(1 of 10) e1700298

Facile Synthesis of Unsymmetrical Trialkoxysilanols:

(RO)2(R0 O)SiOH
Scott R. Docherty,a Deven P. Estes,b and Christophe Cop

eret*
Department of Chemistry and Applied Biology, ETH Zu€rich, Vladimir-Prelog-Weg 1-5, CH-8093, Zu
€rich, Switzerland,
e-mail: ccoperet@ethz.ch

Trialkoxysilanols, (RO)3SiOH, are useful as ligands in transition-metal complexes because they provide models for
silica-supported metal sites or precursors for the thermolytic precursor approach. However, their synthesis is mostly
limited to symmetrical ones, where all RO ligands are the same. However, unsymmetrically substituted
trialkoxysilanols could offer significant advantages over their symmetrical counterparts by facilitating crystallization of
complexes, lowering crystallographic disorder, changing the thermal properties of the complexes made, and making
the addition of pendant functional groups possible. Herein, a simple, general synthetic procedure yielding
unsymmetrical trialkoxysilanols (RO)2(R0 O)SiOH is presented using imidazole as a promoter.

Keywords: silanol, surface models, silica, Lewis base catalyzed reactions, metal siloxide complexes.

in particular tris-tert-butoxysilanol (HOSi(OtBu)3, TBOS)

Introduction
Molecular silanols are often used as molecular mimics
of surface silanols due to the ease of preparation and
characterization of molecular complexes in compar-
ison with the corresponding silica-supported surface
species. The molecular species have been shown to
have similar reactivity and structural features to their
surface analogues.[1 – 19] They are useful in gathering
spectroscopic signatures of possible surface species
and to better understand the specificity of surface
bound species,[20] with the ultimate goal to obtain
structure–property relationships.[8][21][22] The most
typical examples are tris-alkyl/aryl and tris-alkylsilanols
(-OSiR3),[9][16][17][19][23] trialkoxysilanols (-OSi(OR)3),[2][3][8]
[10][22][24][25]
or polyhedral oligomeric silsesquioxane
(POSS) ligands.[1][5 – 7][19] Each family provides a differ-
ent environment and offers specific advantages.[18]
For example, trialkylsilanols, in particular tris-tert-butyl-
silanol, are very bulky and can provide access to very
low coordinated species.[9][23][26][27] Tris-alkoxy-silanols,
a substituted trisalkoxysilanols would help by solving
Current address: School of Chemistry, University of
Edinburgh, Joseph Black Building, David Brewster Road,
EH9 3FJ Edinburgh, UK.
b and the thermal decomposition temperature.
Current address: Institute for Technical and
Macromolecular Chemistry, RWTH Aachen, Worringerweg
2, DE-52074 Aachen, Germany.
are on the other hand much better models for silica
surfaces, since they provide a more similar electronic
environment to silica than trialkylsilanols. In addition,
this ligand can help stabilize many species, because
they can easily adopt various hapticities.[24] Finally, the
TBOS ligand provides a very good entry to the so-
called thermolytic precursor (TMP) approach, allowing
the synthesis of well-defined mixed metal oxide and
supported single-site catalysts,[3][8][11][12][21][22] or the
generation of luminescent or magnetic particles.[25][28]
[29]
However, as with most models, they are not always
ideal, since they do not provide the steric shielding and
the diversity of coordination environments of a metal
oxide surface. In addition, these molecular TBOS deriva-
tives often have problems with crystallization, such as
formation of multicrystals, twinning, or high disorder,
that make the X-ray diffraction data difficult or impossi-
ble to interpret.[11] In addition, trisalkoxysilanols are
often thermally sensitive and give insoluble silicates
upon extended heating. In principle, these problems
can all be solved by varying/tuning the substituents of
these siloxide ligands. Specifically, unsymmetrically
problems of disorder in crystallization, while simultane-
ously enabling fine tuning of the electronic properties
However, reports of the synthesis of unsymmetri-
cal silanols are scarce. Trisalkoxysilanols are typically

DOI: 10.1002/hlca.201700298 Helv. Chim. Acta 2018, 101, e1700298 © 2018 Wiley-VHCA AG, Zurich, Switzerland
 Helv. Chim. Acta 2018, 101, e1700298
Scheme 1. Synthetic scheme for synthesis of unsymmetrically
substituted trialkoxysilanols.
synthesized by the three-step procedure shown in
Scheme 1.[4][30][31] The first step consists of addition
of two equivalents of alcohol to SiCl4 in the pres-
ence of pyridine making bis-alkoxy-silyldichloride 1.
This step must be carried out with bulky alcohols,
such as tBuOH, since smaller alcohols also produce
the monoalkoxy, and trisalkoxy species, along with
insoluble silicates. In Step IIa, reaction of 1 with the
appropriate KOR salt produces the desired asymmet-
ric silyl chloride species (2). Alternatively (Step IIb),
heating 1 with one equivalent of another alcohol in
the presence of pyridine also leads to mixed silyl
chloride 2. The final step (Step III) consists of the
reaction of 2 with H2O in the presence of pyridine
to produce the desired silanol (3). The current syn-
thetic method for synthesis of unsymmetrical sila-
nols is however not ideal, due to either the harsh
conditions required for the synthesis or extremely
long reaction times (vide infra). We therefore provide
herein an alternative and improved general synthesis
of unsymmetrically substituted trialkoxysilanols using
imidazole as a promoter.
Results and Discussion
We initially attempted to use the route shown in
Scheme 1 to synthesize the desired complex 2c as it
would allow the introduction of a chelating olefin
group. However, reaction of the potassium alkoxide
derivative with 1 led to preferential elimination of the
olefin functionality (Eqn 1), producing mostly bis-
silylchloride product 4 (73%) instead of 2c. This proba-
bly occurs by elimination of 2-methylbutadiene from
2c (elimination of tertiary alkyl groups from alkoxy-
silanols is well documented)[12][32] followed by
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condensation of the silanol product with another
equivalent of 1. Method-IIb did not yield any of the
desired product after heating 3 with HOC-
Me2(CH=CH2) and pyridine for 18 h, with no reaction
occurring. Clearly, a more general method is needed
for the synthesis of unsymmetrical silanols.
Inspired by reports of imidazole promoted substi-
tution reactions,[33 – 38] we find that replacing pyri-
dine with imidazole as base greatly improves the
yield of both Steps IIb and III. The reaction of 1
with HOCMe2(vinyl) at 50 °C for 18 h in the pres-
ence of imidazole gives 71% of the desired product
(2c). These findings are in line with those of Corey
and co-workers regarding silyl protecting groups.[34]
This finding is quite general. The reaction of
(tBuO)2SiCl2 with a variety of alcohols (Eqn 2,
Table 1); in the presence of imidazole provide higher
yields of the desired products by comparison with
the protocol using pyridine. The biggest difference
is observed for sterically challenging substrates like
tertiary alcohols. Imidazole also gives much better
results than pyridine for bulky aryl alcohols such as
2,4,6-trimethylphenol, while pyridine performs better
for para-cresol. However, in the case of primary
alcohols, the very fast reaction has so far yielded
only multiple products.
Imidazole also outperforms pyridine at the hydroly-
sis of silylchlorides (step III). The results of the hydroly-
sis of several different asymmetric silylchlorides (Eqn
3) are shown in Table 2. Using imidazole as a base
gives quantitative yield in all the cases after 18 h at
room temperature. In contrast, the use of pyridine
leads to a decrease in yields with bulkier alcohols. In
fact, for silanol 3c, hydrolysis of 2c with water and
pyridine in diethyl ether is still not complete after
5 days, while this reaction is quantitative at room
temperature in 18 h with imidazole. In contrast, the
difference between imidazole and pyridine is negligi-
ble for the hydrolysis of less sterically encumbered
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 Helv. Chim. Acta 2018, 101, e1700298

Table 1. Comparison of reaction of (tBuO)2SiCl2 with various alcohols in the presence of either imidazole or pyridine
Alcohol a-carbon Conversion Conversion Conversion
(no base)[a] (pyridine)[a] (imidazole)[a]

2a 2° 0% 73% 97%

2b 3° 0% 0% 65%

2c 3° – 0% 71%

2d Aromatic 0% 84% 75%

2e Aromatic 0% 25% 90%

[a]
Reaction parameters: 1:1 alcohol/bis-tert-butoxybischlorosilane, 1.1 equivalents of facilitating base (where applicable), 0.21 M
(toluene), heating at 50 °C for 18 h. NMR yields.

Table 2. Hydrolysis of (tBuO)2(RO)SiCl in the presence of either

pyridine or imidazole
R-group a-carbon Conversion Conversion
(pyridine)[a] (imidazole)[a]

3a 2° 100% 100%
Since Mayr and coworkers have shown that rates of
substitution with pyridine are usually faster than with
imidazole, this is probably not due to imidazole
3b 3° 27% 100%
enhancing the rate of substitution (k2 is not faster
with imidazole).[40] Rather, since imidazole is thermo-
dynamically more basic than pyridine (imidazolium
3c 3° 60%[b] 100% pKa = 6.3 in DMSO, pyridinium pKa = 3.5 in DMSO),[41]
a larger concentration of the ion pair intermediate will
likely be formed with imidazole than pyridine (K1 is
3d Aromatic – 100% larger for imidazole than pyridine), leading to faster
overall substitution. Since imidazole is also smaller
than pyridine, attack of bulkier alcohols on the less
3e Aromatic 95% 100% sterically hindered imidazole ion pair will probably be
faster than with the more sterically hindered pyridine
ion pair (k2 for bulky alcohols is smaller when
[a]
Reaction parameters: 1.15 equivalents of facilitating base, B = pyridine than when B = imidazole).
130 equivalents H2O, 0.3 M (diethyl ether), room temperature
for 18 h. [b] same concentrations/stoichiometry, reflux for 24 h.

silylchlorides. The substitution reaction in the presence

of base is thought to occur through the formation of
an ion pair intermediate through substitution of the
chloride by the base, as illustrated in Scheme 2.[39] Scheme 2. Possible mechanism for synthesis of (RO)2(R0 O)SiCl.

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 Helv. Chim. Acta 2018, 101, e1700298
Figure 1. ORTEP diagram of (tBuO)2(2,4,6-(CH3)3C6H2SiOH (3e)
(50% probability) showing intramolecular hydrogen bonding
(C–H hydrogens omitted for clarity).
This synthesis can be readily scaled-up. For
instance, the synthesis of 3e using 15 g of the precur-
sor, (tBuO)2SiCl2, reached full conversion according to
NMR analysis, yielding 15.7 g of pure (tBuO)2(2,4,6-
Me3–C6H2O)SiCl (74% yield of isolated product). With
imidazole used as a base, the hydrolysis in Et2O/H2O
yielded 14.3 g of pure material (96% yield of isolated
product), for a total yield of 51% over three steps. The
product 3e is readily crystallized from a mixture of
diethyl ether and cyclohexane (see Supporting Infor-
mation for full details). This compound was further
characterized by X-ray crystallography (Figure 1, CCDC
1821646). The crystals did not show any twinning or
multicrystal formation and did not have any problems
with disorder in the structure, such as is common for
HOSi(OtBu)3.
Conclusions
We have shown that the synthesis of unsymmetrically
substituted trialkoxysilanols can be accomplished via
the assistance of imidazole in the reaction, in contrast
to the more classical approach. Imidazole is an essen-
tial component that increases the yield of unsymmet-
rically substituted silylchlorides as well as the yield of
silylchloride hydrolysis to form the desired silanols.
This result is general for a variety of different alcohols
and silylchlorides, in particular for bulky alkoxides. This
synthesis is easily scalable and can be used to make
larger batches of silanol in high overall yield. Some of
these silanols show desired properties such as ease of
crystallization and ease of X-ray diffraction analysis.
This method can also be used to synthesize silanols
with pendant functional groups that may be useful in
coordination chemistry. In addition, the milder
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reaction conditions offered by this method (less pro-
longed heating) make it particularly attractive for the
preparation of more thermally sensitive silanols. We
are currently exploring this approach to prepare tai-
lored precursors and surface mimics.
Experimental Section
General Considerations
Unless otherwise noted, all manipulations were under-
taken using conventional air-free techniques (glove box
(Ar) and Schlenk techniques (Ar)). Pentane, diethyl ether,
dichloromethane, heptane, and toluene were purified
using double MBraun SPS alumina columns, and stored
over activated Molecular Sieves (4  A, Merck) in an argon
atmosphere. Tetrahydrofuran (THF) was distilled from
purple Na0/benzophenone under Ar and stored over
activated molecular sieves (4 A, Merck). CD2Cl2 was vac-
uum distilled from P2O5 and stored under argon. C6D6
and (D8)THF were vacuum distilled from purple Na0/
benzophenone. Pyridine, pent-4-en-2-ol, tert-butyl alco-
hol, and 2-methylbut-3-en-2-ol were distilled from CaH2
onto activated molecular sieves (4  A, Merck), under
argon. Silicon tetrachloride (SiCl4) was used as pur-
chased (ABCR, 99.999% pure). 2,4,6-Trimethylphenol
was sublimed under vacuum and further dried by dis-
solving in pentane and stirring over activated molecular
sieves (4 A, Merck). Imidazole was recrystallized from
dry dichloromethane and further dried by dissolving in
pentane and stirring over activated molecular sieves
(4 
A, Merck). 4-Methylphenol was distilled under argon
and stored at 20 °C. All reagents described were
stored under argon. Celiteâ and Molecular Sieves (4  A,
Merck) were activated under high vacuum overnight at
300 °C. Deionized water was collected from Merck Milli-
pore Synergyâ Water Purification System. Na2SO4, NaH,
and CaH2 were used as received (Sigma-Aldrich).
IR (infrared) spectra were recorded on a Thermo
Fischer ScientificTM Nicolet 6700 FT-IRTM equipped with a
PIKE technologies GladiATRTM or a Bruker FT-IR Alpha
spectrometer with ATR-IR attachment and are
reported as absorption maxima in cm1. Peak intensi-
ties are described using the convention strong (s),
medium (m), and weak (w). A typical experiment con-
sisted of the measurement of transmission in 16 scans
in the range 4000 – 400 cm1, unless otherwise
declared. Spectra were analyzed using Thermo Scien-
tificTM OMNICTM Specta Software.
High resolution mass spectra (HR-EI-MS) were mea-
sured by the mass spectrometry service of the ‘Labo-
ratorium fu €r Organische Chemie der ETH Zu €rich’.
Values are given as mass per unit charge (m/z) and
the proportional intensity (given in %) of the base
© 2018 Wiley-VHCA AG, Zurich, Switzerland
 Helv. Chim. Acta 2018, 101, e1700298
peak. Elemental analysis was performed by the
microelemental analysis service of the ‘Laboratorium
€r Organische Chemie der ETH Zu
fu €rich, Mikroelemental-
analytisches Laboratorium der ETH Zu €rich’.
Solution H-NMR, C-NMR, Si-NMR, 1H,13C-HSQC,
1 13 29
1 13
H, C-HMBC, 1H,1H-COSY, 1H,1H-NOESY, 1H,29Si-HMBC,
DEPT-45 DEPT-90, and DEPT-135 spectra were
obtained on Brukerâ DRX 300 spectrometer (7.05 T,
Larmor Frequency: 300 MHz (1H), 75.5 MHz (13C),
59.6 MHz (29Si)), in deuterated methylene chloride
(CD2Cl2), deuterated tetrahydrofuran ((D8)THF), deuter-
ated benzene (C6D6) or deuterated chloroform (CDCl3)
at room temperature. The 1H and 13C chemical shifts
are referenced relative to residual solvent peaks.[41][42]
Chemical shifts are reported in parts per million [ppm]
and coupling constants (NJX-X) are given in Hertz [Hz].
Where appropriate, signal multiplicity has been con-
densed to a single letter format, i.e.: s = singlet,
d = doublet, t = triplet, q = quartet, m = multiplet. Sol-
vent peaks are denoted with an asterisk. Unless noted,
13
C spectra were recorded using 1024 scans.
General Procedure – Reaction of (tBuO)SiCl2 (1) with
Alcohol in the Presence of Base
A measured amount of bis-tert-butoxybischlorosilane
(1; 1.00 g, 4.08 mmol) was dissolved in toluene
(20 mL). Pyridine (1.1 equivalents, 4.50 mmol) was
added to this solution, followed by ROH (1 equiva-
lent). The resulting mixture was heated, with stirring,
to 50 °C for 18 h. NMR was used to quantify yield,
using both substrate and product as reference.
A typical example. The reactions were monitored
in the same way for all substrates.
General Procedure – Hydrolysis of (tBuO)2(RO)SiCl
(tBuO)2(RO)SiCl (2) was dissolved in diethyl ether
(0.3 M). Pyridine or imidazole (1.1 equivalents) was
added, followed by 130 equivalents of deionized
water. The resulting mixture was stirred at room tem-
perature for 18 h. NMR yields were recorded.
A typical example. The reactions were monitored
in the same way for all substrates.
Synthesis and Characterization of Pure (tBuO)2(RO)SiCl
Samples
Di-tert-butoxy(dichloro)silane ((tBuO)2SiCl2; 1). To
pyridine (27.0 mL, 330 mmol) in heptane (200 mL),
SiCl4 (18.4 mL, 160 mmol) was added dropwise. A sig-
nificant amount of white precipitate formed immedi-
ately. Then tert-butyl alcohol (30.4 mL, 320 mmol) was
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added, and the resulting mixture was heated to
115 °C for 3 h. After cooling, the mixture was filtered
over Celiteâ and solvent was removed in vacuo, to
yield 28.2 g (115 mmol, 72%). NMR analysis indicated
high purity (> 99%). 1H-NMR (300 MHz, C6D6): 1.27 (s).
Di-tert-butoxy(chloro)(pent-4-en-2-yloxy)silane ((tBuO)2-
(CH2CHCH2CH(CH3)O)SiCl; 2a). To (tBuO)2SiCl2 (1;
1.00 g, 4.08 mmol) in toluene (20 mL), imidazole
(306 mg, 4.50 mmol) was added, followed by 4-penten-
2-ol (0.420 mL, 4.08 mmol). The resulting mixture was
heated, while stirring, at 50 °C for 18 h. The reaction
mixture was filtered and the remaining solid washed
with toluene (3 9 5 mL). The filtrate and combined
washings were collected. The solvent was removed
from the filtrate in vacuo. 883 mg was obtained. Distilla-
tion at 94 °C under vacuum yielded 843 mg
(2.86 mmol, 70%) of a colorless oil, which was analyzed
by EI-MS, 1H-NMR, 13C-NMR, 1H,13C-HSQC, 1H,13C-HMBC,
1 29
H, Si-HMBC, DEPT-45/90/135, elemental analysis (EA;
C and H) and ATR-IR. IR (ATR): 2977m, 2932w, 1392w,
1367m, 1244w, 1184w, 1060s, 914m, 832w, 816w, 696m,
650m. 1H-NMR (300 MHz, C6D6): 5.93 – 5.77 (br. m, 1 H,
H2C=CH-R); 5.08 – 5.02 (m, 1 H, trans-H2C=CH–R);
5.02 – 4.98 (m, 1 H, cis-H2C=CH–R); 4.27 (sextet, 1 H,
J = 6, R–O–CH(CH3)R0 ); 2.38 – 2.15 (m, 2 H, CH2=CH–
CH2–R); 1.36 (s, 18 H, CH3) 13C-NMR (75.5 MHz, C6D6):
135.0; 117.0; 75.2; 70.4; 43.5 31.2; 22.3. 29Si-NMR
(59.6 MHz, C6D6): 84. EI-MS: base peak: 279.1182
([M  15]+, C12H24ClO3Si+; calc. 279.1178 (Dm/z
= 0.0004 amu, 1.4 ppm)); 281 (36, [M  13]+), 280 (16,
[M  14]+), 279 (100, [M  15]+), 255 (29, [M  39]+),
253 (88, [M  41]+), 223 (14, [M  71]+), 197 (23,
[M  97]+), 165 (35, [M  129]+), 143 (15, [M  151]+),
141 (51, [M  153]+), 69 (28, [M  224]+), 57 (84,
[M  237]+). Anal. calc.: C 51.49, H: 9.24; found: C 52.95,
9.23.
Tri-tert-butoxy(chloro)silane ((tBuO)3SiCl; 2b). To
(tBuO)2SiCl2 (1; 1.00 g, 4.08 mmol) in toluene (20 mL),
imidazole (306 mg, 4.50 mmol) was added, followed
by tert-butyl alcohol (0.390 mL, 4.11 mmol). The
resulting mixture was heated, while stirring, at 50 °C
for 72 h. The mixture was filtered, and the remaining
solid washed with toluene (3 9 5 mL). The filtrate
and washings were combined. The solvent was
removed from the filtrate in vacuo. Distillation at
100 °C under vacuum yielded 470 mg (1.66 mmol,
41%) of a colorless oil, which was analyzed by 1H-
NMR. 1H-NMR (300 MHz, C6D6): 1.37.
Di-tert-butoxy(chloro)[(2-methylbut-3-en-2-yl)oxy]silane
((tBuO)2(CH2CHC(CH3)2O)SiCl; 2c). Solid Potassium-1,1-
dimethylallyloxide (1.504 g, 12.1 mmol) was added
slowly at 0 °C over 1 h, while stirring, to di-tert-butoxy-
dichlorosilane (1; 2.504 g, 10.2 mmol) dissolved in dry
© 2018 Wiley-VHCA AG, Zurich, Switzerland
 Helv. Chim. Acta 2018, 101, e1700298
THF (95 mL). The resulting mixture was stirred at room
temperature for 2 h, and refluxed for 12 h. The result-
ing solution was filtered through Celiteâ, and the sol-
vent removed in vacuo yielding 2.1 g of crude product.
Distillation under vacuum at 78 °C yielded 1.64 g
(5.6 mmol, 55%) of a colorless oil, which was analyzed
by EI-MS, 1H-NMR, 13C-NMR, 1H,13C-HSQC, 1H,13C-HMBC,
1 29
H, Si-HMBC, and ATR-IR. IR (ATR): 2977m, 1366m,
1241w, 1179m, 1149w, 1069s, 919m, 831w, 692m, 638m.
1
H-NMR (300 MHz, C6D6): 6.02 (dd, J = 17.3, 10.8, 1 H,
H2C=CH–R); 5.24 (dd, J = 17.3, 1.3, 1 H, trans-H2C=CH–
R); 4.93 (dd, J = 10.8, 1.3, 1 H, cis-H2C=CH–R); 1.47 (s, 6
H, CH3); 1.37 (s, 18 H, CH3(tBuO-)). 13C-NMR (75.5 MHz,
C6D6): 145.5; 110.9; 76.6; 75.2; 31.2; 29.3. 29Si-NMR
(59.6 MHz, C6D6): 91. EI-MS: base peak: 279.1176
([M  15]+, C12H24ClO3Si+; calc. 279.1176, (Dm/z = 0,
0 ppm)); 281 (36, [M  13]+), 280 (16, [M  14]+), 279
(100, [M  15]+), 237 (24, [M  57]+), 223 (17,
[M  71]+), 211 (17, [M  83]+), 181 (15, [M  113]+),
167 (35, [M  127]+), 157 (33, [M  137]+), 155 (92,
[M  139]+), 69 (30, [M  224]+), 57 (88, [M  237]+).
Di-tert-butoxy(chloro)(4-methylphenoxy)silane (tBuO)2-
(4-CH3C6H4O)SiCl; 2d). To (tBuO)2SiCl2 (1; 1.00 g,
4.08 mmol) in toluene (16 mL), imidazole (308 mg,
4.52 mmol) was added, followed by 4 mL of a 1.02 M
toluene solution of 4-methylphenol. The resulting mix-
ture was heated, while stirring, at 50 °C for 18 h. The
mixture was filtered, and the remaining solid washed
with toluene (3 9 5 mL). The filtrate and combined
washings were collected. The solvent was removed
from the filtrate in vacuo, yielding 1.063 g of crude
product. Distillation at 139 °C under vacuum yielded a
colorless oil (110 mg, 0.35 mmol), analyzed by EI-MS,
1
H-NMR, 13C-NMR, 1H,13C-HSQC, 1H,13C-HMBC, 1H,29Si-
HMBC, COSY, elemental analysis (EA; C and H), and
ATR-IR. IR (ATR): 2978m, 2933w, 1613w, 1510s, 1472s,
1392m, 1368m, 1246m, 1188m, 1067s, 1030w, 1018w,
949s, 818m, 801w, 693m, 650m, 635m. 1H-NMR
(300 MHz, (D8)THF): 7.03 (s, 2 H, 3,5-positions 4-
methylphenoxy); 6.88 (s, 2 H, 2,6-positions 4-methyl-
phenoxy; assigned using COSY, stronger correlation
with methyl group in 4 position. (see SI Figure 3.1.9));
2.25 (s, 3 H, C–CH3 (position 4 on 4-methylphenoxy);
1.39 (s, 18 H, C-CH3 (tBuO)). 13C-NMR (75.5 MHz, C6D6):
151.6; 131.9; 130.3; 119.9; 76.3; 31.2; 20.6. 29Si-NMR
(59.6 MHz, C6D6): -89 ppm. EI-MS: 316.1258 (M+,
C15H25ClO3Si+: 316.1256 (Dm/z = 0.0002 amu,
0.6 ppm)); 318 (26, [M + 2]+), 316 (73, +), 303 (27,
[M  13]+), 301 (78, [M  15]+), 247 (35, [M  69]+),
245 (100, [M  71]+), 206 (28, [M  110]+), 205 (20,
[M  111]+), 204 (84, [M  112]+), 57 (21,
[M  187]+). Anal. calc.: C 57.02, H 7.95; found: C
56.85, H 8.05.
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Di-tert-butoxy(chloro)(2,4,6-trimethylphenoxy)silane
((tBuO)2(2,4,6-(CH3)3C6H2O)SiCl; 2e). To (tBuO)2-
SiCl2 (1; 1.00 g, 4.08 mmol) in toluene (20 mL), imida-
zole (308 mg, 4.52 mmol) was added, followed by
2,4,6-trimethylphenol (554 mg, 4.07 mmol). The result-
ing mixture was heated, while stirring, at 50 °C for
18 h. The mixture was filtered and the remaining solid
washed with toluene (3 9 5 mL). The filtrate and
combined washings were collected. The solvent was
removed from the filtrate in vacuo. Distillation at
136 °C under static vacuum yielded 878 mg
(2.55 mmol, 63%) of a colorless oil, which was ana-
lyzed by EI-MS, 1H-NMR, 13C-NMR, 1H,13C-HSQC,
1 13
H, C-HMBC, 1H,29Si-HMBC, 29Si-NMR, elemental anal-
ysis (EA; C and H), and ATR-IR. IR (ATR): 2978m, 2932w,
1485m, 1392w, 1367m, 1314w, 1233m, 1191m, 1157m,
1071s, 1030m, 968m, 933m, 852m, 832w, 813w, 731w,
692m, 639s. 1H-NMR (300 MHz, C6D6): 6.74 (s, 2 H, 3,5-
positions 2,4,6-trimethylphenoxy); 2.43 (s, 6 H, C-CH3
(positions 2 & 6 on 2,4,6-trimethylphenoxy)); 2.11 (s, 3
H, C-CH3 (position 4 on 2,4,6-trimethylphenoxy); 1.30
(s, 18 H, C-CH3 (tBuO)). 13C-NMR (75.5 MHz, (D8)THF):
149.2; 131.9; 129.6; 128.7; 76.5; 31.2; 20.4; 17.8. 29Si-
NMR (59.6 MHz, C6D6): 89. EI-MS: 344.1569 (M+,
C17H29ClO3Si+: 344.1569 (Dm/z = 0.0000 amu,
0 ppm)); 346 (20, [M + 2]+), 344 (62, M+), 331 (31,
[M  13]+), 329 (85, [M  15]+), 288 (19, [M  56]+),
275 (20, [M  69]+), 273 (60, [M  71]+), 234 (32,
[M  110]+), 233 (36, [M  111]+), 232 (100,
[M  112]+), 231 (56, [M  113]+), 57 (81,
[M  187]+). Anal. calc.: C 59.01, H 8.47; found: C
59.19, H 8.49.
Synthesis and Characterization of Pure (tBuO)2(RO)SiOH
Samples
Di-tert-butyl Pent-4-en-2-yl Hydrogen Orthosilicate
((tBuO)2(CH2CHCH2CH(CH3)O)SiOH; 3a). (tBuO)2(CH2CH
CH2CH(CH3)O)SiCl (2a; 100 mg, 0.34 mmol) was dis-
solved in a biphasic mixture of water (1.0 mL) and
diethyl ether (1.5 mL), pyridine was added (30 lL,
0.38 mmol) and the resulting mixture was stirred for
18 h at room temperature. The organic phase was iso-
lated, washed three times with ice-cold distilled water
and dried over Na2SO4. The solution was filtered and
solvent was removed under reduced pressure. The
crude yield of the product was 84 mg. Distillation
under vacuum (95 °C), yielded 19 mg (0.07 mmol,
21%) of a clear oil. The product was analyzed by EI-
MS, 1H-NMR, 13C-NMR, 1H,13C-HSQC, 1H,13C-HMBC,
1 29
H, Si-HMBC, DEPT-90/135, elemental analysis (EA; C
and H), and ATR-IR. IR (ATR): 3406 (w, br.), 2974m,
2932w, 2907w, 1474w, 1458w, 1390w, 1379w, 1366m,
© 2018 Wiley-VHCA AG, Zurich, Switzerland
 Helv. Chim. Acta 2018, 101, e1700298
1242w, 1190m, 1131w, 1057s, 1026w, 1010m, 949w,
911s, 828w, 815w, 772w, 745w, 698m, 639w. 1H-NMR
(300 MHz, C6D6): 6.01 – 5.85 (m, 1 H, H2C=CH–R);
5.12 – 5.09 (m, 1 H, trans-H2C=CH–R); 5.08 – 5.02 (m,
1 H, cis-H2C=CH–R); 4.22 (sextet, J = 6.1, 1 H, O-CHRR0 );
2.46 – 2.35 (m, 1 H, R-CH2-CH(R0 )O); 2.30 – 2.19 (m, 1
H, R-CH2-CH(R0 )O); 1.38 (s, 18 H, CH3); 1.26 (d, J = 6.1,
3 H, CH3). 13C-NMR (75.5 MHz, C6D6): 136.0; 116.873.0;
69.3; 44.1; 31.6; 23.0. 29Si-NMR (59.6 MHz, C6D6): 88.
EI-MS: base peak: 261.1523 ([M  15]+, C12H24O3SiOH:
261.1517, (Dm/z = 0.0006 amu, 2.3 ppm)); 262, (18,
[M  14]+), 261 (100, [M  15]+), 235 (88, [M  41]+),
205 (26, [M  71]+), 203 (29, [M  73]+), 179 (24,
[M  97]+), 163 (21, [M  113]+), 147 (52,
[M  129]+), 135 (19, [M  139]+), 119 (16,
[M  157]+), 79 (27, [M  197]+), 69 (22, [M  207]+),
57 (87, [M  219]+). Anal. calc.: C 52.40, H: 9.94; found:
C 56.48, H 10.21.
Tri-tert-butyl Hydrogen Orthosilicate ((tBuO)3SiOH;
3b). (tBuO)3SiCl (2b; 225 mg, 0.71 mmol) was dis-
solved in diethyl ether (2.7 mL), imidazole was added
(64 mg, 0.94 mmol) followed by deionized water
(1.8 mL). The resulting mixture was stirred for 18 h at
room temperature. The organic phase was isolated
and washed three times with ice-cold distilled water
(3 9 2 mL), and dried over Na2SO4. The organic com-
ponent was filtered, and the solvent was removed
under reduced pressure. The yield of the product was
198 mg (93%). The product, a white solid, could be
used without further purification. The product was
analyzed by 1H-NMR to confirm formation of silanol.
Known compound, commercially available tris-tert-
butoxysilanol (Sigma–Aldrich, 99.9999%) used as refer-
ence. 1H-NMR (300 MHz, C6D6): 1.40.
Di-tert-butyl 2-Methylbut-3-en-2-yl Hydrogen
Orthosilicate ((tBuO)2(CH2CHC(CH3)2O)SiOH; 3c).
(tBuO)2(CH2CHC(CH3)2O)SiCl (2c; 1.35 g, 4.58 mmol)
was dissolved in a diethyl ether (18 mL). Imidazole was
added (362 mg, 5.31 mmol), followed by deionized
water (12 mL). The resulting mixture was stirred for
18 h at room temperature. The organic phase was iso-
lated and washed three times with ice-cold distilled
water, and subsequently dried over Na2SO4. The solu-
tion was filtered, and solvent was removed under
reduced pressure. Distillation under vacuum (68 °C),
yielded 812 mg (1.00 mmol, 21%) of a colorless oil. The
product was analyzed by EI-MS, 1H-NMR, 13C-NMR,
1 13
H, C-HSQC, 1H,13C-HMBC, 1H,29Si-HMBC, elemental
analysis, and ATR-IR. IR (ATR): 3399 (br.), 2974m, 1365m,
1240m, 1182m, 1153w, 1053s, 1041s, 1011s, 914m,
825m, 696s. 1H-NMR (300 MHz, C6D6): 6.08 (dd, J = 17.3,
10.9, 1 H, H2C=CH–R); 5.26 (dd, J = 17.3, 1.6, 1 H, trans-
H2C=CH–R); 4.93 (dd, J = 10.9, 1.6, 1 H, cis-H2C=CH–R);
www.helv.wiley.com (7 of 10) e1700298
2.07 (br. s, OH); 1.47 (s, 6 H, CH3); 1.39 (s, 18 H, CH3). 13C-
NMR (75.5 MHz, C6D6): 146.7; 110.3; 74.5; 72.8; 31.4;
29.5. 29Si-NMR (59.6 MHz, C6D6): 91. EI-MS: base peak:
261.1523 ([M  15]+, C12H24O3SiOH+; calc. 261.1517,
(Dm/z = 0.0006 amu, 2.3 ppm)); 262 (18, [M  14]+),
261 (100, [M  15]+), 235 (88, [M  41]+), 205 (26,
[M  71]+), 203 (29, [M  73]+), 179 (24, [M  97]+),
163 (21, [M  113]+), 147 (52, [M  129]+), 135 (19,
[M  139]+), 119 (16, [M  157]+), 79 (27, [M  197]+),
69 (22, [M  207]+), 57 (87, [M  219]+). Anal. calc.: C
56.69, H 10.34; found: C 56.48, H 10.21.
Di-tert-butyl 4-Methylphenyl Hydrogen Orthosili-
cate ((tBuO)2(4-(CH3)C6H4O)SiOH; 3d). (tBuO)2(4-
CH3C6H4O)SiCl (2d; 60 mg, 0.19 mmol) was dissolved
in diethyl ether (1 mL), imidazole was added (16 mg,
0.24 mmol) followed by deionized water (0.7 mL). The
resulting mixture was stirred for 18 h at room temper-
ature. The organic phase was isolated and washed
three times with ice cold distilled water, and dried
over Na2SO4. The organic component was filtered,
and solvent was removed under reduced pressure.
The yield of the product was 50 mg (0.17 mmol,
88%). The product, a colorless oil, was analyzed by EI-
MS, 1H-NMR, 13C-NMR, 1H,13C-HSQC, 1H,13C-HMBC,
1 29
H, Si-HMBC, and ATR-IR. IR (ATR): 3420 (m, br.),
2975m, 2931s, 2873w, 1613m, 1511s, 1473w, 1391m,
1366m, 1262m, 1245m, 1191m, 1063s, 1016m, 942m,
819s, 794w, 695m, 645m, 620w. 1H-NMR (300 MHz,
(D8)THF): 7.04 (s, 2 H, 3,5-positions 4-methylphenoxy);
6.93 (s, 2 H, 2,6-positions 4-methylphenoxy)); 2.54 (s, 1
H, OH); 2.29 (s, 3 H, C-CH3 (position 4 on 4-
methylphenoxy); 1.36 (s, 18H, C-CH3 (tBuO)). 13C-NMR
(75.5 MHz, CDCl3): 151.8; 130.8; 129.8; 119.2; 74.0; 31.3;
20.6. 29Si-NMR (59.6 MHz, C6D6): 91. EI-MS: base
peak: 298.1598 (M+, C15H26O4Si+; calc. 298.159, (Dm/z
= 0.0003 amu, 1.01 ppm)); 298 (59, M+), 283 (44,
[M  15]+), 228 (15, [M  70]+), 227 (100, [M  71]+),
186 (34, [M  112]+), 57 (21, [M  231]+).
Di-tert-butyl 2,4,6-Trimethylphenyl Hydrogen
Orthosilicate ((tBuO)2(2,4,6-(CH3)3C6H2O)SiOH; 3e).
(tBuO)2(2,4,6-(CH3)3C6H2O)SiCl (2e; 400 mg, 1.16 mmol)
was dissolved in diethyl ether (4 mL), imidazole was
added (91 mg, 1.34 mmol) followed by deionized
water (2.7 mL). The resulting mixture was stirred for
18 h at room temperature. The organic phase was iso-
lated and washed three times with ice-cold distilled
water, and subsequently dried over Na2SO4. The
organic component was filtered, and the solvent was
removed under reduced pressure. The yield of the
product was 214 mg (0.65 mmol, 56%). The product,
a white solid, could be used without further purifica-
tion. The product was analyzed by EI-MS, 1H-NMR,
13
C-NMR, 1H,13C-HSQC, 1H,13C-HMBC, 1H,29Si-HMBC,
© 2018 Wiley-VHCA AG, Zurich, Switzerland
 Helv. Chim. Acta 2018, 101, e1700298

Table 3. Crystallographic parameters for (tBuO)2(2,4,6-(CH3)3- ether solution of crude 3e. X-ray crystallographic
C6H2SiOH (3e, CCDC 1821646)[a] parameters are given below in Table 3.
Crystallographic Data for (tBuO)2(2,4,6-(CH3)3C6H2SiOH

Molecular formula C17H30O4Si Supplementary Material

Formula weight 326.51 Supporting information for this article is available on the
Temp [K] 106(2)
WWW under https://doi.org/10.1002/hlca.201700298.
Crystal system Triclinic
Space group P-1
Cell constants Acknowledgements
a [
A] 8.7114(6)
b [
A] 9.1397(6) The authors would like to thank the Swiss National
c [
A] 12.2709(8) Science Foundation, ETH Zu €rich, and the ETH Postdoc-
a [deg] 79.721(4)
toral Fellowship for funding. The authors would also
b [deg] 85.966(4)
c [deg] 83.915(4)
like to thank Dr. Daniel Silverio and Dr. Keith Searles for
Z 2 helpful discussions during the course of this work.
V [
A3] 954.585
Abs coeff [mm1] 0.137
Calc. density [g cm3] 1.136
Author Contribution Statement
F(000) 356 S. R. D. performed and developed the synthetic proto-
Crystal dimensions [mm]
col. D. E. and C. C. conceived the project. S. R. D., D. E.,
Wavelength [ A] 0.71073
h,k,l ranges collected 11 ≤ h ≤ 11, 12 ≤ and C. C. wrote the manuscript.
k ≤ 12, 16 ≤ l ≤ 16
h range for data collection [deg] 1.689 – 28.469 References
Number of reflns collected 17620
Number of unique reflns [1] W. A. Herrmann, R. Anwander, V. Dufaud, W. Scherer,
Number of parameters 209 ‘Molecular Siloxane Complexes of Rare Earth Metals–Model
Data to parameter ratio Systems for Silicate-Supported Catalysts?’, Angew. Chem.
Refinement method Int. Ed. 1994, 33, 1285 – 1286.
R1 [2] D. P. Estes, A. K. Cook, E. Lam, L. Wong, C. Cop
eret, ‘Under-
wR2 standing the Lewis Acidity of Co(II) Sites on a Silica Sur-
[a]
face’, Inorg. Chem. 2017, 56, 7731 – 7736.
CCDC-1821646 contain(s) the supplementary crystallographic [3] D. P. Estes, G. Siddiqi, F. Allouche, K. V. Kovtunov, O. V.
data for this work. These data can be obtained free of charge Safonova, A. L. Trigub, I. V. Koptyug, C. Cop
eret, ‘C–H Acti-
from The Cambridge Crystallographic Data Centre via vation on Co, O Sites: Isolated Surface Sites versus Molec-
www.ccdc.cam.ac.uk/data_request/cif. ular Analogs’, J. Am. Chem. Soc. 2016, 138,
14987 – 14997.
[4] J. Beckmann, D. Dakternieks, A. Duthie, M. L. Larchin, E. R.
DEPT-45/90/135, elemental analysis (EA; C and H), and T. Tiekink, ‘tert-Butoxysilanols as Model Compounds for
Labile Key Intermediates of the Sol–Gel Process: Crystal
ATR-IR. IR (ATR): 3334 (m, broad), 2974m, 2923w,
and Molecular Structures of (t-BuO)3SiOH and HO[(t-BuO)2-
2869w, 1482m, 1391w, 1364m, 1313m, 1233m, 1193m, SiO]2H’, Appl. Organomet. Chem. 2003, 17, 52 – 62.
1157w, 1044s, 1010s, 968m, 907m, 851m, 828m, 804w, [5] R. Duchateau, T. W. Dijkstra, R. A. van Santen, G. P. A. Yap,
735w, 693s, 627w. 1H-NMR (300 MHz, C6D6): 6.79 (s, 2 ‘Silsesquioxane Models for Silica Surface Silanol Sites with
H, 3,5 positions 2,4,6-trimethylphenoxy); 2.40 (s, 6 H, Adjacent Siloxide Functionalites and Olefin Polymerization
C-CH3 (positions 2 & 6 on 2,4,6-trimethylphenoxy)); Catalysts Thereof’, Chem. Eur. J. 2004, 10, 3979 – 3990.
[6] E. A. Quadrelli, J.-M. Basset, ‘On Silsesquioxanes’ Accuracy
2.15 (s, 3 H, C-CH3 (position 4 on 2,4,6-trimethylphe-
as Molecular Models for Silica-Grafted Complexes in
noxy); 2.00 (s, 1 H,Si-OH); 1.30 (s, 18 H, C-CH3 (tBuO)). Heterogeneous Catalysis’, Coord. Chem. Rev. 2010, 254,
13
C-NMR (75.5 MHz, C6D6): 147.5; 127.8; 126.6; 126.4; 707 – 728.
70.6; 28.00; 17.8; 15.1. 29Si-NMR (59.6 MHz, C6D6): 93. [7] T. W. Dijkstra, R. Duchateau, R. A. van Santen, A. Meetsma,
EI-MS: base peak: 326.1906 (M+, C17H29O3SiOH+; calc. G. P. A. Yap, ‘Silsesquioxane Models for Geminal Silica Sur-
316.1908, (Dm/z = 0.0002 amu, 0.61 ppm)); 326, (50, face Silanol Sites. A Spectroscopic Investigation of Different
M+), 311 (56, [M  15]+), 255 (18, [M  71]+), 214 (57, Types of Silanols’, J. Am. Chem. Soc. 2002, 124,
9856 – 9864.
[M  112]+), 213 (100, [M  113]+), 57 (56, [8] J. Jarupatrakorn, T. D. Tilley, ‘Silica-Supported, Single-Site
[M  269]+). Anal. calc.: C 62.33, H 9.18; found: C Titanium Catalysts for Olefin Epoxidation. A Molecular Pre-
62.54, H 9.26. Crystals suitable for X-ray diffraction cursor Strategy for Control of Catalyst Structure’, J. Am.
were grown by slow evaporation of a 1:1 cyclohexane Chem. Soc. 2002, 124, 8380 – 8388.

www.helv.wiley.com (8 of 10) e1700298 © 2018 Wiley-VHCA AG, Zurich, Switzerland

 Helv. Chim. Acta 2018, 101, e1700298
[9] R. L. Miller, R. Toreki, R. E. LaPointe, P. T. Wolczanski, G. D.
Van Duyne, D. C. Roe, ‘Syntheses, Carbonylations, and
Dihydrogen Exchange Studies of Monomeric and Dimeric
Silox (tert-Bu3SiO-) Hydrides of Tantalum: Structure of
[(silox)2TaH2]2’, J. Am. Chem. Soc. 1993, 115, 5570 – 5588.
[10] S. N. Ko €nig, C. Maichle-Mo €ssmer, K. W. To€rnroos, R. Anwan-
der, ‘Siloxide Complexes of Chromium(II), Manganese(II),
Cobalt(II), and Chromium(III) Incorporating Potassium(I)’, Z.
Naturforsch. B 2014, 69, 1375 – 1383.
[11] K. L. Fujdala, A. G. Oliver, F. J. Hollander, T. D. Tilley, ‘Tris
(tert-butoxy)siloxy Derivatives of Boron, Including the Bor-
onous Acid HOB[OSi(OtBu)3]2 and the Metal (Siloxy)boryl-
oxide Complex Cp2Zr(Me)OB[OSi(OtBu)3]2: A Remarkable
Crystal Structure with 18 Independent Molecules in Its
Asymmetric Unit’, Inorg. Chem. 2003, 42, 1140 – 1150.
[12] K. W. Terry, P. K. Gantzel, T. D. Tilley, ‘Chromium(II) and
Chromium(III) Tri-tert-butoxysiloxy Complexes’, Inorg.
Chem. 1993, 32, 5402 – 5404.
[13] R. Murugavel, V. Chandrasekhar, H. W. Roesky, ‘Discrete
Silanetriols: Building Blocks for Three-Dimensional Metal-
lasiloxanes’, Acc. Chem. Res. 1996, 29, 183 – 189.
[14] R. Murugavel, A. Voigt, M. G. Walawalkar, H. W. Roesky,
‘Hetero- and Metallasiloxanes Derived from Silanediols,
Disilanols, Silanetriols, and Trisilanols’, Chem. Rev. 1996, 96,
2205 – 2236.
[15] R. Murugavel, M. Bhattacharjee, H. W. Roesky, ‘Organosi-
lanetriols: Model Compounds and Potential Precursors for
Metal-Containing Silicate Assemblies’, Appl. Organomet.
Chem. 1999, 13, 227 – 243.
[16] P. D. Lickiss, ‘Polysilanols’, in ‘The Chemistry of Organic Sili-
con Compounds’, John Wiley & Sons, Ltd., 2001, pp.
695 – 744.
[17] P. D. Lickiss, ‘The Synthesis and Structure of Organosi-
lanols’, in ‘Advances in Inorganic Chemistry’, Vol. 42, Ed. A.
G. Sykes, Academic Press, 1995, pp. 147 – 262.
[18] C. Krempner, ‘Role of Siloxides in Transition Metal Chem-
istry and Homogeneous Catalysis’, Eur. J. Inorg. Chem.
2011, 1689 – 1698.
[19] V. Chandrasekhar, R. Boomishankar, S. Nagendran, ‘Recent
Developments in the Synthesis and Structure of Organosi-
lanols’, Chem. Rev. 2004, 104, 5847 – 5910.
[20] C. Cop
eret, A. Comas-Vives, M. P. Conley, D. P. Estes, A.
Fedorov, V. Mougel, H. Nagae, F. N
~ez-Zarur, P. A.
un
Zhizhko, ‘Surface Organometallic and Coordination Chem-
istry toward Single-Site Heterogeneous Catalysts: Strate-
gies, Methods, Structures, and Activities’, Chem. Rev. 2016,
116, 323 – 421.
[21] M. P. Conley, M. F. Delley, G. Siddiqi, G. Lapadula, S.
Norsic, V. Monteil, O. V. Safonova, C. Cop
eret, ‘Polymer-
ization of Ethylene by Silica-Supported Dinuclear CrIII
Sites Through an Initiation Step Involving C–H Bond
Activation’, Angew. Chem. Int. Ed. 2014, 53,
1872 – 1876.
[22] C. Nozaki, C. G. Lugmair, A. T. Bell, T. D. Tilley, ‘Synthesis,
Characterization, and Catalytic Performance of Single-Site
Iron(III) Centers on the Surface of SBA-15 Silica’, J. Am.
Chem. Soc. 2002, 124, 13194 – 13203.
[23] S. A. Strazisar, P. T. Wolczanski, ‘Insertion of H2C=CHX
(X = F, Cl, Br, OiPr) into (tBu3SiO)3TaH2 and b-X-Elimination
from (tBu3SiO)3HTaCH2CH2X (X = OR): Relevance to
www.helv.wiley.com (9 of 10) e1700298
ZieglerNatta Copolymerizations’, J. Am. Chem. Soc. 2001,
123, 4728 – 4740.
[24] G. Lapadula, M. P. Conley, C. Cop
eret, R. A. Andersen, ‘Syn-
thesis and Characterization of Rare Earth Siloxide Com-
plexes, M[OSi(OtBu)3]3(L)x Where L is HOSi(OtBu)3 and
x = 0 or 1’, Organometallics 2015, 34, 2271 – 2277.
[25] G. Lapadula, D. Trummer, M. P. Conley, M. Steinmann, Y.-F.
Ran, S. Brasselet, Y. Guyot, O. Maury, S. Decurtins, S.-X. Liu,
C. Cop
eret, ‘One-Photon Near-Infrared Sensitization of
Well-Defined Yb(III) Surface Complexes for NIR-to-NIR Sin-
gle Nanoparticle Imaging’, Chem. Mater. 2015, 27,
2033 – 2039.
[26] R. E. Douthwaite, P. T. Wolczanski, E. Merschrod,
‘[(silox)2ReO]2 (silox = tBu3SiO) Contains a ReRe Bond
and Terminal Oxo Ligands’, Chem. Commun. 1998,
2591 – 2592.
[27] R. E. LaPointe, P. T. Wolczanski, J. F. Mitchell, ‘Carbon
Monoxide Cleavage by (silox)3Ta (silox = tert-Bu3SiO-)’, J.
Am. Chem. Soc. 1986, 108, 6382 – 6384.
[28] F. Allouche, G. Lapadula, G. Siddiqi, W. W. Lukens, O.
Maury, B. Le Guennic, F. Pointillart, J. Dreiser, V. Mougel, O.
Cador, C. Cop
eret, ‘Magnetic Memory from Site Isolated
Dy(III) on Silica Materials’, ACS Centr. Sci. 2017, 3,
244 – 249.
[29] N. Rendo
n, A. Bourdolle, P. L. Baldeck, H. Le Bozec, C.
Andraud, S. Brasselet, C. Coperet, O. Maury, ‘Bright Lumi-
nescent Silica Nanoparticles for Two-Photon Microscopy
Imaging via Controlled Formation of 4,4’-Diethylaminos-
tyryl-2,2’-bipyridine Zn(II) Surface Complexes’, Chem. Mater.
2011, 23, 3228 – 3236.
[30] H. J. Backer, H. A. Klasens, ‘Esters Mixtes de L’acide
T
etrathioorthosilicique’, Recl. Trav. Chim. Pays-Bas 1942, 61,
500 – 512.
[31] G. Schott, L. Engelbrecht, H. J. Holdt, ‘Silanole, XV. Alkoxy-
silanole – partielle Kiesels€aureester’, Z. Anorg. Allgem.
Chem. 1979, 459, 177 – 186.
[32] Y. Abe, I. Kijima, ‘Alkoxysilanes. IV. Preparation of Alkoxysi-
loxy Derivatives of Titanium’, Bull. Chem. Soc. Jpn. 1970,
43, 466 – 469.
[33] S. K. Verma, B. N. Acharya, M. P. Kaushik, ‘Imidazole-Cata-
lyzed Monoacylation of Symmetrical Diamines’, Org. Lett.
2010, 12, 4232 – 4235.
[34] E. J. Corey, A. Venkateswarlu, ‘Protection of Hydroxyl
Groups as Tert-Butyldimethylsilyl Derivatives’, J. Am. Chem.
Soc. 1972, 94, 6190 – 6191.
[35] M. N. Khan, S. Pal, S. Karamthulla, L. H. Choudhury, ‘Imida-
zole as Organocatalyst for Multicomponent Reactions:
Diversity Oriented Synthesis of Functionalized Hetero- and
Carbocycles Using In situ-Generated Benzylidenemalononi-
trile Derivatives’, RSC Adv. 2014, 4, 3732 – 3741.
[36] S. Jones, J. Northen, A. Rolfe, ‘Catalytic Phosphorylation
Using a Bifunctional Imidazole Derived Nucleophilic Cata-
lyst’, Chem. Commun. 2005, 3832 – 3834.
[37] F.-M. Gautier, S. Jones, S. J. Martin, ‘Asymmetric Reduction
of Ketimines with Trichlorosilane Employing an Imidazole
Derived Organocatalyst’, Org. Biomol. Chem. 2009, 7,
229 – 231.
[38] P. Nieri, S. Carpi, S. Fogli, B. Polini, M. C. Breschi, A.
Podesta, ‘Cholinesterase-Like Organocatalysis by Imidazole
and Imidazole-Bearing Molecules’, Sci. Rep. 2017, 7, 45760.
© 2018 Wiley-VHCA AG, Zurich, Switzerland
 Helv. Chim. Acta 2018, 101, e1700298

[39] P. Patschinski, C. Zhang, H. Zipse, ‘The Lewis Base-Cata-
lyzed Silylation of Alcohols–A Mechanistic Analysis’, J. Org.
Chem. 2014, 79, 8348 – 8357.
[40] H. Mayr, A. R. Ofial, ‘Philicities, Fugalities, and Equilibrium
Constants’, Acc. Chem. Res. 2016, 49, 952 – 965.
[41] K. Izutsu, ‘Acid-Base Dissociation Constants in Dipolar
Aprotic Solvents’, Blackwell Scientific Publications, Oxford,
UK, 1990.
[42] G. R. Fulmer, A. J. M. Miller, N. H. Sherden, H. E. Gottlieb,
A. Nudelman, B. M. Stoltz, J. E. Bercaw, K. I. Goldberg,
‘NMR Chemical Shifts of Trace Impurities: Common Labora-
tory Solvents, Organics, and Gases in Deuterated Solvents
Relevant to the Organometallic Chemist’, Organometallics
2010, 29, 2176 – 2179.
Received December 22, 2017
Accepted January 31, 2018

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