Bi- and tridentate silicon-based acceptor molecules

Article abstract of DOI:10.1515/znb-2017-0031

Triethynylphenylsilane (1), trivinylphenylsilane (2), diethynyldiphenylsilane (3) and diphenyldivinylsilane (4) were reacted with chlorodimethylsilane yielding the corresponding hydrosilylation products. To increase their Lewis acidity, the Si-Cl functions were directly transferred into Si-C6F5 units by salt elimination reactions leading to the (semi-) flexible molecules 5-8 bearing two or three Lewis-acidic sidearms. With the aim of providing host-guest complexes, the air-stable and readily soluble compounds 5-8 were converted with N- and O-Lewis bases of different size and geometry. In all cases, NMR spectroscopic investigations reveal no formation of Lewis acid-base complexes. X-ray diffraction experiments of host compounds 5-7 show intermolecular aryl perfluoroaryl interactions of dispersion nature in the solid state. By hydrosilylation of 1 with trichlorosilane the more Lewisacidic all-trans-tris[(trichlorosilyl)vinyl]phenylsilane (9) was obtained. Its Lewis acidity was further increased by fluorination to yield all-trans-tris[(trifluorosilyl)vinyl] phenylsilane (10); the conversion with nitrogen containing Lewis bases ends up in the formation of insoluble precipitates.

Full text of DOI:10.1515/znb-2017-0031

Z. Naturforsch. 2017; 72(6)b: 383–391
Jan Horstmann, Jan-Hendrik Lamm, Till Strothmann, Beate Neumann, Hans-Georg Stammler
and Norbert W. Mitzel*
Bi- and tridentate silicon-based acceptor
molecules
DOI 10.1515/znb-2017-0031
be considered as the direct opposite of poly-Lewis bases,
however, the chemistry of the latter compounds (the most
prominent examples are crown ethers, cryptands, etc.)
are much better explored and well understood. Neverthe-
less, the chemistry of poly-Lewis acids became a rapidly
growing field within the last years and various compounds
have been described in the literature [1–7].
Received February 20, 2017; accepted March 31, 2017
Abstract: Triethynylphenylsilane (1), trivinylphenylsilane
(2), diethynyldiphenylsilane (3) and diphenyldivinylsi-
lane (4) were reacted with chlorodimethylsilane yielding
the corresponding hydrosilylation products. To increase
their Lewis acidity, the Si–Cl functions were directly
transferred into Si–C6F5 units by salt elimination reactions
leading to the (semi-) flexible molecules 5–8 bearing two
or three Lewis-acidic sidearms. With the aim of provid-
ing host-guest complexes, the air-stable and readily solu-
ble compounds 5–8 were converted with N- and O-Lewis
bases of different size and geometry. In all cases, NMR
spectroscopic investigations reveal no formation of Lewis
acid-base complexes. X-ray diffraction experiments of
host compounds 5–7 show intermolecular aryl…perfluoro-
aryl interactions of dispersion nature in the solid state. By
hydrosilylation of 1 with trichlorosilane the more Lewis-
acidic all-trans-tris[(trichlorosilyl)vinyl]phenylsilane (9)
was obtained. Its Lewis acidity was further increased by
fluorination to yield all-trans-tris[(trifluorosilyl)vinyl]
phenylsilane (10); the conversion with nitrogen contain-
ing Lewis bases ends up in the formation of insoluble
precipitates.
Prominent examples of bidentate Lewis acids are,
for instance, 1,2-bis(difluoroboranyl)ethane [8], being
able to form complexes with methanolate ions, or the
rigid 1,2-bis(organostannyl)benzene [9] host and the
fluorinated ortho-disilylbenzenes [10]. The latter com-
pounds have been demonstrated to be excellent fluoride
ion acceptors. Other well-known examples of bidentate
Lewis hosts contain aluminium [11–14], gallium [13–18],
indium [19, 20] or mercury [21, 22] as Lewis acid functions.
Important contributions in the field of cyclic tridentate
tin- or silicon-based Lewis acids stem from Jurkschat and
co-workers [23–25], as well as from Jung and Xia [26] or
Wong Chi Man et al. [27]. Tridentate Lewis acids in which
the active sites are embedded in noncyclic structures are
often generated by hydroalumination [14] or hydrogal-
lation reactions [15]. In the course of our investigations
in the field of polydentate Lewis acids we synthesized a
wide range of compounds containing two [28–30], three
Keywords: dispersion interactions; poly-Lewis acids; [31–35], four [30, 36] and six [33, 37] Lewis-acidic func-
X-ray diffraction experiments.
tionalities. Common to all examples are Lewis-acid func-
tions attached to a more or less rigid organic framework
like alkynyl-anthracenes, -tribenzotriquinacenes or -trisi-
lacyclohexanes. Very recently, we reported bidentate Si-
and Ga-Lewis-acidic host structures with just one silicon
atom as core unit, being able to form – in part polymeric
– host-guest adducts with fluoride ions or neutral N-donor
molecules [38, 39].
1 Introduction
Molecules containing multiple Lewis-acidic receptor
moieties are also known as poly-Lewis acids. They can
*Corresponding author: Norbert W. Mitzel, Chair of Inorganic and
Structural Chemistry, Faculty of Chemistry and Center for Molecular
Materials CM2, Bielefeld University, Universitätsstraße 25, D-33615
Bielefeld, Germany, Fax: +(0)521 106 6026,
2 Results and discussion
Trichlorophenylsilane was converted with ethynyl- or
vinyl magnesium bromide to yield the corresponding tri-
substituted phenylsilanes 1 and 2 (Scheme 1), according
to our previously published procedures for the generation
of the doubly ethynyl- and vinyl-substituted compounds 3
E-mail: mitzel@uni-bielefeld.de
Jan Horstmann, Jan-Hendrik Lamm, Till Strothmann, Beate Neumann
and Hans-Georg Stammler: Chair of Inorganic and Structural Chemistry,
Faculty of Chemistry and Center for Molecular Materials CM2, Bielefeld
University, Universitätsstraße 25, D-33615 Bielefeld, Germany
Brought to you by | Cornell University Library
Authenticated
Download Date | 7/3/17 10:07 AM

ꢁꢁꢁꢂ
ꢀJ. Horstmann et al.: Bi- and tridentate silicon-based acceptor molecules
384ꢀ
are all of the same lengths within experimental errors
H
[Si(1)–C(7) 1.821(3) Å, Si(1)–C(9) 1.827(3) Å and Si(1)–C(11)
1.830(3) Å]. The central silicon atom is tetrahedrally coor-
dinated as it is indicated by the C−Si(1)–C angles ranging
from 108.0(1)° [C(9)–Si(1)–C(11)] to 111.0(2)° [C(1)–Si(1)–
C(9)]. All ethynyl units are close to linearity [Si(1)–C(7)–
C(8) 176.5(3)° to Si(1)–C(11)–C(12) 178.5(3)°].
As it is displayed in Scheme 2, the di- and triethynyl-
silanes 1 and 3 as well as the di- and trivinylsilanes 2 and
4 were converted with chloro(dimethyl)silane in the pres-
ence of Karstedt’s catalyst to generate the corresponding
hydrosilylation all-trans-products. These were directly
reacted with (pentafluorophenyl)magnesium bromide to
yield the desired perfluorophenyl-substituted bi- and tri-
dentate silanes 5–8 (yields about 90%) as air- and mois-
ture-stable compounds [40].
PhSi
PhSi
H
i)
1
H
PhSiCl3
ii)
2
Scheme 1:ꢁSynthesis of the organic backbones 1 and 2. Reagents
and conditions: i) ethynylmagnesium bromide, THF, 0°C to r.t., 14 h,
80%; ii) vinylmagnesium chloride, THF, r.t., 16 h, 74%.
We also used trichlorosilane and dichloromethylsi-
lane to transform compounds 1–4 to the corresponding
hydrosilylated species. However, the subsequent reac-
tion with the perfluoroaryl Grignard compound led to an
undefined mixture of products – in part of extremely low
solubility – which could not be separated successfully.
Besides the NMR spectroscopic and mass spectrometric
characterization of the C6F5-substituted silylsilanes, the
molecular structures of all solid products 5–7 (compound
8 is of oily consistency) were elucidated by X-ray diffrac-
tion experiments (Figs. 2–4).
and 4 [38]. The products were isolated as colourless crys-
talline material (1) or as colourless liquid (2). Their iden-
tity was proven by multinuclear NMR spectroscopy as well
as by mass spectrometry or elemental analysis.
Single crystals of triethynylphenylsilane (1), suit-
able for X-ray diffraction experiments, were grown from
n-hexane at room temperature; the molecular structure
in solid state is depicted in Fig. 1. The Si(1)–C(1) bond
[1.848(3) Å] to the phenyl substituent is slightly longer
than the Si(1)–C bonds to the ethynyl substituents, which
Due to intermolecular dispersive-type C6H5···C6F5
interactions and H···F contacts, all pentafluorophenyl
substituents of 5, 6 and 7 are directed to the same side.
Compounds 5 and 6 form strands (Figs. 2b and 3b), in
which the electron rich phenyl substituent is interacting
with pentafluorophenyl groups of another molecule. The
shortest centroid(C6F5)···centroid(C6H5) distances to a
H
i)
SiMe2(C6F5)
Ph4−nSi
Ph4−nSi
n
n
1 n = 3
3 n = 2
5 n = 3
7 n = 2
Fig. 1:ꢁMolecular structure of triethynylphenylsilane (1) in the
solid state. Displacement ellipsoids are drawn at the 50% prob-
ability level. Hydrogen atoms of the phenyl substituent are omitted
for clarity. Selected bond lengths (Å) and angles (deg): Si(1)–C(1)
1.848(3), Si(1)–C(7) 1.821(3), Si(1)–C(9) 1.827(3), Si(1)–C(11)
1.830(3), C(7)–C(8) 1.173(4), C(9)–C(10) 1.176(4), C(11)–C(12)
1.174(4); C(1)–Si(1)–C(7) 110.0(1), C(1)–Si(1)–C(9) 111.0(1), C(1)–Si(1)–
C(11) 110.1(1), C(7)–Si(1)–C(9) 109.5(1), C(7)–Si(1)–C(11) 108.0(1),
C(9)–Si(1)–C(11) 108.1(1), Si(1)–C(7)–C(8) 176.5(3), Si(1)–C(9)–C(10)
177.3(3), Si(1)–C(11)–C(12) 178.5(3).
SiMe2(C6F5)
i)
Ph4−nSi
Ph4−nSi
n
n
2 n = 3
6 n = 3
8 n = 2
4 n = 2
Scheme 2:ꢁSynthesis of the bi- and tridentate Lewis acids 5–8.
Reagents and conditions: i) 1. HSiMe2Cl (neat), Karstedt’s catalyst,
r.t., 1 h; 2. BrMgC6F5, THF, r.t. to reflux, 2 h, 85% to 92% over all.
Brought to you by | Cornell University Library
Authenticated
Download Date | 7/3/17 10:07 AM

ꢂꢁꢁꢁ
J. Horstmann et al.: Bi- and tridentate silicon-based acceptor moleculesꢀ
ꢀ385
Fig. 3:ꢁMolecular structure of tris[(pentafluorophenyl)dimethylsi-
lylethyl]phenylsilane (6) (a) and a representative strand (b) in the
solid state. Displacement ellipsoids are drawn at the 50% prob-
ability level. Hydrogen atoms of the phenyl substituents are omitted
for clarity. Selected bond lengths (Å) and angles (deg): Si(1)–C(1)
1.886(8), Si(1)–C(11) 1.868(9), Si(1)–C(21) 1.872(9), Si(1)–C(31)
1.910(9), C(1)–C(2) 1.543(12), C(11)–C(12) 1.511(12), C(21)–C(22)
1.530(11), C(2)–Si(2) 1.880(8), C(12)–Si(3) 1.870(9), C(22)–Si(4)
1.867(8), Si(2)–C(5) 1.926(10), Si(3)–C(15) 1.943(9), Si(4)–C(25)
1.931(8); Si(1)–C(1)–C(2) 112.0(5), C(1)–C(2)–Si(2) 113.1(6), Si(1)–
C(11)–C(12) 114.0(6), C(11)–C(12)–Si(3) 117.1(6), Si(1)–C(21)–C(22)
113.8(5), C(21)–C(22)–Si(4) 115.8(5), C(2)–Si(2)–C(5) 106.6(4), C(12)–
Si(3)–C(15) 109.6(4), C(22)–Si(4)–C(25) 111.7(4).
Fig. 2:ꢁMolecular structure of all-trans-tris[(pentafluorophenyl)-
dimethylsilylvinyl]phenylsilane (5) (a) and a representative strand
(b) in the solid state. Displacement ellipsoids are drawn at the 50%
probability level. Hydrogen atoms of the phenyl substituents are
omitted for clarity. Selected bond lengths (Å) and angles (deg):
Si(1)–C(1) 1.859(2), Si(1)–C(11) 1.867(3), Si(1)–C(21) 1.867(3), Si(1)–
C(31) 1.882(2), C(1)–C(2) 1.331(3), C(11)–C(12) 1.345(4), C(21)–C(22)
1.331(4), C(2)–Si(2) 1.859(3), C(12)–Si(3) 1.865(3), C(22)–Si(4)
1.872(3), Si(2)–C(5) 1.909(2), Si(3)–C(15) 1.904(2), Si(4)–C(25)
1.902(2); Si(1)–C(1)–C(2) 128.6(2), C(1)–C(2)–Si(2) 122.5(2), Si(1)–
C(11)–C(12) 122.3(2), C(11)–C(12)–Si(3) 129.2(2), Si(1)–C(21)–C(22)
126.2(2), C(21)–C(22)–Si(4) 123.8(2), C(2)–Si(2)–C(5) 106.7(1), C(12)–
Si(3)–C(15) 106.1(1), C(22)–Si(4)–C(25) 105.7(1).
molecule generated by the glide plane in 5 are 3.936(2) Å, 4,4′-bipyridine and 1,3,5-trimethoxybenzene as Lewis
whereas in 6 six crystallographically independent basic guest species. However, in neither case the forma-
strands can be obtained all generated by translation tion of host-guest complexes could be revealed by NMR
along the crystallographic a axis showing centroid–cen- spectroscopy, as the resonances of host- and guest com-
troid distances in the range from 3.817(5) to 4.893(6) Å. pounds in the mixture are not shifted compared to the
In 7, in which the pentafluorophenyl substituents show pure species.
interactions with two different molecules, the shortest
Inspired by the solid state structures of compounds
centroid(C6F5)···centroid(C6H5) distances in the solid state 5–7, showing dispersion intermolecular C6H5···C6F5 inter-
were found with 3.685(1) Å to the neighbouring molecule actions, we explored the option whether the (semi-) flex-
generated by the glide plane and 3.740(1) Å to the one ible (perfluoroaryl)silylsilanes 5–8 can serve as two- or
generated by translation along the a axis, resulting in three-fold π-acceptor substrates. To investigate a potential
the formation of crosslinked strands. In co-crystals con- co-crystallisation of external electron-rich aryl systems, we
taining phenyl substituents and C6F6, the length of such added tolane (diphenylacetylene), anthracene, triptycene
π–π interactions falls over a range from 3.5 to 3.8 Å [41, or triphenylsilane to solutions of 5–8 in dichloromethane
42]. In this case, the hexafluorobenzene enables shorter and n-hexane [41]. Despite numerous attempts, we found
aryl···perfluoroaryl contacts than the substituted ones of no evidence for the formation of such dispersion-driven
5, 6 and 7.
complexes, neither by crystallization nor by NMR spectro-
Within the scope of our project, we reacted products scopic techniques.
5–8 with equimolar amounts of some neutral N- and
As already mentioned above, triethynylphenylsilane
O-containing Lewis bases. To cover a wide range of differ- (1) was also reacted with trichlorosilane to form all-trans-
ent sizes as well as of various kinds, numbers and orienta- tris(trichlorosilylvinyl)phenylsilane (9). As shown in
tions of the donor atoms, we used pyridine, 1,3,5-triazine, Scheme 3, the corresponding tris(trifluorosilyl) species 10
Brought to you by | Cornell University Library
Authenticated
Download Date | 7/3/17 10:07 AM

ꢁꢁꢁꢂ
ꢀJ. Horstmann et al.: Bi- and tridentate silicon-based acceptor molecules
386ꢀ
Fig. 5:ꢁMolecular structure of tris(trichlorosilylvinyl)phenylsilane
(9) in the solid state. Displacement ellipsoids are drawn at the
50% probability level. Hydrogen atoms of the phenyl substituent
are omitted for clarity. Selected bond lengths (Å) and angles (deg):
Si(1)–C(1) 1.874(3), Si(1)–C(3) 1.874(4), Si(1)–C(5) 1.863(3), C(1)–C(2)
1.332(4), C(3)–C(4) 1.337(5), C(2)–Si(2) 1.840(3), C(4)–Si(3) 1.844(4),
Si(2)–Cl(1) 2.026(1), Si(2)–Cl(2) 2.032(1), Si(2)–Cl(3) 2.029(1),
Si(3)–Cl(4) 2.018(2), Si(3)–Cl(5) 2.033(2); Si(1)–C(1)–C(2) 124.9(2),
Si(1)–C(3)–C(4) 124.4(3), C(1)–C(2)–Si(2) 124.4(2), C(3)–C(4)–Si(3)
122.9(3), Cl(1)–Si(2)–Cl(2) 107.6(1), Cl(2)–Si(2)–Cl(3) 108.0(1),
Cl(1)–Si(2)–Cl(3) 108.7(1), Cl(4)–Si(3)–Cl(5) 108.9(1), Cl(5)–Si(3)–
Cl(5′) 106.6(1). Symmetry equivalent atoms are generated by the
operation 1ꢂ−ꢂx, y, z.
Fig. 4:ꢁMolecular structure of bis[(pentafluorophenyl)dimethylsilyl-
vinyl]diphenylsilane (7) in the solid state. Displacement ellipsoids
are drawn at the 50% probability level. Hydrogen atoms of the
phenyl substituents are omitted for clarity. Selected bond lengths
(Å) and angles (deg): Si(1)–C(1) 1.858(2), Si(1)–C(11) 1.873(2), Si(1)–
C(21) 1.872(2), Si(1)–C(27) 1.872(2), C(1)–C(2) 1.332(2), C(11)–C(12)
1.340(2), C(2)–Si(3) 1.854(2), C(12)–Si(2) 1.866(2), Si(2)–C(15)
1.905(2), Si(3)–C(5) 1.911(2); Si(1)–C(1)–C(2) 123.7(1), C(1)–C(2)–Si(3)
124.7(1), Si(1)–C(11)–C(12) 123.3(1), C(11)–C(12)–Si(2) 125.4(1), C(2)–
Si(3)–C(5) 108.3(1), C(12)–Si(2)–C(15) 107.9(1).
H
i)
SiX3
PhSi
PhSi
3
3
X = Cl
1
9
ii)
10 X = F
Scheme 3:ꢁSynthesis of the tridentate Lewis acids 9–10. Reagents
and conditions: i) HSiCl3 (neat), Karstedt’s catalyst, r.t., 1 h, 97%;
ii) SbF3, pentane, r.t., 25 h, 90%.
is accessible by conversion of 9 with SbF3 in pentane at
ambient temperature avoiding Si–C bond cleavage [43].
Single crystals of the tridentate silicon Lewis acids 9
and 10, suitable for X-ray diffraction experiments, were
grown from Et2O at room temperature; the molecular
structures in the solid state are shown in Figs. 5 and 6.
In contrast to 10, the solid state structure of 9 displays
a mirror plane through the phenyl substituent and the
vinylic sidearm Si(1)–C(3)–C(4)–Si(3). The C=C double
bonds of 9 and 10 are all of the same length within their
experimental errors [1.330(4) Å]. The C−Si bond lengths
Fig. 6:ꢁMolecular structure of tris(trifluorosilylvinyl)phenylsilane
(10) in the solid state. Displacement ellipsoids are drawn at the
50% probability level. Hydrogen atoms of the phenyl substitu-
ent are omitted for clarity. Selected bond lengths (Å) and angles
(deg): Si(1)–C(1) 1.862(3), Si(1)–C(7) 1.878(3), Si(1)–C(9) 1.873(3),
Si(1)–C(11) 1.868(3), C(7)–C(8) 1.330(4), C(9)–C(10) 1.324(4),
C(11)–C(12) 1.323(4), C(8)–Si(2) 1.817(3), C(10)–Si(3) 1.816(3),
C(12)–Si(4) 1.819(3), Si(2)–F(1) 1.566(2), Si(2)–F(2) 1.569(2),
Si(2)–F(3) 1.557(2), Si(4)–F(9) 1.551(2); Si(1)–C(7)–C(8) 124.6(2),
C(7)–C(8)–Si(2) 124.5(2), Si(1)–C(9)–C(10) 125.7(3), C(9)–C(10)–
Si(3) 123.8(3), Si(1)–C(11)–C(12) 123.7(2), C(11)–C(12)–Si(4)
124.6(2), F(1)–Si(2)–F(2) 105.4(2), F(5)–Si(3)–F(6) 103.3(2), F(7)–
to the trifluorosilyl groups [C(10)–Si(3) 1.816(3) Å to Si(4)–F(9) 108.5(2).
Brought to you by | Cornell University Library
Authenticated
Download Date | 7/3/17 10:07 AM

ꢂꢁꢁꢁ
J. Horstmann et al.: Bi- and tridentate silicon-based acceptor moleculesꢀ
ꢀ387
C(12)–Si(4) 1.819(3) Å] are slightly shorter than the cor-
responding ones to the trichlorosilyl groups [C(2)–Si(2)
4 Crystal structure determinations
1.840(3) Å and C(4)–Si(3) 1.844(4) Å]. This agrees well Suitable crystals of the compounds 1, 5, 6 and 7 were
with the increased Lewis acidity of 10. Due to the elec- obtained by evaporating saturated solutions of n-hex-
tron-withdrawing character of fluorine, the Si−Cl bond ane, 9 and 10 from Et2O solutions. They were coated with
lengths [Si(3)–Cl(4) 2.018(2) Å to Si(3)–Cl(5) 2.033(2) Å] paratone-N oil, selected, mounted on a glass fibre and
are remarkably longer than the Si−F bonds [Si(4)–F(9) transferred onto the goniometer and into the cryostream
1.551(2) Å to Si(2)–F(2) 1.569(2) Å].
of the diffractometer. Data collections were performed at
We tried to convert the air and moisture sensitive tri- 100.0(2) K on a SuperNova diffractometer, using mono-
dentate Lewis acids 9 and 10 with equimolar amounts of chromated Cu-Kα radiation for 1, 5, 6 and 10 and mono-
some neutral Lewis bases. Oxygen-containing Lewis bases chromatized Mo-Kα radiation for 7 and 9.
like diethyl ether, 1,4-dioxane, 1,3,5-trioxane and 1,3,5-tri-
Using Olex2, the structures were solved by Direct
methoxybenzene show no reaction, neither observed Methods and refined by full-matrix least-squares cycles
in NMR spectra nor by crystallisation. The absence of (program Shelx-97) [45, 46]. Crystal and refinement
an adduct formation is also obvious from the fact that details, as well as the CCDC numbers for each structure
donor-free crystals of 9 and 10 were grown from Et2O determination are provided in Table 1.
solutions. Nitrogen containing Lewis bases like pyridine,
CCDC 1531692-15316697 contain the supplementary
1,4-diazabicyclo[2.2.2]octane, TMEDA or 1,3,5-triazine led crystallographic data for this paper. These data can be
to the formation of colourless precipitates. These solid obtained free of charge from The Cambridge Crystallo-
compounds were insoluble in any common solvents. The graphic Data Centre via www.ccdc.ac.uk/data_request/cif.
conversion of 10 with pyridine gave crystals of tetrafluoro-
bispyridinesilicon(IV) after a week, indicating a decompo-
sition of the Lewis acid [44].
5 Experimental section
3 Conclusion
5.1 General
The triply unsaturated silicon-centred species triethynyl- All reactions using organometallic reagents were carried
phenylsilane (1) and trivinylphenylsilane (2) were synthe- out under an anhydrous, inert atmosphere of nitrogen or
sized via salt-elimination reactions. Compounds 1 and 2 argon using standard Schlenk and glovebox techniques.
and the bidentate analogues diethynyldiphenylsilane (3) THF (dried over potassium) and pentane (dried over
and divinyldiphenylsilane (4) were converted into the two- LiAlH4) were freshly distilled before use. Ethynylmagne-
and three-fold pentafluorophenyl substituted species sium bromide (0.5 m in THF) and vinylmagnesium chlo-
5–8 via hydrosilylation and salt elimination reactions. ride (1.9 m in THF) were purchased from Acros Organics.
These air stable bi- and tridentate Lewis acids show no Trichlorophenylsilane (from FLUKA), trichlorosilane
reaction to nitrogen and oxygen containing Lewis bases. (FLUKA) and chloro(dimethyl)silane (FLUKA) were con-
In the solid state, 5, 6 and 7 display dispersion-driven densed before use. Karstedt’s catalyst (from ABCR) and
intermolecular Ar···Arf interactions. 5 and 6 crystallize bromopentafluorobenzene (Fluorochem) were used
in strands with centroid(C6F5)···centroid(C6H5) distances without further purifications. The syntheses of diethy-
ranging from 3.817(5) to 4.893(6) Å, whereas the strands nyldiphenylsilane (3) and divinyldiphenylsilane (4) as
of 7 are crosslinked by C6H5···C6F5 distances of 3.685(1) well as the procedure of hydrosilylation are described
and 3.740(1) Å. However, no interactions of compounds elsewhere [38]. NMR spectra were recorded on a Bruker
5–8 with any electron rich aryl compounds could be DRX 500 and a Bruker Avance III 500 HD instrument. The
observed. The more Lewis-acidic tris(trifluorosilylvinyl) chemical shifts (δ) were measured in ppm with respect
1
phenylsilane (10) was synthesized by fluorination of the to the solvent (C6D6: H NMR, δꢀ=ꢀ7.16 ppm, 13C NMR,
tris(trichlorosilyl) compound 9, which was generated by δꢀ=ꢀ128.06 ppm) or referenced externally (29Si: SiMe4, 19F:
hydrosilylation of 1 with trichlorosilane. The conversion CFCl3). EI mass spectra were recorded using an Autospec
of 10 with nitrogen containing Lewis bases leads to insol- Xmagnetic sector mass spectrometer with EBE geometry
uble precipitates, whereas oxygen containing bases show (Vacuum Generators, Manchester, UK) equipped with
no interactions.
a standard EI source. Samples were introduced by push
Brought to you by | Cornell University Library
Authenticated
Download Date | 7/3/17 10:07 AM

ꢁꢁꢁꢂ
ꢀJ. Horstmann et al.: Bi- and tridentate silicon-based acceptor molecules
388ꢀ
Table 1:ꢁCrystallographic data for 1, 5, 6, 7, 9 and 10.
ꢁ
1
ꢁ
5
ꢁ
6
ꢁ
7
ꢁ
9
ꢁ
10
Empirical formula
Mr
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
C12H8Si
180.27
376
Monoclinic
Pc
12.3799(13)ꢃ
11.7758(6) ꢃ
7.3475(4)
96.593(8)
1064.06(14)ꢃ
4
1.13
1.5
133.0
−14ꢂ≤ꢂhꢂ≤ꢂ14 ꢃ
−14ꢂ≤ꢂkꢂ≤ꢂ14
−8ꢂ≤ꢂlꢂ≤ꢂ8
15 686
3587
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
C36H29F15Si4
858.95
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
C36H35F15Si4
865.00
5304
Monoclinic
P21
10.04213(9)ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
C32H26F10Si3
684.80
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
C12H11Cl9Si4
586.62
584
ꢃ
ꢃ
ꢃ
C12H11F9Si4
438.57
1760
Orthorhombic
Pbca
6.7112(2)
17.6920(6)
30.4841(10)
90
F(000), e
Crystal system
Space group
a, Å
1744
1400
Monoclinic
P21/c
10.7869(3)
18.5948(5)
19.3875(5)
100.516(2)
3823.41(17)ꢃ
4
1.49
2.4
144.0
−13ꢂ≤ꢂhꢂ≤ꢂ13 ꢃ
−22ꢂ≤ꢂkꢂ≤ꢂ21
−23ꢂ≤ꢂlꢂ≤ꢂ23
71 866
7514
0.0818
6182
502
Monoclinic
P21/n
9.3040(2)
17.7490(4)
19.8628(5)
101.787(3)
Orthorhombicꢃ
Pmn21
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
16.3606(4)
6.38123(13)
11.3405(2)
90
b, Å
55.8944(7)
21.0381(2)
93.3013(9)
11789.1(2)
12
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
c, Å
ꢃ
ꢃ
β, deg
V, Å3
3210.93(14)ꢃ
4
1183.95(4)
2
3619.5(2)
8
Z
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ρcalcd., gꢂcm−3
μ, mm−1
θmax, deg
Index ranges h, k, l
1.46
1.42
0.2
60.0
−13ꢂ≤ꢂhꢂ≤ꢂ13 ꢃ
−24ꢂ≤ꢂkꢂ≤ꢂ24
−27ꢂ≤ꢂlꢂ≤ꢂ27
53 339
9348
0.0486
7633
410
1.65
1.61
2.3
1.3
3.9
134.0
55.0
144.3
−11ꢂ≤ꢂhꢂ≤ꢂ11 ꢃ
−66ꢂ≤ꢂkꢂ≤ꢂ59
−25ꢂ≤ꢂlꢂ≤ꢂ25
−21ꢂ≤ꢂhꢂ≤ꢂ21
−8ꢂ≤ꢂkꢂ≤ꢂ8
−14ꢂ≤ꢂlꢂ≤ꢂ14
20 030
2801
−8ꢂ≤ꢂhꢂ≤ꢂ8
−21ꢂ≤ꢂkꢂ≤ꢂ21
−37ꢂ≤ꢂlꢂ≤ꢂ37
64 007
3566
Reflexes collected
Independent reflexes
Rint
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
17 8151
39 725
0.0628
37404
3010
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
0.0467
3335
235
0.0367
0.0970
0.0401
0.1005
1.038
0.0337
2742
124
0.1063
2994
227
Observed refl. (Iꢂ>ꢂ2 σ(I)) ꢃ
Parameters
R1, (Iꢂ>ꢂ2 σ(I))
wR2, (Iꢂ>ꢂ2 σ(I))
R1 (all data)
wR2 (all data)
GoF
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
0.0541
0.1493
0.0638
0.1583
1.062
0.0741
0.1966
0.0775
0.2006
1.030
0.0447
0.1194
0.0571
0.1299
1.053
0.0201
0.0510
0.0207
0.0514
1.049
0.33/−0.19
1531696
c)
0.0470
0.1115
0.0570
0.1183
1.045
0.49/−0.37
1531697
–
ρmax/ρmin, e Å−3
CCDC No.
0.37/−0.16 ꢃ
0.46/−0.84 ꢃ
1.80/−0.58 ꢃ
0.53/−0.34 ꢃ
1531692
ꢃ
ꢃ
1531693
ꢃ
ꢃ
1531694
ꢃ
ꢃ
1531695
ꢃ
ꢃ
Remarks
a)
–
b)
–
a) Flack parameter 0.05(3); b) merohedral twin (BASF 0.62); c) Flack parameter −0.02(3).
rod in aluminum crucibles. Ions were accelerated by 8 kV. 82.2 ppm. − 29Si{1H} NMR (99 MHz, C6D6): δꢀ=ꢀ−70.2 ppm. −
Elemental analyses were performed with CHNS elemental EI-MS (70 eV): m/zꢀ=ꢀ179.1, 154.1, 129.1, 103.0, 77.0. −
analyzer HEKAtech EURO EA.
Elemental analysis calcd. (%) for C12H8Si (Mrꢀ=ꢀ180.28):
C 79.95, H 4.47; found C 80.10, H 4.53.
5.2 Triethynylphenylsilane (1)
5.3 Trivinylphenylsilane (2)
Trichlorophenylsilane (4.0 mL, 25 mmol) was added
dropwise to a mixture of ethynylmagnesium bromide Trichlorophenylsilane (4.8 mL, 30 mmol) was added drop-
solution (160 mL, 80 mmol) in THF (50 mL) at 0°C. The wise to a mixture of vinylmagnesium chloride solution
mixture was warmed to ambient temperature, stirred for (50 mL, 95 mmol) with THF (100 mL) at ambient tempera-
14 h and all volatile compounds were removed in vacuo. ture and stirred for 16 h. Ice (50 g) was added and all vola-
The remaining brownish solid was washed with diethyl tile compounds were removed in vacuo. The remaining
ether (25 mL), the solvent was removed from the organic brownish solid was washed with DCM (60 mL), the solvent
filtrate and the colourless residue was purified by dis- was removed from the organic filtrate and the colourless
tillation (80°C, 10−2 mbar) to yield triethinylphenylsilane residue was purified by distillation (68°C, 3 mbar) to yield
as crystalline material. Yield: 3.6 g (20 mmol, 80%). trivinylphenylsilane as oily liquid. Yield: 4.1 g (22 mmol,
1
− H NMR (500 MHz, C6D6): δꢀ=ꢀ7.91 (m, 2H, o-PhH), 7.11 74%). − 1H NMR (500 MHz, CDCl3): δꢀ=ꢀ7.55 (m, 2H, o-PhH),
13
(m, 3H, m-/p-PhH), 1.99 (s, 3H, CH) ppm. − C{1H} NMR 7.39 (m, 3H, m-/p-PhH), 6.34 (dd, Jꢀ=ꢀ20.1, 14.6 Hz, 3H,
(125 MHz, C6D6): δꢀ=ꢀ134.7, 131.3, 130.3, 128.6, 97.3, α-H), 6.21 (dd, Jꢀ=ꢀ14.6, 4.0 Hz, 3H, β-Z-H), 5.83 (dd,
Brought to you by | Cornell University Library
Authenticated
Download Date | 7/3/17 10:07 AM

ꢂꢁꢁꢁ
J. Horstmann et al.: Bi- and tridentate silicon-based acceptor moleculesꢀ
ꢀ389
13
19
Jꢀ=ꢀ20.1, 4.0 Hz, 3H, β-E-H) ppm. − C{1H} NMR (125 MHz, −2.3 ppm. − F NMR (282 MHz, CDCl3): δꢀ=ꢀ−127.6 (dd, 6F,
CDCl3): δꢀ=ꢀ136.1, 135.2, 134.6, 133.9, 129.6, 128.0 ppm. Jꢀ=ꢀ25.0, 9.8 Hz), −151.7 (tt, 3F, Jꢀ=ꢀ20.4, 3.4 Hz), −161.2 (m,
29
−
29Si{1H} NMR (99 MHz, CDCl3): δꢀ=ꢀ−23.9 ppm. − EI-MS 6F) ppm. − Si{1H} NMR (99 MHz, CDCl3): δꢀ=ꢀ2.2 (SiMe2),
(70 eV): m/zꢀ=ꢀ186.1, 158.1, 107.1, 82.1, 67.0.
2.9 (PhSi) ppm. – EI-MS (70 eV): m/zꢀ=ꢀ864.2, 849.2, 787.2,
759.2, 685.2, 611.2, 461.1, 371.2, 309.1, 287.1, 249.1, 225.1,
187.1, 135.1, 121.1, 77.1.
5.4 all-trans-Tris[(pentafluorophenyldimethy-
lsilyl)vinyl]phenylsilane (5)
5.6 all-trans-Bis[(pentafluorophenyldimethy-
Magnesium turnings (120 mg, 5.1 mmol) and bromo-
pentafluorobenzene (0.60 mL, 4.8 mmol) were refluxed
lsilyl)vinyl]diphenylsilane (7)
in Et2O (20 mL) for 45 min. At ambient temperature, Magnesium turnings (90 mg, 3.8 mmol) and bromo-
tris(chlorodimethylsilylvinyl)phenylsilane (0.74 g, pentafluorobenzene (0.39 mL, 3.2 mmol) were refluxed
1.2 mmol), dissolved in THF (20 mL) was added and the in Et2O (5 mL) for 1 h. At ambient temperature,
mixture was refluxed for 2 h, quenched with sat. aqueous bis(chlorodimethylsilylvinyl)diphenylsilane (0.54 g,
NH4Cl solution (10 mL) and extracted with n-hexane 1.3 mmol), dissolved in THF (5 mL), was added and the
(20 mL). All volatiles of the combined organic phases mixture was refluxed for 1 h, quenched with sat. aqueous
were removed in vacuo. Recrystallisation (n-hexane) NH4Cl solution (5 mL) and extracted with n-hexane
afforded
tris[(pentafluorophenyldimethylsilyl)vinyl] (10 mL). All volatiles of the combined organic phases were
phenylsilane as crystalline solid. Yield: 0.95 g (1.1 mmol, removed in vacuo. Crystallisation from n-hexane afforded
92%). − 1H NMR (500 MHz, CDCl3): δꢀ=ꢀ7.47 (m, 2H, o-PhH), bis[(pentafluorophenyldimethylsilyl)vinyl]diphenylsilane
7.40 (m, 3H, m-/p-PhH), 6.86 (s, 6H, PhSiCHCH), 0.51 (s, as crystalline brownish solid. Yield: 0.72 g (1.1 mmol, 85%).
13
1
18H, CH3) ppm. − C{1H} NMR (125 MHz, CDCl3): δꢀ=ꢀ152.2, − H NMR (500 MHz, CDCl3): δꢀ=ꢀ7.49 (m, 4H, o-PhH), 7.40
149.0, 146.4, 142.4, 137.5, 135.3, 133.6, 129.9, 128.2, −1.9 ppm. (m, 6H, m-/p-PhH), 7.04 (d, Jꢀ=ꢀ22.5 Hz, 2H, Ph2SiCH), 6.89
−
19F NMR (282 MHz, CDCl3): δꢀ=ꢀ−126.4 (dd, 6F, Jꢀ=ꢀ24.6, (d, Jꢀ=ꢀ22.5 Hz, 2H, Ph2SiCHCH), 0.51 (s, 12H, CH3) ppm. −
10.6 Hz), −151.5 (tt, 3F, Jꢀ=ꢀ20.0, 3.4 Hz), −161.3 (m, 6F) ppm. 13C{1H} NMR (125 MHz, CDCl3): δꢀ=ꢀ152.3, 149.1, 146.8, 142.2,
19
−
29Si{1H} NMR (99 MHz, CDCl3): δꢀ=ꢀ−26.7 (PhSi), −11.2 137.4, 135.7, 133.7, 129.9, 128.2, 109.6, −1.8 ppm. − F NMR
(SiMe2) ppm. − EI-MS (70 eV): m/zꢀ=ꢀ858.2, 843.2, 633.2, (282 MHz, CDCl3): δꢀ=ꢀ−127.1 (dd, 4F, Jꢀ=ꢀ24.9, 10.3 Hz), −151.6
607.2, 523.1, 472.1, 371.1, 309.1, 225.1, 145.1, 139.1, 135.1, (tt, 2F, Jꢀ=ꢀ20.5, 3.5 Hz), −161.3 (m, 4F) ppm. − 29Si{1H} NMR
+
125.1, 77.1. − HRMS (EI, 70 eV): Calcd. for C36H29F15Si4Na : (99 MHz, CDCl3): δꢀ=ꢀ−22.2 (Ph2Si), −10.7 (SiMe2) ppm. −
881.09990; found 881.10229; deviation [ppm]: 2.71, devia- EI-MS (70 eV): m/zꢀ=ꢀ684.2, 607.2, 534.1, 433.2, 349.1, 207.1,
tion [mmu]: 2.39.
201.1, 197.1, 183.1, 135.1, 105.1, 77.1.
5.5 Tris[(pentafluorophenyldimethylsilyl)-
ethyl]phenylsilane (6)
5.7 Bis[(pentafluorophenyldimethylsilyl)-
ethyl]diphenylsilane (8)
Magnesium turnings (75 mg, 3.1 mmol) and bromopen- Magnesium turnings (30 mg, 3.8 mmol) and bromo-
tafluorobenzene (0.25 mL, 2.0 mmol) were refluxed in pentafluorobenzene (0.15 mL, 1.2 mmol) were refluxed
Et2O (13 mL) for 2 h. At 0°C, tris(chlorodimethylsilylethyl) in Et2O (10 mL) for 2 h. At ambient temperature,
phenylsilane (0.24 g, 0.5 mmol), dissolved in THF (13 mL), bis(chlorodimethylsilylethyl)diphenylsilane
(0.17
g,
was added and the mixture was warmed to ambient tem- 0.40 mmol), dissolved in THF (10 mL), was added and the
perature, quenched with sat. aqueous NH4Cl solution mixture was refluxed for 1 h. The mixture was quenched
(5 mL) and extracted with DCM (10 mL). All volatiles of the with sat. aqueous NH4Cl solution (5 mL) and extracted with
combined organic phases were removed in vacuo. Recrys- n-hexane (20 mL). All volatiles of the combined organic
tallisation (n-hexane) afforded tris[(pentafluorophenyldi- phases were removed in vacuo affording bis[(pentafluo-
methylsilyl)ethyl]phenylsilane as crystalline solid. Yield: rophenyldimethylsilyl)vinyl]diphenylsilane as brownish
1
1
0.39 g (0.45 mmol, 90%). − H NMR (500 MHz, CDCl3): oil. Yield: 0.25 g (0.36 mmol, 90%). − H NMR (500 MHz,
δꢀ=ꢀ7.36 (m, 5H, o-/m-/p-PhH), 0.72 (s, 12H, PhSiCH2CH2), CDCl3): δꢀ=ꢀ7.45 (m, 4H, o-PhH), 7.37 (m, 6H, m-/p-PhH), 1.02
0.39 (s, 18H, CH3) ppm. − 13C{1H} NMR (125 MHz, CDCl3): δꢀ=ꢀ (m, 4H, Ph2SiCH2), 0.80 (m, 4H, Ph2SiCH2CH2), 0.40 (s, 12H,
149.1, 142.0, 137.3, 135.9, 134.2, 129.4, 128.0, 109.9, 8.3, 3.1, CH3) ppm. − 13C{1H} NMR (125 MHz, CDCl3): δꢀ=ꢀ149.2, 142.1,
Brought to you by | Cornell University Library
Authenticated
Download Date | 7/3/17 10:07 AM

ꢁꢁꢁꢂ
390ꢀ ꢀJ. Horstmann et al.: Bi- and tridentate silicon-based acceptor molecules
137.3, 135.4, 135.0, 129.5, 128.1, 110.0, 8.3, 3.9, −2.2 ppm.
References
−
19F NMR (282 MHz, CDCl3): δꢀ=ꢀ−127.5 (dd, 4F, Jꢀ=ꢀ25.0,
9.9 Hz), −151.8 (tt, 2F, Jꢀ=ꢀ20.5, 3.4 Hz), −161.2 (m, 4F) ppm.
− 29Si{1H} NMR (99 MHz, CDCl3): δꢀ=ꢀ−3.9 (Ph2Si), 2.1 (SiMe2)
ppm. − EI-MS (70 eV): m/zꢀ=ꢀ688.2, 673.2, 662.5, 647.5, 587.2,
583.2, 509.2, 435.2, 287.2, 253.1, 201.1, 183.1, 147.1, 105.1, 77.1.
[1] B. Dietrich, Pure Appl. Chem. 1993, 65, 1457.
[2] F. P. Schmidtchen, M. Berger, Chem. Rev. 1997, 97, 1609.
[3] P. D. Beer, D. K. Smith, Prog. Inorg. Chem. 1997, 46, 1.
[4] M. M. G. Antonisse, D. N. Reinhoudt, Chem. Commun. 1998, 4,
443.
[5] P. D. Beer, Acc. Chem. Res. 1998, 31, 71.
[6] P. D. Beer, P. A. Gale, Angew. Chem. Int. Ed. 2001, 32, 486.
[7] J. W. Steed, Chem. Soc. Rev. 2009, 38, 506.
[8] D. F. Shriver, M. J. Biallas, J. Am. Chem. Soc. 1967, 89, 1078.
[9] R. Altmann, K. Jurkschat, M. Schürmann, D. Dakternieks,
A. Duthie, Organometallics 1998, 17, 5858.
5.8 all-trans-Tris[(trichlorosilyl)vinyl]phenyl-
silane (9)
Triethynylphenylsilane (64 mg, 0.36 mmol) was dis-
solved in trichlorosilane (0.5 mL, 5.0 mmol), one drop of
Karstedt’s catalyst (1 m in xylene) was added at ambient
[10] K. Tamao, T. Hayashi, Y. Ito, M. Shiro, J. Am. Chem. Soc. 1990,
112, 2422.
[11] M. Layh, W. Uhl, Polyhedron 1990, 9, 277.
temperature and the pale yellow mixture was stirred for [12] W. Uhl, M. Matar, J. Organomet. Chem. 2002, 664, 110.
[13] W. Uhl, A. Hepp, H. Westenberg, S. Zemke, E.-U. Würthwein,
1 h. Removing of all volatiles afforded tris[(trichlorosilyl)-
vinyl]phenylsilane as a colourless solid. Yield: 205 mg
J. Hellmann, Organometallics 2010, 29, 1406.
[14] W. Uhl, J. Bohnemann, D. Heller, A. Hepp, M. Layh, Z. Anorg.
(0.35 mmol, 97%). − 1H NMR (500 MHz, CDCl3): δꢀ=ꢀ7.50 (m,
Allg. Chem. 2012, 638, 68.
5H, o-/m-/p-PhH), 7.30 (d, Jꢀ=ꢀ22.0 Hz, 3H, PhSiCH), 6.69 (d,
Jꢀ=ꢀ22.0 Hz, 3H, PhSiCHCH) ppm. − 13C{1H} NMR (125 MHz,
CDCl3): δꢀ=ꢀ150.3, 146.3, 135.40, 131.5, 129.0, 128.6 ppm.
[15] W. Uhl, H. R. Bock, F. Breher, M. Claesener, S. Haddadpour,
B. Jasper, A. Hepp, Organometallics 2007, 26, 2363.
[16] W. Uhl, M. Claesener, A. Hepp, Organometallics 2008, 27, 2118.
[17] W. Uhl, D. Kovert, S. Zemke, A. Hepp, Organometallics 2011,
30, 4736.
−
29Si{1H} NMR (99 MHz, CDCl3): δꢀ=ꢀ−24.4 (PhSi), −6.4
(SiCl3) ppm. − Elemental analysis calcd. (%) for C12H11Cl9Si4
(Mrꢀ=ꢀ586.63): C 24.57, H 1.89; found C 24.87, H 1.97.
[18] P. Jutzi, J. Izundu, H. Sielemann, B. Neumann, H.-G. Stammler,
Organometallics 2009, 28, 2619.
[19] M. Tschinkl, A. Schier, J. Riede, F. P. Gabbaï, Inorg. Chem. 1997,
36, 5706.
[20] F. P. Gabbaï, A. Schier, J. Riede, D. Schichl, Organometallics
1996, 15, 4119.
[21] J. D. Beckwith, M. Tschinkl, A. Picot, M. Tsunoda, R. Bachman,
F. P. Gabbaï, Organometallics 2001, 20, 3169.
[22] M. Melaimi, F. P. Gabbaï, Z. Anorg. Allg. Chem. 2012, 638, 1667.
[23] K. Jurkschat, H. G. Kuivila, S. Liu, J. A. Zubieta, Organometallics
1989, 8, 2755.
[24] M. Schulte, G. Gabriele, M. Schürmann, K. Jurkschat, A. Duthie,
D. Dakternieks, Organometallics 2003, 22, 328.
[25] M. Schulte, M. Schürmann, K. Jurkschat, Chem. Eur. J. 2001, 7,
347.
[26] M. E. Jung, H. Xia, Tetrahedron Lett. 1988, 29, 297.
[27] D. Brondani, F. H. Carré, R. J. P. Corriu, J. J. E. Moreau, M. Wong
Chi Man, Angew. Chem. Int. Ed. Engl. 1996, 35, 324.
[28] J. Chmiel, B. Neumann, H.-G. Stammler, N. W. Mitzel, Chem.
Eur. J. 2010, 16, 11906.
[29] J.-H. Lamm, P. Niermeier, A. Mix, J. Chmiel, B. Neumann,
H.-G. Stammler, N. W. Mitzel, Angew. Chem. Int. Ed. 2014, 53,
7938.
[30] J.-H. Lamm, J. Horstmann, J. H. Nissen, J.-H. Weddeling,
B. Neumann, H.-G. Stammler, N. W. Mitzel, Eur. J. Inorg. Chem.
2014, 4294.
5.9 all-trans-Tris[(trifluorosilyl)vinyl]phenyl-
silane (10)
Tris[(trichlorosilyl)vinyl]phenylsilane (60 mg, 0.10 mmol)
and antimony trifluoride (210 mg, 1.2 mmol) were dis-
solved in pentane (2 mL) and stirred for 25 h at ambient
temperature. Filtration, removing all volatiles from the fil-
trate and removing of antimony trichloride by sublimation
(50°C, 10−2 mbar) afforded tris[(trifluorosilyl)vinyl]phenyl-
silane as a colourless solid. Yield: 40 mg (91 μmol, 90%).
− 1H NMR (500 MHz, CDCl3): δꢀ=ꢀ7.48 (m, 5H, o-/m-/p-PhH),
7.47 (d, Jꢀ=ꢀ23.1 Hz, 3H, PhSiCH), 6.45 (dq, Jꢀ=ꢀ23.1, 3.3 Hz,
3H, PhSiCHCH) ppm. − 13C{1H} NMR (125 MHz, CDCl3):
δꢀ=ꢀ156.2, 135.8 (q, Jꢀ=ꢀ25.6 Hz), 135.3, 131.6, 131.5, 129.1 ppm.
− 19F NMR (470 MHz, CDCl3): δꢀ=ꢀ−141.3 (d, Jꢀ=ꢀ3.3 Hz) ppm.
29
− Si{1H} NMR (99 MHz, CDCl3): δꢀ=ꢀ−24.2 (PhSi), −78.7 (q,
Jꢀ=ꢀ268.4 Hz, SiF3) ppm.
Acknowledgments: The authors thank Klaus-Peter Mester
for recording NMR spectra, Brigitte Michel for performing
CHN analyses and Heinz-Werner Patruck for measuring
mass spectra. We gratefully acknowledge financial sup-
port from Deutsche Forschungsgemeinschaft DFG, grant
MI-477/28-1 in the SPP 1807 “Control of London dispersion
interactions in molecular chemistry”.
[31] E. Weisheim, C. G. Reuter, P. Heinrichs, Yu. V. Vishnevskiy,
A. Mix, B. Neumann, H.-G. Stammler, N. W. Mitzel, Chem. Eur. J.
2015, 21, 12436.
[32] E. Weisheim, A. Schwartzen, L. Kuhlmann, B. Neumann,
H.-G. Stammler, N. W. Mitzel, Eur. J. Inorg. Chem. 2016, 1257.
[33] E. Weisheim, L. Büker, B. Neumann, H.-G. Stammler, N. W.
Mitzel, Dalton Trans. 2016, 45, 198.
Brought to you by | Cornell University Library
Authenticated
Download Date | 7/3/17 10:07 AM

ꢂꢁꢁꢁ
J. Horstmann et al.: Bi- and tridentate silicon-based acceptor moleculesꢀ
ꢀ391
[34] J. Tomaschautzky, B. Neumann, H.-G. Stammler, A. Mix,
N. W. Mitzel, Dalton Trans. 2017, 46, 1645.
[40] A. D. Dilman, D. E. Arkhipov, A. A. Korlyukov, V. P. Ananikov,
V. M. Danilenko, V. A. Tartakovsky, J. Organomet. Chem. 2005,
690, 3680.
[41] A. S. Batsanov, J. A. K. Howard, T. B. Marder, E. G. Robins, Acta
Crystallogr. 2001, C57, 1303.
[42] M. W. Day, A. J. Matzger, R. H. Grubbs, Exp. Cryst. Structure Det.
1999, CCDC 136214.
[43] N. W. Mitzel, K. Vojinović, T. Foerster, H. E. Robertson,
K. B. Borisenko, D. W. H. Rankin, Chem. Eur. J. 2005, 11, 5114.
[44] V. A. Bain, R. C. G. Killean, M. Webster, Acta Crystallogr. 1969,
B25, 156.
[35] J. Tomaschautzky, B. Neumann, H.-G. Stammler, A. Mix,
N. W. Mitzel, Dalton Trans. 2017, 46, 1112.
[36] U. H. Strasser, B. Neumann, H.-G. Stammler, R. J. F. Berger,
N. W. Mitzel Z. Naturforsch. 2014, 69b, 1061.
[37] E. Weisheim, B. Neumann, H.-G. Stammler, N. W. Mitzel,
Z. Anorg. Allg. Chem. 2016, 642, 329.
[38] J. Horstmann, M. Niemann, K. Berthold, A. Mix,
B. Neumann, H.-G. Stammler, N. W. Mitzel, Dalton Trans.
2017, 46, 1898.
[39] J. Horstmann, M. Hyseni, A. Mix, B. Neumann, H.-G. Stammler,
N. W. Mitzel, Angew. Chem. Int. Ed. Engl. 2017, accepted.
doi: 10.1002/anie.201701303.
[45] G. M. Sheldrick, Acta Crystallogr. 2008, A64, 112.
[46] O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard,
H. Puschmann, J. Appl. Crystallogr. 2009, 42, 339.
Brought to you by | Cornell University Library
Authenticated
Download Date | 7/3/17 10:07 AM