Controlled Synthesis and Molecular Structures of Methoxy-, Amino-, and Chloro-Functionalized Disiloxane Building Blocks

Article abstract of DOI:10.1002/zaac.202000049

Functionalized disiloxane units with defined structures are interesting molecular models for investigating the reactivity and chemoselectivity in transformations that are of interest in synthesis, surface chemistry, and materials science. (Mes)PhSi(OMe)

Full text of DOI:10.1002/zaac.202000049

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.202000049
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Controlled Synthesis and Molecular Structures of Methoxy-,
Amino-, and Chloro-Functionalized Disiloxane Building Blocks
Noel Angel Espinosa-Jalapa[a] and Jonathan O. Bauer*[a]
Dedicated to Professor Manfred Scheer on the Occasion of his 65th Birthday
Abstract. Functionalized disiloxane units with defined structures are (Mes)PhSi(OMe)(OSiPh3) (3) were followed, one via the aminometh-
interestingmolecular models for investigating the reactivity and
chemoselectivity in transformations that are of interest in synthesis,
oxysilane (Mes)PhSi(OMe)(NC4H8) (2) and the other via the chlorodi-
siloxane (Mes)PhSiCl(OSiPh3) (6). The amino-substituted disiloxane
surface chemistry, and materials science. (Mes)PhSi(OMe)2 (1) (Mes)PhSi(NC4H8)(OSiPh3) (4) was obtained from the chloro deriva-
(Mes = mesityl) and (Mes)PhSiCl2 (5) were chosen as starting com- tive 6 with N-pyrrolidinyllithium, but the same reaction starting from
pounds for the controlled synthesis of methoxy-, amino-, and chloro- compound 3 was not successful. All provided disiloxanes were struc-
functionalized unsymmetric disiloxanes. Two synthesis routes towards
turally characterized by X-ray crystallography.
Functionalized disiloxanes in particular have interesting
properties and are a valuable class of compounds because they
represent the smallest structural segment of more complex si-
loxane networks and surfaces, and are therefore ideal candi-
dates for model studies.[12] Unsymmetrically substituted func-
tional disiloxanes are synthetically challenging. The introduc-
tion of a triphenylsilyl group enables the study of functional
group reactivity on only one silicon atom. Another advantage
of Ph3E units (E = group 14 element) is that the crystallization
tendency of molecules, which are otherwise difficult to crys-
tallize, can be increased significantly.[13] This allows studying
the effects of functional groups directly attached to a silicon
atom on structural parameters of the siloxane bond in the mo-
lecular crystalline material.
Herein, we set out to investigate synthetic paths towards
the racemic triphenylsilyl-substituted methoxy-, amino-, and
chloro-functionalized disiloxanes 3, 4, and 6 (Scheme 1),
which are reactive building blocks for targeted further transfor-
mations depending on the chemical purpose. The molecular
structures of all disiloxanes were elucidated by single-crystal
X-ray diffraction analysis.
Introduction
The siloxane bond (Si–O–Si) is a ubiquitous structural mo-
tive in nature and in our daily live.[1] It is the basis for silicate
minerals,[2] used by marine organisms for building skeletons,[3]
and has broad technical applications as inorganic-organic hy-
brid polymers (silicones) and in materials science.[4] Smaller
siloxane units with defined structures are interesting molecular
models for mimicking complex silicate materials in nature and
in technical processes.[5]
The development of preparative methods for providing func-
tionalized siloxane units is of great interest.[6] Organoalkoxy-
siloxanes turned out to be important building blocks for the
controlled construction of siloxane-based materials with pre-
cisely defined structures and functionalities, and some impres-
sive contributions to their synthesis have been discovered re-
cently.[7] Even an asymmetric approach to enantiomerically
pure silicon-stereogenic alkoxysiloxanes using aminometh-
oxysilanes, a synthetically valuable class of reagents,[8] has
been reported previously.[9] The design of complex siloxane-
based structures with a high degree of functionality generally
requires an easy and targeted transformation of functional
groups without attacking the siloxane framework.[10] In ad-
dition to alkoxysilanes that are sometimes quite inert com-
pounds, amino- and chlorosilanes play an important role as
precursors for synthetic purposes.[11]
Results and Discussion
Mesityl(dimethoxy)phenylsilane (1), synthesized from mes-
ityltrimethoxysilane via methoxy/phenyl exchange, was cho-
sen as suitable starting compound, since the steric requirement
of the mesityl group guaranteed a high degree of chemoselec-
tivity over several nucleophilic substitution steps (Scheme 1).
In the first step, reaction of dimethoxysilane 1 with N-pyrrolid-
inyllithium in hexane at reflux resulted in the formation of the
mixed-functionalized aminomethoxysilane 2 in 83% isolated
yield. This type of reaction has been studied in detail and pro-
vides synthetically useful intermediates for subsequent chemo-
selective transformations because of the presence of two reac-
* Dr. J. O. Bauer
E-Mail: jonathan.bauer@ur.de
[a] Institut für Anorganische Chemie
Fakultät für Chemie und Pharmazie
Universität Regensburg
Universitätsstraße 31
93053 Regensburg, Germany
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH &
Co. KGaA. · This is an open access article under the terms of the
Creative Commons Attribution-NonCommercial-NoDerivs Li-
cense, which permits use and distribution in any medium, provided
the original work is properly cited, the use is non-commercial and
no modifications or adaptations are made.
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Scheme 1. Functionalization paths starting from mesityl(dimethoxy)phenylsilane (1) towards the racemic methoxy-, amino-, and chlorodisilox-
anes 3, 4, and 6.
tive functionalities within the same molecule that behave dif- which range around two separate areas with extreme values
ferently in chemical reactions with different nucleo- of 145.1(2)° and 169.5(2)°,[16] whereas hexaphenyldisiloxane
philes.[8,9,14] When the reaction was carried out at room tem- exhibits a linear Si–O–Si bond.[17]
perature, compound 2 was formed with a conversion of only
38% after 20 h. The reduced reactivity can be explained by
the increased steric shielding by the mesityl group, since the
same reaction under same conditions using dimethoxydiphen-
ylsilane leads to full conversion.[8] Heating a solution of
(Mes)PhSi(OMe)(NC4H8) (2) and triphenylsilanol in toluene
at reflux for 15
h led to chemoselective substitution
of the amino group and gave the methoxydisiloxane
(Mes)PhSi(OMe)(OSiPh3) (3) in good yield (79%) (Path a,
Scheme 1). However, no conversion was observed when per-
forming the reaction at room temperature. This model reaction
with a racemic and sterically demanding aminomethoxysilane
provides important information that can be transferred to pos-
sible stereospecific reactions with optically enriched starting
compounds, since it is known that the Si–N bond is stereo-
specifically cleaved when hydroxy-containing compounds at-
tack a stereogenic silicon center.[9,15]
Compound 3 crystallized from a tetrahydrofuran solution
layered with pentane at –30 °C in the monoclinic crystal sys-
tem, space group P21/n, as colorless blocks suitable for single-
crystal X-ray diffraction analysis (Figure 1). The methoxy-sub-
stituted silicon atom in the mesitylmethoxydisiloxane 3 differs
only marginally from an ideal tetrahedral coordination with
angles ranging from 107.29(9)° [O(2)–Si(1)–C(10)] to
110.91(9)° [C(10)–Si(1)–C(1)]. The Si(1)–O(2)–Si(2) bond an-
gle of 147.37(8)° is slightly smaller than the respective angle
Figure 1. Molecular structure of compound 3 in the crystal. Selected
bond lengths /Å and angles /°: C(1)–Si(1) 1.868(2), C(10)–Si(1)
1.851(2), C(16)–O(1) 1.383(2), C(17)–Si(2) 1.864(2), C(23)–Si(2)
1.858(2), C(29)–Si(2) 1.8572(19), O(1)–Si(1) 1.6148(13), O(2)–Si(1)
1.6218(13), O(2)–Si(2) 1.6247(13), C(16)–O(1)–Si(1) 131.11(14),
Si(1)–O(2)–Si(2) 147.37(8), O(1)–Si(1)–O(2) 107.85(8), O(1)–Si(1)–
C(10) 110.32(8), O(2)–Si(1)–C(10) 107.29(9), O(1)–Si(1)–C(1)
110.73(9), O(2)–Si(1)–C(1) 109.63(8), C(10)–Si(1)–C(1) 110.91(9).
The search for new reagents for mild surface modifications
of the previously described methoxypentaphenyldisiloxane is a worthwhile goal.[18] In this context, aminosilanes can be
[150.72(9)°],[8] but differs significantly from the Si–O–Si an- regarded as an atom-economic class of silylation reagents and
gle in the naphthylmethoxydisiloxane [164.97(9)°].[9] These si- have a number of advantages over chlorosilanes and alkoxy-
loxane bond angles are in good agreement with the angles silanes in terms of surface functionalization; mild and additive-
found in the molecular structures of Ph2Si(OH)(OSiPh3), free reaction conditions, formation of easy-to-separate by-
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products and slow surface reactions allow for controlled mono- tural parameters may indicate hyperconjugative delocalization
functionalization.[19] We therefore attempted to convert me- of oxygen lone electron pairs into adjacent antibonding orbit-
thoxydisiloxane 3 to the N-pyrrolidinyl-substituted derivative als.[20] However, the Cl–Si(1) bond length [2.0847(6) Å] is in
(Mes)PhSi(NC4H8)(OSiPh3) (4) to provide access to another the typical range for triaryl- and alkyl/aryl-substituted
synthetically useful class of siloxane building blocks. How- chlorosilanes and shows no noticeable elongation in the crys-
ever, direct substitution of the silicon-bound methoxy group talline molecular structure.[21] Instead, the C(10)–Si(1) bond
by N-pyrrolidinyllithium was unsuccessful even under toluene of 1.8726(16) Å is remarkably longer than the respective bond
reflux over a period of 20 hours, presumably due to the in- in disiloxane 3 [1.851(2) Å].
creased steric bulkiness around the silicon atom. Based on this
Chlorodisiloxane 6 opens access to both the amino (4) and
finding, we modified our approach to compound 4 and exam- the methoxy derivative (3) (Scheme 1). Heating a solution of
ined a synthetic route via chlorosilanes (Scheme 1), also start- compound 6 with N-pyrrolidinyllithium at hexane reflux gave
ing from (Mes)PhSi(OMe)2 (1). Compound 1 was readily chemoselectively (Mes)PhSi(NC4H8)(OSiPh3) (4) in 72%
chlorinated using excess thionyl chloride and catalytic amounts yield after 15 h, whereas methanolysis of 6 in the presence of
of pyridine hydrochloride and led to dichlorosilane 5 in 68% triethylamine at room temperature smoothly led to methoxydi-
yield. The applicability of this reaction was impressively dem- siloxane 3 in 65% yield (Path b, Scheme 1).
onstrated by Muzavarov and Rebrov for the stepwise construc-
N-Pyrrolidinyldisiloxane 4 crystallized from hot hexane in
tion of organopolysiloxane dendrimers.[10] Next, the Si–O–Si the triclinic crystal system, space group P1, as colorless plates
backbone was built up by straightforward monosubstitution re- suitable for single-crystal X-ray diffraction analysis (Figure 3).
action of compound 5 with lithium triphenylsiloxide in tetra- The silicon atom Si1 of aminodisiloxane 4 shows a slightly
hydrofuran at room temperature, with the chlorodisiloxane 6 distorted tetrahedral coordination ranging from 106.49(7)°
¯
being formed in very good isolated yield (92%).
[O–Si(1)–C(1)] to 111.89(7)° [N–Si(1)–C(10)], which is com-
(Mes)PhSiCl(OSiPh3) (6) crystallized from
a
tetra- parable to compounds 3 and 6. The Si(2)–O–Si(1) bond angle
hydrofuran solution layered with pentane at –30 °C in the tri- of 148.62(8)° lies between the angles of the other two mesityl-
¯
clinic crystal system, space group P1, as colorless blocks suit- disiloxanes. The almost ideal planar geometry around the ni-
able for single-crystal X-ray diffraction analysis (Figure 2). trogen atom [sum of angles: 359.9(4)°] is possibly the result
The angles around the Si1 atom in the chlorodisiloxane 6 range of a pronounced lone-pair electron density transfer from the
from 106.76(5)° [O–Si(1)–Cl] to 114.25(7)° [C(1)–Si(1)– nitrogen atom towards the N–Si bond, which leads to a short
C(10)] and thus deviate more from the ideal tetrahedral angle N–Si(1) bond length of 1.7127(14) Å.[22] This might also be
than in the methoxy derivative. The Si(1)–O–Si(2) bond angle the reason for a slight increase of the O–Si(1) bond length
[153.60(8)°] is larger than in compound 3 as well as in com- [1.6324(12) Å] compared with the respective bond in the mo-
pound 4 (see below). Also noticeable in disiloxane 6 is the lecular structures of disiloxanes 3 and 6.
significantly shorter O–Si(1) bond length of 1.6109(12) Å
compared to the O–Si(2) bond [1.6390(12) Å]. These struc-
Figure 3. Molecular structure of compound 4 in the crystal. Selected
bond lengths /Å and angles /°: C(1)–Si(1) 1.8864(17), C(10)–Si(1)
Figure 2. Molecular structure of compound 6 in the crystal. Selected
1.8657(17), C(20)–Si(2) 1.8699(17), C(26)–Si(2) 1.8692(17), C(32)–
bond lengths /Å and angles /°: C(1)–Si(1) 1.8677(17), C(10)–Si(1) Si(2) 1.8661(16), N–Si(1) 1.7127(14), O–Si(1) 1.6324(12), O–Si(2)
1.8726(16), C(16)–Si(2) 1.8638(16), C(22)–Si(2) 1.8669(16), C(28)–
Si(2) 1.8646(16), Cl–Si(1) 2.0847(6), O–Si(1) 1.6109(12), O–Si(2)
1.6390(12), Si(1)–O–Si(2) 153.60(8), O–Si(1)–C(1) 112.31(7), O–
Si(1)–C(10) 106.78(6), C(1)–Si(1)–C(10) 114.25(7), O–Si(1)–Cl
106.76(5), C(1)–Si(1)–Cl 108.09(5), C(10)–Si(1)–Cl 108.33(6).
1.6258(12), C(16)–N–C(19) 110.17(14), C(16)–N–Si(1) 129.80(12),
C(19)–N–Si(1) 119.97(12), Si(2)–O–Si(1) 148.62(8), O–Si(1)–N
107.03(7), O–Si(1)–C(10) 109.70(7), N–Si(1)–C(10) 111.89(7), O–
Si(1)–C(1) 106.49(7), N–Si(1)–C(1) 111.11(7), C(10)–Si(1)–C(1)
110.42(7).
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crystal structure of 3 was solved with SHELXS-97 and the crystal
Conclusions
structures of 4 and 6 were solved with SHELXT 2018/2 using
Olex2.[26–29] All crystal structures were refined based on F2 with the
In summary, we presented the synthesis and molecular struc-
tures of three unsymmetrically substituted new disiloxanes full-matrix least-squares method (SHELXL-2018/3)[27,30,31] using the
SHELX program package as implemented in WinGX.[32] A multi-scan
equipped with Si–O (3), Si–N (4), and Si–Cl (6) functions,
absorption correction using spherical harmonics as implemented in
respectively. They are model systems to further investigate
SCALE3 ABSPACK was employed. The non-hydrogen atoms were
their suitability as building blocks for the targeted design of
refined using anisotropic displacement parameters. All hydrogen atoms
more complex functional siloxane frameworks. The reactivity
were placed in idealized geometric positions and each was assigned a
and chemoselectivity studies on racemic precursors used in this
fixed isotropic displacement parameter based on a riding-model with
work provide valuable information that are also of interest for
future studies on stereospecific transformations using enantio-
Uiso(H) = 1.2Ueq(C) for the methylene (CH2) and aromatic (CH)
hydrogen atoms and Uiso(H) = 1.5Ueq(C) for the methyl (CH3)
merically enriched functionalized silanes. Furthermore, crys-
tallographic data for small disiloxane units in which only one
hydrogen atoms. The C–H distances constrained to 0.98 Å for the
methyl groups, to 0.97 Å for the methylene groups, and to 0.95 Å (3)
silicon atom is bound to another heteroatom are scarce but and 0.93 Å (4, 6) for the aryl groups. Figure 1, Figure 2, and Figure 3
were created using Mercury 4.1.0.[33]
interestingmolecular models to study influences on structural
parameters of the Si–O–Si backbone. The Si–O–Si bond angle
Crystallographic data (excluding structure factors) for the structures in
can differ considerably when compared with related molecules,
this paper have been deposited with the Cambridge Crystallographic
which results from the interplay between steric and electronic
effects.
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting
the depository numbers CCDC-1981219 (3), CCDC-1981220 (6),
and CCDC-1981221 (4) (Fax: +44-1223-336-033; E-Mail:
deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk)
Experimental Section
General Remarks: All experiments were performed in an inert atmo-
Crystal Data and Structure Refinement of 3: Colorless blocks,
sphere of purified nitrogen by using standard Schlenk techniques or
an MBraun Unilab 1200/780 glovebox. Glassware was heated at
140 °C prior to use. Diethyl ether, hexane, pentane, tetrahydrofuran,
and toluene were dried and degassed with a MBraun SP800 solvent
0.30ϫ0.20ϫ0.20 mm3, C34H34O2Si2, Mr = 530.79 g·mol–1, mono-
clinic, space group (Nr.) P21/n (14), a = 7.8554(4) Å, b = 18.7946(12)
Å, c = 19.8423(12) Å, β = 90.926(5)°, V = 2929.1(3) Å3, Z = 4, ρ =
1.204 g·cm–3, μ = 0.150 mm–1. 21716 reflections collected with Θ in
purification system. 2-Bromomesitylene (98%, Sigma–Aldrich), n-
the range 2.322 – 24.997°, index ranges –9 Յ h Յ 9, –21 Յ k Յ
butyllithium (2.5 m solution in hexane, Sigma–Aldrich), phenyllithium
22, –23 Յ l Յ 23, 5164 independent reflections (Rint = 0.0564), 347
(1.9 m solution in dibutyl ether, Sigma–Aldrich), pyrrolidine (99%,
parameters with 0 restraints gave final R indices R1 = 0.0379 and wR2
Sigma–Aldrich), tetramethoxysilane (98%, ABCR), trichlorophenylsi-
= 0.0475 [data with I Ͼ 2σ(I)]. R1 = 0.0855, wR2 = 0.0496 (all data),
lane (97%, Sigma–Aldrich), triphenylsilanol (98%, Sigma–Aldrich),
goodness-of-fit on F2
= 1.000, largest electron density peak
triethylamine (Merck, 99%), pyridine hydrochloride (Merck, 98%),
thionyl chloride (99%, Merck), and magnesium turnings (99%,
Merck) were used without further purification. Mesityltrimethoxysil-
ane was synthesized according to a published procedure.[23] Dichlo-
romesitylphenylsilane (5) has been reported previously,[24] but was
prepared according to a modified procedure; the new protocol is pre-
sented herein. [D6]benzene used for NMR spectroscopy was dried with
Na/K amalgam. NMR spectra were recorded on a Bruker Avance 400
spectrometer (400.13 MHz) at 25 °C. Chemical shifts (δ) are reported
in parts per million (ppm). 1H and 13C{1H} NMR spectra are refer-
enced to tetramethylsilane (SiMe4, δ = 0.0 ppm) as external standard,
with the deuterium signal of the solvent serving as internal lock and
the residual solvent signal as an additional reference. 29Si{1H} NMR
spectra are referenced to SiMe4 (δ = 0.0 ppm) as external standard.
For the assignment of the multiplicities the following abbreviations
were used: s = singlet, m = multiplet. High resolution mass spectrome-
try was carried out on a Jeol AccuTOF GCX and an Agilent Q-TOF
6540 UHD spectrometer. Elemental analyses were performed on a Va-
rio MICRO cube apparatus.
0.223 e·Å–3, largest hole –0.267 e·Å–3.
Crystal Data and Structure Refinement of 4: Colorless plates,
0.37ϫ0.21ϫ0.04 mm3, C37H39NOSi2, Mr = 569.87 g·mol–1, triclinic,
¯
space group (Nr.) P1 (2), a = 9.5542(4) Å, b = 12.6193(5) Å, c =
14.6829(7) Å, α = 103.043(4)°, β = 92.016(4)°, γ = 111.301(4)°, V =
1593.35(13) Å3, Z = 2, ρ = 1.188 g·cm–3, μ = 1.226 mm–1. 10793 re-
flections collected with Θ in the range 3.889 – 74.077°, index ranges
–8 Յ h Յ 11, –15 Յ k Յ 13, –18 Յ l Յ 17, 6164 independent reflec-
tions (Rint = 0.0305), 373 parameters with 0 restraints gave final R
indices R1 = 0.0449 and wR2 = 0.1180 [data with I Ͼ 2σ(I)]. R1
=
0.0498, wR2 = 0.1225 (all data), goodness-of-fit on F2 = 1.027, largest
electron density peak 0.797 e·Å–3, largest hole –0.553 e·Å–3.
Crystal Data and Structure Refinement of 6: Colorless blocks,
0.19ϫ0.18ϫ0.09 mm3, C33H31ClOSi2, Mr = 535.21 g·mol–1, triclinic,
¯
space group (Nr.) P1 (2), a = 9.34760(10) Å, b = 10.9306(2) Å, c =
14.8126(2) Å, α = 104.5680(10)°, β = 96.9890(10)°, γ = 94.2340(10)
°, V = 1445.31(4) Å3, Z = 2, ρ = 1.230 g·cm–3, μ = 2.141 mm–1. 16989
reflections collected with Θ in the range 4.204 – 74.104°, index ranges
–11 Յ h Յ 11, –13 Յ k Յ 13, –18 Յ l Յ 17, 5763 independent
reflections (Rint = 0.0207), 337 parameters with 0 restraints gave final
R indices R1 = 0.0381 and wR2 = 0.1093 [data with I Ͼ 2σ(I)]. R1 =
0.0394, wR2 = 0.1106 (all data), goodness-of-fit on F2 = 1.048, largest
electron density peak 0.453 e·Å–3, largest hole –0.446 e·Å–3.
X-ray Crystallography: Single-crystal X-ray diffraction analysis of 3
was performed on an Oxford Diffraction CCD Xcalibur S dif-
fractometer equipped with a Sapphire3 CCD detector at 173(2) K using
graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å). Single-
crystal X-ray diffraction analyses of 4 and 6 were performed on a
GV50 diffractometer equipped with a TitanS2 CCD detector at 123(1)
K using Cu-Kα radiation (λ = 1.54184 Å). Data collection and re-
duction were performed using the CrysAlisPro software system (Ver-
sion 1.171.33.55 for 3 and Version 1.171.40.66a for 4 and 6).[25] The
Synthesis of (Mes)PhSi(OMe)2 (1): Phenyllithium (14.3 mL of a
1.9 m solution in dibutyl ether, 27.0 mmol) was added dropwise to
a solution of mesityltrimethoxysilane (6.49 g, 27.0 mmol) in pentane
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(140 mL) at –68 °C over a period of 20 minutes. The resulting light
(s, 3 H, OCH3), 6.71 (s, 2 H, HAr), 7.09–7.15 (m, 12 H, HPh), 7.70 (m,
red suspension was then allowed to slowly warm up to room tempera- 2 H, HPh), 7.76 (m, 6 H, HPh). 13C{1H} NMR (100.62 MHz, C6D6):
ture and kept stirring for 15 h. The suspension was filtered through a δ = 21.1 [s, Ar(p-CH3)], 24.6 [s, Ar(o-CH3)], 50.2 (s, OCH3), 128.1
fritted column layered with Celite® and the remaining solids washed (s, CPh), 128.2 (s, CPh), 129.6 (s, Cipso(Ar)), 130.0 (s, CPh), 130.1 (s,
with pentane (2ϫ20 mL). All volatiles of the filtrate were removed in
vacuo. The brownish oily residue was purified by Kugelrohr distil-
C
meta(Ar)), 134.3 (s, CPh), 135.7 (s, CPh), 135.9 (s, CPh), 136.8 (s, CPh),
140.0 (s, Cpara(Ar)), 145.9 (s, Cortho(Ar)). 29Si{1H} NMR (79.49 MHz,
lation (110 °C oven temperature, 1.3ϫ10–2 mbar) to give compound C6D6): δ = –33.3 (s, SiOCH3), –18.1 (s, SiPh3). HRMS (EI+):
2 (6.33 g, 22.1 mmol, 82%) as a colorless oil. 1H NMR (400.13 MHz, C34H34O2Si2 calcd. m/z for [M+] 530.20918; found 530.21062.
C6D6): δ = 2.10 [s, 3 H, Ar(p-CH3)], 2.56 [s, 6 H, Ar(o-CH3)], 3.40 C34H34O2Si2: calcd. C 76.93, H 6.46%; found C 77.21, H 6.41%.
(s, 6 H, OCH3), 6.71 (s, 2 H, HAr), 7.16 (m, 3 H, HPh), 7.74 (m, 2 H,
Synthesis of (Mes)PhSiCl2 (5): Thionyl chloride (8.7 mL, 120 mmol)
HPh). 13C{1H} NMR (100.62 MHz, C6D6): δ = 21.1 [s, Ar(p-CH3)],
was added to a mixture of compound 1 (5.73 g, 20.0 mmol) and pyr-
24.0 [s, Ar(o-CH3)], 49.8 (s, OCH3), 126.3 (s, Cipso(Ar)), 128.1 (s, CPh),
idine hydrochloride (240 mg, 2.0 mmol) at room temperature with stir-
ring. The reaction mixture was refluxed for 8 h. After cooling down
to room temperature, all volatiles were removed in vacuo. The yellow
129.6 (s, Cmeta(Ar)), 130.1 (s, CPh), 134.6 (s, CPh), 135.5 (s, CPh), 140.1
(s, Cpara(Ar)), 146.2 (s, Cortho(Ar)). 29Si{1H} NMR (79.49 MHz, C6D6):
δ = –25.4 (s) ppm. HRMS (EI+): C17H22O2Si calcd. m/z for [M+]
286.13836; found 286.13762. C17H22O2Si: calcd. C 71.30, H 7.74%;
found C 71.43, H 7.66%.
oily residue was purified by Kugelrohr distillation (110 °C oven tem-
perature, 4.6ϫ10–2 mbar) to give compound 5 (4.01 g, 13.6 mmol,
68%) as a pale yellow oil. 1H NMR (400.13 MHz, C6D6): δ = 2.00
[s, 3 H, Ar(p-CH3)], 2.36 [s, 6 H, Ar(o-CH3)], 6.60 (s, 2 H, HAr), 7.07
Synthesis of (Mes)PhSi(OMe)(NC4H8) (2): n-Butyllithium (6.2 mL
(m, 3 H, HPh), 7.71 (m, 2 H, HPh). 13C{1H} NMR (100.62 MHz,
of a 2.5 m solution in hexane, 15.4 mmol) was added dropwise to a
C6D6): δ = 20.7 [s, Ar(p-CH3)], 24.9 [s, Ar(o-CH3)], 125.3 (s,
solution of pyrrolidine (1.09 g, 15.4 mmol) in hexane (80 mL) at
Cipso(Ar)), 128.4 (s, Cpara(Ar)), 130.2 (s, Cmeta(Ar)), 130.9 (s, CPh), 133.3
–30 °C. The resulting white suspension was then allowed to slowly
warm up to room temperature and kept stirring for 1 h. The reaction
mixture was transferred by means of a PTFE tube in one portion to a
solution of 1 (3.68 g, 12.8 mmol) in hexane (40 mL) at ambient tem-
perature. The resulting suspension was refluxed for 15 h. After cooling
down to room temperature, the mixture was filtered through a fritted
column layered with Celite® and the remaining solids washed with
hexane (2ϫ20 mL). All volatiles of the filtrate were removed in
vacuo. The oily residue was purified by Kugelrohr distillation (110 °C
oven temperature, 1.3ϫ10–3 mbar) to give compound 2 (3.45 g,
(s, CPh), 136.7 (s, CPh), 141.6 (s, Cpara(Ar)), 145.1 (s, Cortho(Ar)).
29Si{1H} NMR (79.49 MHz, C6D6): δ = 4.7 (s) ppm. HRMS (EI+):
C15H16SiCl2 calcd. m/z for [M+] 294.03928; found 294.03938.
C15H16SiCl2: calcd. C 61.02, H 5.46%; found C 60.98, H 5.40%.
Synthesis of (Mes)PhSiCl(OSiPh3) (6): n-Butyllithium (4.0 mL of a
2.5 m solution in hexane, 10.0 mmol) was added dropwise to a solution
of triphenylsilanol (2.76 g, 10.0 mmol) in tetrahydrofuran (20 mL) at
–30 °C. The clear colorless solution was then allowed to slowly warm
up to room temperature and kept stirring for 1 h. A solution of com-
pound 5 (2.95 g, 10.0 mmol) in tetrahydrofuran (10 mL) was added to
the reaction mixture by means of a PTFE tube at –30 °C. The resulting
clear mixture was allowed to slowly warm up to room temperature and
kept stirring for 5 h. Then, the mixture was concentrated to around
15 mL volume. Lithium chloride was precipitated by adding pentane
(40 mL) to the concentrated solution under vigorous stirring. The mix-
ture was stirred for 30 min, the solids left to sediment, and the mother
liquor recovered by means of filtration through a PTFE tube. All vola-
tiles of the filtrate were removed in vacuo yielding pure compound 6
as a pale beige solid (4.92 g, 9.2 mmol, 92%). Colorless crystals suit-
able for single-crystal X-ray diffraction analysis were obtained from a
concentrated tetrahydrofuran solution layered with pentane at –30 °C
within one week. 1H NMR (400.13 MHz, C6D6): δ = 2.00 [s, 3 H,
Ar(p-CH3)], 2.41 [s, 6 H, Ar(o-CH3)], 6.63 (s, 2 H, HAr), 6.97 (m, 2
H, HPh), 7.02 (m, 1 H, HPh), 7.09 (m, 9 H, HPh), 7.61 (m, 2 H, HPh),
7.71 (m, 6 H, HPh). 13C{1H} NMR (100.62 MHz, C6D6): δ = 21.0 [s,
Ar(p-CH3)], 25.1 [s, Ar(o-CH3)], 127.0 (s, Cipso(Ar)), 128.1 (s, CPh),
128.2 (s, CPh), 130.1 (s, CPh), 130.3 (s, Cmeta(Ar)), 130.5 (s, CPh), 133.7
(s, CPh), 135.0 (s, CPh), 135.8 (s, CPh), 137.5 (s, CPh), 141.0 (s,
1
10.6 mmol, 83%) as a colorless oil. H NMR (400.13 MHz, C6D6): δ
= 1.56 (m, 4 H, NCH2CH2), 2.15 [s, 3 H, Ar(p-CH3)], 2.49 [s, 6 H,
Ar(o-CH3)], 3.00–3.10 (m, 4 H, NCH2CH2), 3.46 (s, 3 H, OCH3), 6.81
(s, 2 H, HAr), 7.20 (m, 3 H, HPh), 7.68 (m, 2 H, HPh). 13C{1H} NMR
(100.62 MHz, C6D6): δ = 21.1 [s, Ar(p-CH3)], 24.2 [s, Ar(o-CH3)],
26.9 (s, NCH2CH2), 47.6 (s, NCH2CH2), 50.3 (s, OCH3), 128.1 (s,
CPh), 129.1 (s, Cipso(Ar)), 129.5 (s, Cmeta(Ar)), 129.6 (s, CPh), 135.2 (s,
CPh), 137.4 (s, CPh), 139.3 (s, Cpara(Ar)), 145.9 (s, Cortho(Ar)). 29Si{1H}
NMR (79.49 MHz, C6D6): δ = –23.2 (s) ppm. HRMS (EI+):
C20H27NOSi calcd. m/z for [M+] 325.18564; found 325.18350.
C15H25NOSi: calcd. C 73.39, H 8.36, N 4.30%; found C 73.73, H
8.00, N 4.15%.
Synthesis of (Mes)PhSi(OMe)(OSiPh3) (3): Procedure (a) A mixture
of compound 2 (1.78 g, 5.48 mmol) and triphenylsilanol (1.51 g,
5.48 mmol) in toluene (40 mL) was refluxed for 15 h. After cooling
down to room temperature, all volatiles were removed in vacuo and
the obtained residue was dissolved in the minimum volume of tetra-
hydrofuran. The clear colorless concentrated solution was layered with
pentane and stored at –30 °C. Within 5 days, colorless crystals of com-
pound 3 suitable for single-crystal X-ray diffraction analysis were
formed (2.29 g, 4.32 mmol, 79%). Procedure (b): A mixture of com-
pound 6 (2.34 g, 4.37 mmol) and triethylamine (1.32 g, 13.1 mmol) in
methanol (10 mL) was stirred for 5 h at room temperature yielding a
C
para(Ar)), 145.6 (s, Cortho(Ar)). 29Si{1H} NMR (79.49 MHz, C6D6): δ
= –18.85 (s), –16.4 (s) ppm. HRMS (EI+): C33H31ClOSi2 calcd. m/z
for [M+] 534.15965; found 534.16142. C33H31ClOSi2: calcd. C 74.05,
H 5.84%; found C 73.89, H 5.97%
pale beige suspension. Then, all volatiles were removed in vacuo and Synthesis of (Mes)PhSi(NC4H8)(OSiPh3) (4): n-Butyllithium
the oily residue washed with hexane (20 mL). The crude solid was (2.6 mL of a 2.5 m solution in hexane, 6.43 mmol) was added dropwise
suspended in diethyl ether (30 mL) and the formed triethylammonium
chloride filtered off through a pad of Celite®. After the remaining
solids had been washed again with diethyl ether (2ϫ10 mL), the fil-
to a solution of pyrrolidine (457 mg, 6.43 mmol) in hexane (20 mL) at
–30 °C. The resulting white suspension was then allowed to slowly
warm up to room temperature and kept stirring for 1 h. A solution of
trates were collected and dried in vacuo. Compound 3 was obtained compound 6 (2.86 g, 5.35 mmol) in hexane (20 mL) was added to the
as a colorless solid (1.51g, 2.84 mmol, 65%). 1H NMR (400.13 MHz,
reaction mixture by means of a PTFE tube at ambient temperature.
C6D6): δ = 2.07 [s, 3 H, Ar(p-CH3)], 2.48 [s, 6 H, Ar(o-CH3)], 3.27 The resulting suspension was refluxed for 15 h. After cooling down to
Z. Anorg. Allg. Chem. 2020, 1–8
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© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Braun, C. Limberg, Z. Anorg. Allg. Chem. 2017, 643, 1581–1588;
room temperature, the mixture was filtered through a fritted column
g) J. O. Bauer, C. Strohmann, Inorg. Chim. Acta 2018, 469, 133–
135; h) K. S. Lokare, B. Braun-Cula, C. Limberg, M. Jorewitz,
J. T. Kelly, K. R. Asmis, S. Leach, C. Baldauf, I. Goikoetxea, J.
Sauer, Angew. Chem. Int. Ed. 2019, 58, 902–906; Angew. Chem.
2019, 131, 912–917.
layered with Celite® and the remaining solids washed with hexane
(2ϫ20 mL). The filtrate was concentrated to around 20 mL volume
rendering a beige suspension. The mixture was then refluxed for a
period of 30 min and the hot clear beige solution allowed to slowly
cool down to room temperature yielding compound 4 as colorless crys-
tals suitable for single-crystal X-ray diffraction analysis (2.19 g,
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1
3.85 mmol, 72%). H NMR (400.13 MHz, C6D6): δ = 1.44 (m, 4 H,
NCH2CH2), 2.10 [s, 3 H, Ar(p-CH3)], 2.42 8s, 6 H, Ar(o-CH3)], 2.95–
3.05 (m, 4 H, NCH2CH2), 6.76 (s, 2 H, HAr), 7.08–7.16 (m, 12 H,
HPh), 7.66 (m, 2 H, HPh), 7.70 (m, 6 H, HPh). 13C{1H} NMR
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(100.62 MHz, C6D6):
δ
=
21.0 [s, Ar(p-CH3)], 24.8 [s,
Ar(o-CH3)], 26.9 (s, NCH2CH2), 47.6 (s, NCH2CH2), 127.9 (s, CPh),
128.0 (s, CPh), 129.6 (s, CPh), 129.6 (s, CPh), 129.7 (s, CPh), 129.9 (s,
C
C
meta(Ar)), 134.9 (s, CPh), 135.7 (s, CPh), 136.5 (s, CPh), 139.1 (s,
ipso(Ar)), 139.4 (s, Cpara(Ar)), 145.8 (s, Cortho(Ar)). 29Si{1H} NMR
(79.49 MHz, C6D6): δ = –31.0 (s, SiN), –19.9 (s, SiPh3) ppm. HRMS
(EI+): C37H39NOSi2 calcd. m/z for [M+] 569.25647; found 569.25478.
C37H39NOSi2: calcd. C 77.98, H 6.90, N 2.46%; found C 77.91, H
6.87, N 2.44%.
Acknowledgements
[8] J. O. Bauer, C. Strohmann, Chem. Commun. 2012, 48, 7212–
The Elite Network of Bavaria (ENB), the Bavarian State Ministry of
Science and the Arts (StMWK), and the University of Regensburg are
gratefully acknowledged for financial support. In addition, we thank
Prof. Dr. Manfred Scheer and Prof. Dr. Jörg Heilmann for generous
and continuous support and the provision of research facilities.
7214.
[9] J. O. Bauer, C. Strohmann, Angew. Chem. Int. Ed. 2014, 53, 720–
724; Angew. Chem. 2014, 126, 738–742.
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Keywords: Chemoselectivity; Disiloxanes; Silanes; Silicon;
Structure elucidation
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Received: February 2, 2020
Published Online: ᭿
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Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
N. A. Espinosa-Jalapa, J. O. Bauer* ................................ 1–8
Controlled Synthesis and Molecular Structures of Methoxy-,
Amino-, and Chloro-Functionalized Disiloxane Building
Blocks
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