase (GED, rh1 values, error 1σ).
Figure 1. Molecular structure of 5 in the crystalline state. Displacement ellipso-
ids are drawn at 50 % probability level. Hydrogen atoms are omitted for clarity.
5 (XRD)
6 (XRD)
6 (GED)a
7 (XRD)c
7 (GED)c
φ(CSiSiC) [°]
d (Si–Si) [Å]
177.2(1)
173.7(1)
11.2(8)/
48.1(8)
6.0(3)
8.0(5)
The fluorinated 6 also adopts an anti-conformation in the crystal
[φCSiSiC = 173.7(1)°], with a Si–Si distance [2.338(1) Å] being iden-
tical within experimental error to that in 5. In contrast to 5, 6 con-
sists of dimeric units of inversion symmetry These dimers are
stabilized by aryl-aryl interactions [dcentroids = 3.688(1) Å, Figure 2].
However, there are no such interactions between these and
neighboring dimers.
2.342(1)
2.338(1)
2.386(4)/
2.368(4)
2.381(2)
2.367(5)
dc-c inter. [Å]
dc-c intra. [Å]
–
–
3.688(2)
–
3.93(1)
3.76(1)
–
–
3.76(5)b,c
3.82(5)b
170.4(5)b
179.0(1)
179.2(1)
179.4(1)
178.4(1)
172.8(6)b
173.5(6)b
167.6(3)
168.1(3)
τ (SiCiCp) [°]
a Values are given for the syn- / gauche-conformers. b Dependent parameters,
not refined explicitly.c Only the syn-conformer is present.
Table 2. Energetic differences (ΔE) in kJ mol−1 relative to the most stable con-
former and dihedral angles φ(CSiSiC) for the conformers of 5, 6 and 7 at the
PBE0/TZVP level of theory, with and without GD3(BJ) corrections for dispersion.
Dispersion corrected
Uncorrected for dispersion
Figure 2. Molecular structure and primary aggregation of 6 in the crystal. Dis-
placement ellipsoids are at 50 % probability level. Hydrogen atoms omitted for
clarity. Symmetry operation for generating equivalent positions: 1−x, 1−y, 1−z.
φ(CSiSiC) [°]
ΔE
φ(CSiSiC) [°]
ΔE
5
6
gauche
anti
57.9
179.9
11.5
6.8
0.0
1.5
0.0
3.0
0.0
14.8
64.9
180.0
19.7
4.6
0.0
4.0
0.0
3.7
0.0
0.6
syn
gauche
anticlinal
syn
48.2
54.1
140.7
8.4
141.9
11.2
7
anticlinal
138.4
140.1
Using dispersion-corrected (D3BJ)[8] energy scans (PBE0/TZVP)
along the CSiSiC torsion angle,[27,28] the conformational landsca-
pes of compounds 5–7 were explored; the generated structures
were optimized at the PBE0/TZVP and PBE0(D3BJ)/TZVP levels
of theory (see SI). These potential energy scans predict two stable
conformers for the parent phenyl substituted disilane 5, three for
the fluorinated species 6, and two for the chlorinated 7. Both
predicted conformers of 5 are free of aryl stacking interactions and
adopt, expectedly, stable gauche- and anti-orientations of the
phenyl groups about the Si–Si bond. In contrast, energy scans for
6 and 7 forecast structures with syn-conformation of the aryl
substituents stabilized by aryl-aryl stacking interactions. Optimi-
zing the different suggested structures for 5 yielded gauche- and
anti-conformers of C1 symmetry, the latter one being the most
stable conformer independent of including dispersion. The diffe-
rent tilt of the phenyl groups about the Si–Cipso bond reduces sym-
metry from the expected C2. However, fluoro-compound 6 con-
tains a syn-conformer and this is the sole conformer observed for
7. For 6 the gauche-conformer is lowest in energy. This is possibly
a manifestation of the gauche effect,[29] usually observed for
partially fluorinated ethanes[30] and disilanes.[31] Optimizing the
Figure 3. a) View along the Si–Si axis of 7; b) View on the distorted SiC5 frag-
ment; c) Molecular structure and primary aggregation motif of 7. Displacement
ellipsoids are drawn at 50 % probability level. Hydrogen atoms are omitted for
clarity. Symmetry operation for generating equivalent positions: 2+x, +y, +z.
The crystal structure of the pentachlorophenyl disilane 7 shows a
disorder (50:50, see SI) and adopts a rather unusual eclipsed con-
formation (Figure 3) described by a torsion angle φCSiSiC of barely
6.0(1)°. This is the result of intramolecular C6Cl5···C6Cl5 stacking
interactions [dcentroids = 3.76(1) Å]. These are strong enough to dis-
tort the SiC6Cl5 units from planarity (Figure 3b), i.e. the angle
Si(1)-C(3)-C(6) is 167.6(3)° and Si(2)-C(3)-C(6) is 168.1(3)°.
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conformer found in the gas phase. Modelling the molecular scat-
tering in this way resulted in a disagreement factor of 4.4%. The
syn-conformer adopts a dihedral angle CSiSiC of 8.0(6)° and a
centroid···centroid distance between the C6Cl5 rings of 3.82(5) Å.
Both values are slightly larger than the corresponding parameters
in the solid state (vide supra), but the Si–Si bond [rh1 = 2.367(5) Å,
3σ] is in a comparable range to the corresponding solid-state
parameter [2.381(2) Å]. The gas-phase structure of the fluorina-
ted 6 was fitted (Rf = 3.6%) using a model comprising a syn-
syn-conformers of 6 and 7 under explicit consideration of disper-
sion, the dihedral angles φCSiSiC become smaller and the silicon
atoms bend out of the aryl planes (as described for the solid-state
of 7 above). Dispersion corrections stabilize both syn conformers
– by about 14 kJ mol–1 in the case of 7.
conformer [φCSiSiC = 11.2(8)°] and a gauche-conformer [φCSiSiC
=
48.1(8)°].The preference for a conformer remains ambiguous as
the abundance of the syn-conformer is determined to be 43(13)%
by GED. Thus, the two conformers are present in almost equal
amounts in the gas phase. Despite the larger dihedral angle in the
syn-conformer of 6, the centroid···centroid distance is the same
within experimental error [3.76(5) Å for 6] between the two aryl
substituents in 6 and 7.
For breaking down the main contributions to the interactions bet-
ween the aryl substituents in 5–7, symmetry-adapted perturbation
theory (SAPT) was applied (Figure 6).[33] The chosen conformers
are those experimentally observed in the gas phase and additio-
nally the gauche conformer of 5. Comparing the two gauche-con-
formers of 5 and 6 gives similar induction stabilizations at about
−3 kJ mol–1, but a higher dispersion energy for the fluorinated 6
(6: −22.6, 5: −13.2 kJ mol–1), while the exchange repulsion energy
behaves in a reverse manner (6: 13.1, 5: 21.3 kJ mol–1); the elec-
trostatic contribution stabilizes 5 (−2.0 kJ mol–1) but destabilizes 6
(3.4 kJ mol–1). This can be rationalized to the parallel-displaced
geometry for 5 (similar: benzene dimer in the gas[17]) whereas
electrostatic repulsion in 6 may be due to a fluorine atom located
almost directly above the aryl substituent. Overall, aryl-aryl inter-
actions stabilize 6 by 0.5 kJ mol–1 and 5 by 4.9 kJ mol–1.
Figure 4. Radial distribution curves for the GED refinements of disilanes 6 (top)
and 7 (bottom): experimental values (circles), model (solid line) and difference
curve (lower trace, exp.−model). Vertical sticks represent interatomic distances.
Figure 5. Two views of each of the structures of the gauche- and syn-confor-
mers of 6 and the only occurring conformer of 7 (syn) as determined by gas
electron diffraction (GED).
Figure 6. SAPT decomposition of energy in kJ mol–1 of the interaction between
the conformers found in the gas phase for 5–7.
The aryl moieties in the syn-conformers are closer and interact
more strongly. All energy contributions in 7 are about double as
large as in 6, except the electrostatic term: this is more than four
times larger (6: −5.6, 7: −27.2 kJ mol−1). The importance of elec-
trostatic contributions for interacting aryl rings was recently high-
lighted.[34] The exchange repulsion in syn-6 (36.4 kJ mol−1) out-
weighs the dispersion energy (−31.3 kJ mol–1) by 5 kJ mol–1. In
contrast to that, the large dispersion energy in 7 (−73.0 kJ mol−1)
stabilizes the intramolecular stacking interaction, while exchange
is comparatively smaller 67.2 kJ/mol−1.
Experimental investigations of the conformational characteristics,
relative abundances and structures of disilanes 5 to 7 in the gas
phase were undertaken by means of gas electron diffraction (Fi-
gures 4 and 5, exptl. details see SI). Experimental scattering data
of 5 were recorded, but could so far not be modelled satisfactorily
due complicated dynamics related to large amplitude motions of
the phenyl rings about the Si–C bonds. Related complications
were described in other recent GED studies.[32] As predicted by
the dispersion-corrected QC calculations for 7, syn was the only
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Our work demonstrates the strikingly different ability of phenyl,
pentafluorophenyl and pentachlorophenyl substituents to exert
aryl-aryl stacking interactions. We studied this between the 1,2-
aryl-substituents in tetramethyldilsilane units. While simple hydro-
gen substituted phenyl groups are too weak predetermine aggre-
gation in the solid state or conformers with aryl-aryl interactions in
the gas phase, pentafluorophenyl and pentachloro-phenyl substi-
tuents do so. Interactions between pentafluorophenyl groups are
strong enough to lead to intermolecular aggregation in the solid
and to stabilize an otherwise unfavorable syn-conformer in the
gas phase. Pentachlorophenyl substituents interact so strongly,
that syn is the sole conformation present in the gaseous and solid
states, despite the fact that substantial deformation of the Si-C6Cl5
units has to be overcome. The analysis of interaction contributions
shows the increasing importance of London dispersion along the
series C6H5 < C6F5 < C6Cl5 which is partially compensated by ad-
versely acting exchange interactions and augmented by an elec-
trostatic term, both also with increasing strength along the series.
These results may serve to explain the practically often observed
effect of low solubility of highly chlorinated aryl compounds.
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Funding Information
This work was funded by DFG (German Research Foundation) in
the Priority Program SPP1807 “Control of LD in molecular chemi-
stry”, grant MI477/28-2 and BE4632/2-2, project no. 271386299)
and the core facility GED@BI (grant MI477/35-1, project no.
324757882).
Acknowledgment
We thank Klaus-Peter Mester and Marco Wißbrock for recording
NMR spectra and Barbara Teichner for elemental analyses. We
gratefully acknowledge computation time and QC programs provi-
ded by the RRZK (Universität zu Köln) and the PC2 (Universität
Paderborn).
Keywords: inter/intramolecular π-stacking, solid state structures,
dispersion, bridged arenes, halogenated arenes.
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10.1002/chem.201905727
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
M. Linnemannstöns, J. Schwabedissen,
B. Neumann, H.-G. Stammler, R. J. F.
Berger and N. W. Mitzel*
Page No. – Page No.
Aryl-Aryl Interactions in (aryl-perhalo-
genated) 1,2-Diaryldisilanes
An eclipsed syn-conformation is exclusively observed for Cl5C6-(SiMe2)2-C6Cl5 in
the solid and gaseous phase with strongly distorted Si-C6Cl5 units; it demonstrates
the strikingly different ability of phenyl, pentafluorophenyl and pentachlorophenyl
substituents to exert aryl-aryl stacking interactions.
[a]
M. Sc. M. Linnemannstöns, B. Neumann, Dr. H.-G. Stamm
Prof. Dr. N. W. Mitzel
Lehrstuhl für Anorganische Chemie und Strukturchemie
Fakultät für Chemie, Universität Bielefeld,
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