Hydrosilylation of nitrogen-containing organic compounds: Model studies

Article abstract of DOI:10.1016/j.jorganchem.2019.07.017

1,1,3,3-tetramethyldisiloxane (M₂^H) was used as the hydrosilylating agent for nitrogen-containing alkene derivatives: N-allylaniline (Naa), N-allylcyclohexylamine (Nach), N-allylpiperidine (Nap), 4-vinylpyridine (4VP) and 2-vinylpyri

Full text of DOI:10.1016/j.jorganchem.2019.07.017

Accepted Manuscript
Hydrosilylation of nitrogen-containing organic compounds: Model studies
Aleksandra Chechelska-Noworyta, Maria Owińska, Magdalena Hasik
PII:
S0022-328X(19)30300-6
DOI:
https://doi.org/10.1016/j.jorganchem.2019.07.017
JOM 20866
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 18 February 2019
Revised Date: 9 May 2019
Accepted Date: 15 July 2019
Please cite this article as: A. Chechelska-Noworyta, M. Owińska, M. Hasik, Hydrosilylation of nitrogen-
containing organic compounds: Model studies, Journal of Organometallic Chemistry (2019), doi: https://
doi.org/10.1016/j.jorganchem.2019.07.017.
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ACCEPTED MANUSCRIPT
Hydrosilylation of nitrogen-containing organic compounds: model studies
Aleksandra Chechelska-Noworyta*, Maria Owińska, Magdalena Hasik
AGH−University of Science and Technology, Faculty of Materials Science and Ceramics
Al. Mickiewicza 30, 30-059 Kraków, Poland
*
e-mail: acheche@agh.edu.pl
Abstract
,1,3,3-tetramethyldisiloxane (M ) was used as the hydrosilylating agent for nitrogen-
H
1
2
containing alkene derivatives: N-allylaniline (Naa), N-allylcyclohexylamine (Nach), N-
allylpiperidine (Nap), 4-vinylpyridine (4VP) and 2-vinylpyridine (2VP). Reactions were
0
o
performed in the presence of Pt complex (Karstedt’s catalyst), in toluene, at 60 C, for 24
hours. Their course was followed by gas chromatography and FTIR spectroscopy. Final
1
13
29
hydrosilylation products were characterized by FTIR, H, C and Si NMR spectroscopies as
H
well as by elemental analysis. Total conversion of Si-H groups present in M2 in its reactions
H
with N-allyl compounds was established, the process with Naa being the fastest. M2 reacted
to a significantly lower degree with 2VP, while the reaction with 4VP did not occur. Results
can be explained in terms of possible interactions of nitrogen atoms in alkene derivatives with
Pt centers in the catalyst. The investigations model functionalization of siloxanes with
nitrogen-containing groups via hydrosilylation conducted in the presence of Pt catalysts on
which conflicting results are presented in the literature.
Key words:
siloxanes, tetramethyldisiloxane, hydrosilylation of amines, hydrosilylation of pyridines
1

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1
. Introduction
Nitrogen-containing organic compounds constitute a wide, diverse and important class
of compounds due to nonbonding electron pairs on nitrogen atoms which potentially give
them basic and nucleophilic properties. Presence of the lone electron pairs allows for the
formation of coordinate bonds; therefore these compounds can act as ligands for metal ions or
particles [1-4]. Amines and heterocyclic nitrogen-containing organic compounds can be
transformed in a one-step procedure, by direct alkylation or reaction with an acid, to their salts
which exhibit antibacterial and antifungal activity and are widely used as disinfectants [5-8].
Siloxanes are the organosilicon compounds in which silicon atoms are linked via
oxygen atoms and to each silicon atom one or several (up to three) organic groups are
attached [9]. They occur in linear and cyclic forms, can be low-molecular-weight or
polymeric. A very wide Si-O-Si bond angle (145°) and unique flexibility of the siloxane chain
are characteristic features of the linear molecules [9, 10]. Siloxanes and polysiloxanes are
used in various fields: as ingredients in cosmetic products, maintenance products (e.g. wax),
processing aids (release agents in the processing of plastics, antifoams in the processing of
petroleum), in medical or pharmaceutical preparations, as defoaming agents, paints, coatings,
mechanical fluids, sealants and rubber [11, 12].
Siloxanes and polysiloxanes are susceptible to chemical modifications. Siloxanes
functionalized by organic groups combine unique properties of both, siloxane and organic
parts. In particular, amino groups in siloxane structure render these compounds amphiphilic as
well as make their further transformations possible. Aminosiloxane coatings facilitate
adhesion of glass fibers to polymer matrices and improve strength of glass fiber-polymer
composites [13]. Their layers deposited on the surface of Ti alloy ensure biocompatibility,
while subsequent coupling of the surface amino groups with trans-cinnamaldehyde provides
these implant materials with antimicrobial properties [14]. Aminosiloxanes are applied as
softeners in textile [15] and cosmetic [16] industry. They can also serve as cross-linking
agents for waterborne polyurethanes [17]. Additionally, amine-functionalized polysiloxanes,
due to coordinative ability, can be used for extraction of toxic metal ions from waste water
[
18], as supports for metallic catalysts [19, 20] or as stabilizers for metal nanoparticles [21].
After transformation into quaternary ammonium salts (QAS) they exhibit antimicrobial
properties [22]. Similarly, polysiloxanes modified by other nitrogen-containing moieties, e.g.
imidazolyl or triazolyl groups, can be applied as carriers for metallic catalysts [23, 24]; the
latter, in their salt forms, show biocidal activity [25].
2

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Siloxane compounds containing nitrogen atoms can be obtained by several methods.
Hydrolytic condensation or polycondensation in which alkoxysilanes with incorporated
nitrogen moieties participate is one of the possible routes [18-20, 25-27]. N-methyl-aza-2,2,4-
trimethylsilacyclopentane can serve as the source of aminoalkyl units in siloxanes [21]. Other
methods are based on transformations of functional groups (e.g. azide [28, 29], epoxy [30,
3
1]) previously introduced into molecules of siloxane compounds. Additionally, if appropriate
monomers are available, ring-opening polymerization of cyclic siloxanes containing nitrogen
atoms can be carried out to prepare modified polymers [25].
Organofunctional siloxanes are often synthesized by hydrosilylation [32, 33]. This
reaction involves addition of Si-H groups to multiple carbon-carbon or carbon-heteroatom
bonds and requires the use of a catalyst. In the hydrosilylation of carbon-carbon double bonds,
most suitable for the preparation of organofunctional siloxanes [32, 33], Pt catalysts,
especially the so-called Speier’s (H PtCl dissolved in isopropanol) and Karstedt’s (complex
2
6
0
of Pt and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane) catalysts are very efficient and therefore
their application is well established [34, 35]. Hydrosilylation of nitrogen-containing
unsaturated organic compounds may lead, however, to poisoning of Pt catalysts [34, 35].
Inhibiting effect of amines and aminated polymers on Speier’s catalyst has been documented
[
36]. Because of this, hydrosilylation of some nitrogen-containing compounds, such as
allylamine in the presence of Pt catalysts has been performed after protecting amino group by
t-butylcarbonyl moiety [37, 38]. On the other hand, amines are known as additives that act as
promoters for Pt hydrosilylation catalysts [35]. Moreover, there are reports on successful
functionalization of polyhydromethylsiloxane with N-allylcyclohexylamine moieties [39],
hydride-terminated polydimethylsiloxane [40] and dimethylsiloxane-methylhydrosiloxane
copolymer [41, 42] with 4-vinylpyridine groups or dimethylsiloxane-methylhydrosiloxane
copolymer with the units originating from dimethylallylamine [43] by hydrosilylation using
Pt catalysts.
It should be noted that, up to our knowledge, in the literature there are no systematic
studies on modification of siloxanes or polysiloxanes by hydrosilylation of various nitrogen-
containing unsaturated organic compounds in the presence of Pt catalysts. Therefore we
decided to conduct model investigations in which N-allyl compounds: N-allylaniline (Naa),
N-allylcyclohexylamine (Nach), N-allylpiperidine (Nap) and vinyl nitrogen-containing
compounds: 4-vinylpyridine (4VP), 2-vinylpyridine (2VP) were hydrosilylated by 1,1,3,3-
H
tetramethyldisiloxane (M ). The reactions were conducted using Karstedt’s catalyst, under
2
3

ACCEPTED MANUSCRIPT
o
mild conditions - in toluene, at 60 C. The N-containing compounds selected for our studies
differed in basicity/nucleophicity as well as in molecular structure. The studies have been
aimed at checking how these factors affect hydrosilylation reactions.
It is worth mentioning that, apart from modelling hydrosilylation of N-containing
unsaturated organic compounds catalyzed by a Pt complex, our investigations provide the
H
first, not presented previously in the literature characterization of the reactions between M2
and the chosen N-containing compounds as well as their products. Out of the systems studied
H
in this work, only hydrosilylation of Naa and Nach by M2 performed in the presence of
hexachloroplatinic acid has been described [44]. However, neither the courses of these
processes nor the structures of their products have been disclosed. There is also a patent
which mentions that the disiloxane with two methyl groups and Naa moiety attached to each
Si atom in the molecule can be prepared by another route (from a cyclic aminoorganosilane),
but again no details on the compound are given [45].
2
2
1
. Experimental
.1 Materials
H
,1,3,3-tetramethyldisiloxane (M ) was purchased from ABCR, Germany and used as
2
supplied. Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Karstedt’s catalyst)
was supplied by Sigma-Aldrich as the solution in xylene (2 wt.% of Pt) and used without
further purification. 4-vinylpyridine (4PV), 2-vinylpyridine (2VP), N-allylaniline (Naa) and
N-allylcyclohexylamine (Nach) were purchased from Sigma-Aldrich and purified by vacuum
distillation before use. N-allylpiperidine (Nap) was prepared by the method described in
H
section 2.2. 1,1,1,3,3-pentamethyldisiloxane (MM ) was purchased from ABCR (Germany)
and applied as received. Toluene was supplied by POCh, Poland and was distilled from
sodium-benzophenone prior to use.
Piperidine, sodium hydride 60% in mineral oil and allyl bromide applied in the
preparation of N-allylpiperidine, were purchased from ABCR (Germany), Sigma-Aldrich
(Poland) and Avantor (Poland), respectively and used in the work without purification.
Diethyl ether was purchased from Avantor and, before use, dried using benzophenone and
sodium, and then distilled under Ar.
4

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2
.2. Synthesis of N-allylpiperidine
N-Allylpiperidine was synthesized using the procedure presented in [46]. Thus, in a round-
bottomed flask equipped with a stirring bar 60% NaH solution in mineral oil (7.0 g, 0.117
mol) was suspended in diethyl ether (20.0 ml). Then piperidine (11.6 ml, 10.0 g, 0.117 mol)
was slowly added dropwise and the mixture was stirred for 30 minutes at room temperature.
After that, the flask was placed in an ice bath, cooled to 0°C and the solution of allyl bromide
(10.1 ml, 14.2 g, 0.117 mol) in diethyl ether (40.0 ml) was slowly added via dropping funnel.
The temperature was subsequently increased to room temperature and then the reaction was
carried out for 70 hours. After this time, the reaction mixture was washed with KOH solution
and extracted with diethyl ether. The combined organic layers were washed with water, dried
over anhydrous MgSO and evaporated. The resulting oil was distilled under reduced pressure
4
to obtain N-allylpiperidine as a colorless liquid (7.8 g, 53%). Its chromatographic purity (GC)
1
was 93%. H NMR (CDCl , 400 MHz):
δ
=1.38-1.40 (m, 2H), 1.50-1.56 (m, 4H), 2.33 (br s,
3
1
3
4
2
H), 2.90-2.92 (d, 2H), 5.06-5.13 (m, 2H), 5.79-5.89 (m, 1H); C NMR (CDCl3): δ=24.4,
6.0, 54.5, 62.7, 117.5, 135.7 ppm.
H
2
.3. Functionalization of M2 with nitrogen-containing compounds
H
M2 was functionalized with organic compounds containing a nitrogen atom by
hydrosilylation performed in the presence of Karstedt's catalyst. Reactions were carried out in
a clean and dry Schlenk flask under dry argon atmosphere. Molar ratio of Si-H groups from
the siloxane to CH =CH-CH - or CH =CH- groups from the nitrogen-containing organic
2
2
2
compound equal to 1:1.5 was applied. The excess of organic compound over the Si-H groups
in the siloxane was used to ensure that all Si-H groups were substituted.
H
In a typical run, 0.0085 mol (1.5 ml) of M2 and 0.0255 mol of nitrogen-containing
organic compound (Naa: 3.46 ml, Nap: 3.74 ml, Nach: 3.69 ml, 4VP: 2.76 ml, 2VP: 2.75 ml)
-6
in toluene (3.0 ml) were used. The reactions were catalyzed by 0.17·10 mol of Pt introduced
into the system from Karstedt’s catalyst. The reaction temperature was controlled at 60°C for
2
4 h. Gas chromatograms (GC) and FTIR spectra of the initial reaction mixture as well as the
samples withdrawn after 1, 3 and 24 hours of the process were recorded. Based on GC,
H
changes in the concentrations of the reagents (M , the organic compound) were determined,
2
whereas the measured FTIR spectra served as the basis for establishing the disappearance of
the Si-H groups from the systems. After the reactions, toluene was removed by rotary
5

ACCEPTED MANUSCRIPT
evaporation. Then the remaining mixture was subjected to vacuum distillation in order to
distill off the unreacted N-containing compound. This method was sufficient to separate
H
H
siloxane functionalized by Nach from the excess of Nach. In the case of M /Naa, M /Nap
2
2
H
and M /2VP systems, separation by column chromatography on silica gel using as eluent
2
hexane/dichloromethane mixture, ethyl acetate and hexane/ethyl acetate mixture, respectively
H
was additionally performed. It was, however, inefficient in the isolation of M /2VP product.
2
Additionally, in order to facilitate interpretation of gas chromatograms, the reaction
H
between M2 and Naa was carried out by the described procedure, but using excessive amount
of the siloxane (Si-H : CH =CH-CH - groups molar ratio equal to 1:0.5).
2
2
2
.4. Functionalization of 1,1,1,3,3-pentamethyldisiloxane by N-allylcyclohexylamine
H
Functionalization of 1,1,1,3,3-pentamethyldisiloxane (MM ) by Nach was performed in an
H
H
analogous manner to functionalization of M2 by Nach. 0.0079 mol (1.5 ml) of MM , 0.0119
-6
mol (1.72 ml) of Nach and Karstedt’s catalyst (0.17·10 mol of Pt) in toluene (3 ml) were
used. The reaction temperature was controlled at 60°C for 24 h. After the reaction, toluene
was removed by rotary evaporation. Then the remaining mixture was subjected to vacuum
distillation in order to distill off the unreacted Nach.
2
.5. Characterization methods
1
29
H NMR and Si NMR spectra were recorded on a Bruker Avance III HD (400 MHz)
Spectrometer, using CDCl (δ=7.26 ppm) as solvent. Fourier transform infrared (FTIR)
3
spectra were recorded on a FTIR (BIO-RAD Excalibur) spectrometer, equipped with a
horizontal zinc selenide (ZnSe) ATR sampling accessory. Spectra were obtained after
-1
◦
collecting 32 scans in the 4000 to 550 cm range; incident beam angle was equal to 45 .
Elemental analyses were taken on a Vario El III analyzer (Elementar Analysensysteme
GmbH) after combustion of the analyzed sample in oxygen at 1150 °C. Contents of C, H, N in
the samples reported in the work are the average values of two analyses. The contents of Si
and O in the samples were calculated as the difference: 100%-ƩC,H,N. Gas chromatographic
analyses were performed on a Shimadzu GC2010 chromatograph equipped with thermal
conductivity detector (TCD) and Zebron ZB-1 capillary column (diameter 0.25 mm, length 30
m, liquid phase: polydimethylsiloxane) using helium as a carrier gas. The following
temperature program was used in chromatographic analyses of the reaction courses: detector
6

ACCEPTED MANUSCRIPT
temperature 250°C, sample evaporation temperature 250°C, working column temperature -
initial 60°C maintained for 3 minutes, then increased to 240°C at the rate of 18°C/min. The
isolated, final reaction products were analyzed using this as well as another, longer GC
program: detector temperature 300°C, sample evaporation temperature 250°C, working
column temperature - initial 80°C maintained for 2 minutes, then increased to 280°C at the
rate of 10°C/min.
3
. Results and discussion
In the work, hydrosilylation of carbon-carbon double bonds present in allyl groups
H
of Naa, Nach and Nap as well as those occurring in vinyl groups of 2VP and 4VP with M2
using Karstedt's catalyst was carried out. Conducted reactions are schematically depicted in
Fig 1. The scheme shows both products, i.e. α and β regioisomers, that can be formed during
hydrosilylation; in many hydrosilylation processes, however, the β addition prevails [34].
H
Fig. 1. Scheme of reactions of M2 with the studied nitrogen-containing organic compounds
7

ACCEPTED MANUSCRIPT
In the performed experiments, excess of the nitrogen-containing compound with
H
respect to M2 (allyl or vinyl : Si-H groups molar ratio equal to 1.5:1) was used. Progress of
all reactions was followed by GC and FTIR spectroscopy which enabled us to compare
H
reactivity of the organic compounds towards M2 in the studied conditions. The final, purified
1
13
products were characterized by GC as well as spectroscopic methods − FTIR, H NMR, C
2
9
NMR, Si NMR spectroscopies and, additionally, by elemental analysis.
Results of the investigations, separately for N-allyl and N-containing vinyl
compounds, will be discussed in the following sections.
H
3
.1 Functionalization of M2 with N-allyl compounds
N-allyl compounds applied in the studies contain 6-membered aromatic (Naa) or
aliphatic (Nach, Nap) rings in their structure (Fig. 1). This influences the geometry of the
molecules: aromatic ring in Naa is rigid, planar while the aliphatic ones in Nach and Nap are
flexible, they preferentially adopt chair conformation [47, 48]. Moreover, Naa and Nach are
secondary, whereas Nap is a tertiary amine. Basicity of these compounds changes in the
following order: Naa (pKa=4.17 [49]) < Nap (pKa = 9.68 [50]) < Nach (pKa=10.18 [51]).
This, together with the geometry of the molecule, should influence reactivity of the applied
amines in the performed experiments. Results of our investigations corroborate this statement.
H
Gas chromatograms recorded during the reactions of M2 with Naa, Nach and Nap are
presented in Fig. 2a, Fig. 2b and Fig. 2c, respectively. It can be seen that in all the cases
H
intensities of the peaks originating from M2 (retention time: 1.6 min.) and nitrogen-
containing compounds (retention times: Naa - 8.4 min., Nach - 7.0 min., Nap - 5.1 min.)
lower as the reaction time grows. This indicates successful hydrosilylation in all the systems.
H
Comparison of the chromatograms reveals that the decrease in concentration of M2 is
the fastest during the reaction with Naa: the peak at 1.6 min is very low already after a 3-hour
process (Fig. 2a). Reaction with Nach is the other extreme: it is accompanied by the smallest
H
changes in the concentration of M2 within the first 3 hours (Fig. 2b). It should be noted,
H
however, that after 24 hours the M2 peak disappears completely from the chromatogram of
this system (Fig. 2b). In contrast, it is still seen, but of low intensity, in the chromatograms
corresponding to the 24-hour processes involving Naa and Nap (Fig. 2a, Fig. 2c). Thus, based
on the GC results it can be concluded that out of the studied N-allyl
8

ACCEPTED MANUSCRIPT
toluene
toluene
Naa
H
2
toluene
Nach
H
2
H
2
a)
M
M
c)
M
b)
Nap
after 24h
after 24h
after 24h
after 3h
after 3h
after 1h
after 3h
after 1h
after 1h
initial reaction
mixture
initial reaction
mixture
initial reaction
mixture
0
2
4
6
8
10 12 14 16 18
0
2
4
6
8
10 12 14 16 18
0
2
4
6
8
10 12 14 16 18
Time [min]
Time [min]
Time [min]
H
Fig. 2. Gas chromatograms recorded during the reactions of M with: a) Naa, b) Nach, c) Nap
2
9

ACCEPTED MANUSCRIPT
H
compounds, Naa shows the highest reactivity towards M2 in the applied experimental
conditions. This suggests that low nucleophicity and molecular structure (planar, aromatic
ring) of Naa are advantageous for hydrosilylation.
The peak originating from the nitrogen-containing organic compound is distinct in the
chromatograms of all final reaction mixtures (Fig. 2a-2c). This is expected because, as already
H
mentioned, excessive amounts of Naa, Nach and Nap with respect to M2 were used in the
experiments (section 2.3).
H
Interestingly, after an hour of the reaction between M2 and Naa a new peak at a
higher retention time (12.4 min) appears in the chromatogram; its intensity lowers after
3
hours and it is not present in the chromatogram of the final reaction mixture (Fig. 2a). It can
be supposed that this peak is due to the monosubstituted siloxane. Separation of this product
from the mixture containing unreacted Naa has proved, however, difficult. Similarly to the
disubstituted compound (section 2.3), vacuum distillation is inefficient. Column
chromatography on silica gel, allowing isolation of the disubstituted siloxane, is not effective
in the case of the monosubstituted one, most probably due to the interaction of its Si-H groups
and Si-OH moieties present on silica surface. Therefore, in order to assign the GC peak at
H
1
2.4 min more precisely we performed the reaction of M2 and Naa using the excess of the
siloxane with respect to the amine (Si-H : CH =CH-CH - groups molar ratio equal to 1:0.5,
2
2
H
section 2.3) since such conditions are beneficial for predominant monosubstitution of M2
52]. Gas chromatogram of the final product of this reaction (SI, Fig. S1, curve a) recorded
using the same temperature program as while monitoring the process conducted with the
[
1
13
excess of Naa (section 2.5) shows two distinct peaks at 12.6 and 13.1 min. H and C NMR
spectra (SI, Fig. S2a, b) confirm that this reaction leads mainly to the monosubstituted β
isomer. Hence, the peak at 12.4 min. in the chromatograms measured during modification of
H
M2 with the excess of Naa (Fig. 2a) can be ascribed to the β monosubstituted product. Its
appearance and subsequent disappearance demonstrates a step-wise addition, with the
monosubstituted siloxane being an intermediate product. The absence of this peak in the final
chromatogram shows that the end product is only the disubstituted siloxane, not detected by
our GC measurements, aimed mainly at monitoring the progress of the reaction by following
the disappearance of the starting reagents. It is, however, represented by the peak at 26.0 min
in the chromatogram of the final, purified product measured by another, longer GC program
(SI, Fig. S3a). In such chromatograms, siloxane disubstituted by Nap and Nach moieties give
rise to the peaks at 19.9 and 22.4, 22.7 min., respectively (SI, Fig. S3a). It is worth noting at
1
0

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this point that the final, purified products have been additionally analyzed by the GC method
applied during monitoring the reactions. The peak corresponding to the disubstituted product
H
is seen only in the case of the M /Nap (retention time: 17.0 min., SI Fig. S3b); it is well-
2
H
resolved also in the chromatogram of the final M /Nap reaction mixture (Fig. 2c).
2
H
Gas chromatogram of M2 modified by Naa at the excess of siloxane (Si-H :
CH =CH-CH - groups molar ratio equal to 1:0.5), measured using the longer program (SI,
2
2
Fig. S1, curve b) reveals that the disubstituted product is formed in the reaction as well. This
is consistent with the results reported for hydrosilylation of other compounds with the excess
H
of M2 catalyzed by Karstedt’s complex [52, 53]. The presence of the β disubstituted siloxane
in the final product of this reaction is manifested also by the signal of low intensity at δ=7.8
29
ppm in the Si NMR spectrum (SI, Fig. S2c). In addition, the spectrum contains two
intensive lines at δ=9.8 ppm and δ=-6.3 ppm due to the Si units in the monosubstituted
compound and three lines of low intensities at δ=-6.6, -6.9 and -9.5 ppm that point to the
formation of side products with (as can be judged by the positions of these lines) Si-H bonds
in their molecules. The GC peak at 13.1 min. (SI, Fig. S1, curve a) and at 15.3 min. (SI, Fig.
S1, curve b) must be associated with one of such products. Identification of these compounds
has been, however, beyond the scope of the work.
H
Similarly to the M /Naa system, isolation of the intermediate products in the
2
H
reactions between M2 and Nach or Nap has been ineffective. They are, however, represented
by small peaks at ~11 min. (11.0 and 11.4 min.) in the gas chromatograms recorded during
functionalization of the siloxane with Nach (Fig. 2b) and a range of GC peaks which
appear/disappear during its modification by Nap (Fig. 2c), showing the complex course of this
process.
In accordance with the GC results and as expected for hydrosilylation, FTIR spectra of
all reaction mixtures show gradual lowering in the intensities of the bands corresponding to
H
the Si-H groups, thus marking the progress of M2 modification processes. This is illustrated
by Fig. 3 in which the decrease of the band assigned to the stretching vibrations of the Si-H
-1
H
groups [54] at ~2100 cm in the spectra recorded during modification of M with Naa is
2
presented. Final conversion degrees of the Si-H groups estimated from FTIR spectra (based
-1
on the analysis of the ratios of integral intensities of the band at ~2100 cm and that at 1250
-1
H
H
cm as described in [55, 56]) have been equal to 98.6% (M /Naa sample), 97.0 (M /Nach
2
2
H
sample) and 91.1% (M /Nap sample).
2
1
1

ACCEPTED MANUSCRIPT
initial reaction mixture
after 1h
after 3h
after 24h
2200
2160
2120
2080
-1
Wavenumber [cm ]
Fig.3. FTIR spectra showing the disappearance of the Si–H vibrational band during
H
hydrosilylation of Naa with M2
1
FTIR and H NMR spectra of the final, purified products confirm that the reactions
H
between M2 and N-allyl compounds do occur and are complete. FTIR spectra (Fig. 4), apart
from the lack of the bands due to the Si-H groups, do not contain the bands that would
evidence the presence of allyl groups, appearing in the spectra of the starting N-allyl
-1
compounds (not shown) at 1644 cm (stretching vibrations of C=C bonds [54]) and – in the
-1
case of Nap and Nach – at 3077 cm (asymmetric stretching vibrations of C-H at C=C bonds
[
54]), obscured by the aromatic C-H bands in the spectrum of Naa. Simultaneously, FTIR
-1
-1
spectra show the existence of both, siloxane (strong bands at ~1040 cm and 1250 cm ,
assigned to Si-O-Si asymmetric stretching and C-H in SiCH bending vibrations, respectively
3
-1
[
54]) and organic, N-containing (~1180 cm , C-N bond stretching vibrations, [54], ~3400
-1
H
H
cm in the spectrum of M /Naa, N-H stretching vibrations [54]) parts in the final M
2
2
1
H
functionalization products. This finding is fully corroborated by H NMR spectra of M /Naa
2
H
and M /Nap samples in which all signals assigned to protons present in the modified
2
siloxane can be easily distinguished (SI, Fig. S4a, Fig. S5a). Importantly, multiplets at δ =
1
2

ACCEPTED MANUSCRIPT
H
0
.67-0.63 ppm, 1.72-1.64 ppm (M /Naa, SI, Fig. S4a) and δ = 0.45-0.35 ppm, 1.50-1.40 ppm
2
H
(
M /Nap, SI, Fig. S5a) prove that only the β-product (Fig. 1) is formed in the hydrosilylation
2
H
of Naa and Nap with M . No signals that could be ascribed to the α-product (Fig. 1,
2
according to spectra numerical simulation [57], protons in the α-product should give rise to a
multiplet at δ = 1.32 ppm and a doublet at δ = 1.08 ppm) are detected. The same conclusions
1
3
can be drawn from the C NMR spectra (SI, Fig. S4b and Fig. S5b). Thus, hydrosilylation
H
reactions of Naa and Nap with M2 are very selective: they lead exclusively to the β-adducts.
H
M /N a p
2
H
M /N a ch
2
H
M /N aa
2
4
0 0 0
3 5 0 0
3 0 0 0
2 5 0 0
2 0 0 0
1 5 0 0
1 0 0 0
5 0 0
-
1
W avenum ber [cm ]
H
Fig.4. FTIR spectra of the final, purified products of M2 modification by N-allyl compounds
1
H
Interpretation of the H NMR spectrum of M modified by Nach (Fig. 5a) is not so
2
straightforward as it contains a great number of overlapping lines. Complexity of the
spectrum suggests that during hydrosilylation of Nach α linkages, in addition to the β ones,
may be formed. This makes the system quite complicated since generation of ββ (β-isomer in
H
Fig. 1), αα (α-isomer in Fig. 1), and the mixed, αβ disubstituted M2 is possible. Moreover,
the αα isomer contains two chiral centers and, because of this, it can exist in two
diastereoisomeric forms. In such a mixture, nonequivalent protons occur in similar compoun-
1
3

ACCEPTED MANUSCRIPT
a)
b)
1
H
H
Fig. 5. H NMR spectra of: a) M2 and b) MM modified by Nach
1
4

ACCEPTED MANUSCRIPT
Table 1. Parameters of the signals corresponding to protons in the β and α adducts formed
H
H
1
upon modification of MM and M2 by Nach in the simulated [57] and experimental H NMR
spectra. Symbols referred to multiplicity: m-multiplet, d-doublet, dd-doublet of doublets
Simulated spectrum
δ [ppm] Multiplicity, Integration
m, 2H
Experimental spectrum
a)
Proton
δ [ppm]
Multiplicity, Integration
H
3β (MM /Nach)
0.45-0.49
0.47-0.52
1.41-1.49
1.43-1.51
2.55-2.59
2.57-2.61
0.91
m, 2H
m, 4H
m, 2H
m, 4H
m, 2H
m, 4H
0
.68
H
b)
2β (M /Nach)
m, 4H
m, 2H
2
H
4β (MM /Nach)
1
.61
H
b)
3β (M /Nach)
m, 4H
m, 2H
2
H
5β (MM /Nach)
2
1
.60
.08
H
b)
4β (M /Nach)
m, 4H
d, 3H
2
H
e)
3α (MM /Nach)
−
H
c)
e)
2α (M /Nach)
d, 6H
0.94
−
2
H
e)
4α (MM /Nach)
m, 1H
0.97-1.27
−
H
1.31
c)
e)
3α (M /Nach)
m, 2H
m, 2H
0.99-1.29
−
2
H
d)
5α (MM /Nach)
2.75
dd, 1H
dd, 1H
m
d)
2
.42
2
.76
H
c)
d)
d)
4α (M /Nach)
m, 4H
2.75-2.80
2
2
.36-2.47
m
a)
H
H
protons denoted as in Fig. 5a (M /Nach) and Fig. 5b (MM /Nach);
2
b)
c)
d)
with the assumption that only ββ-disubstituted regioisomer is formed;
with the assumption that only αα-disubstituted regioisomer is formed;
the presence of stereogenic centers in the molecules of α-MM /Nach isomer and αα-
M /Nach isomer causes that (carbon atom 5 – Fig. 5b and 4 – Fig. 5a, respectively)
H
H
2
α
α
causes that protons 5 (Fig. 5b) and 4 (Fig. 5a) are diastereotopic and give two separate
α
α
signals in the spectrum;
e)
a great number of overlapping lines in this region of the spectrum hinder accurate signal
integration and multiplicity determination.
1
nds which causes that the signals in the H NMR spectrum coincide. Therefore we carried
out hydrosilylation of Nach with another disiloxane, namely 1,1,1,3,3-pentamethyldisiloxane
H
(
MM , section 2.4). This process can result in a maximum of two products: α and β
1
monosubstituted regioisomers and thus should give rise to a simpler H NMR spectrum than
H
H
that of functionalized M . We have found that the reaction between MM and Nach proceeds
2
smoothly, giving the product of expected elemental composition (SI, Table S1). The measured
1
H
H NMR spectrum of MM /Nach (Fig. 5b) contains the lines at similar chemical shift values
1
5

ACCEPTED MANUSCRIPT
H
to those found in the spectrum of M /Nach (Fig. 5a). However, multiplets visible in it are
2
H
less complex than the ones occurring in the spectrum of M /Nach. After numerical
2
1
H
simulations [57], the signals visible in the experimental H NMR spectra of both, M /Nach
2
H
and MM /Nach have been assigned to protons occurring in these molecules. In particular, the
H
H
spectra provide strong evidence that during the reactions of Nach with M2 and MM , β as
well as α additions take place. Chemical shifts, multiplicity and integration of the signals due
1
to the protons in β and α linkages in the simulated and experimental H NMR spectra of
H
H
1
MM /Nach and M /Nach are collected in Table 1. In line with the findings based on H
2
13
H
NMR, C NMR spectra (SI, Fig. S6, Fig. S7) show that hydrosilylation of Nach by M and
2
H
MM results in two types of additions.
1
H
Moreover, H NMR - like FTIR - spectra of M functionalized by all studied N-allyl
2
compounds do not contain the signals of protons in the allyl (δ = 5-6 ppm [58]) or Si-H (δ =
4
.7-4.8 ppm [58]) groups. This is a further proof that hydrosilylation in the studied systems is
complete. Similarly, total functionalization by the moieties of Nach has been attained for the
polymeric compound, polyhydromethylsiloxane [39].
2
9
H
2
H
Si NMR spectra of M /Naa and M /Nap exhibit a single line located at δ = 7.8
2
H
H
H
ppm (M /Naa) or δ = 7.5 ppm (M /Nap), whereas that of M /Nach - two double lines at δ
2
2
2
=
7.7, 7.4 ppm and 8.5, 8.4 ppm (Fig. 6). All these signals are in the range where the maxima
attributed to [SiOC ] units in siloxanes are observed [59], originating in the investigated
3
H
1
systems from hydrosilylation of N-allyl compounds with M . In view of the H NMR results
2
2
9
it can be proposed that the signal at δ = 7.4-7.8 ppm, occurring in the Si NMR spectra of all
samples, is due to [SiO(CH ) CH CH CH ] units (β product, Fig. 1) and those at δ = 8.5, 8.4
3
2
2
2
2
H
ppm, seen only in the spectrum of M /Nach – to [SiO(CH ) CH(CH )CH ] units (α product,
2
3 2
3
2
H
Fig. 1). This assignment is corroborated by the spectra of the monosubstituted M2 obtained
by hydrosilylation of other compounds, which contain one or two lines in this range when
exclusively β or β and α isomers are formed in the process, respectively [52, 53]. Splitting of
H
these signals in the spectrum of the disubstituted M /Nach sample signifies formation of the
2
mixture of ββ, αα and αβ products in the reaction. Similar sets of lines have been observed in
2
9
the Si NMR spectrum of 1,1,3,3,5,5-hexamethyltrisiloxane disubstituted by 4-substituted
styrene derivative moieties via hydrosilylation yielding three regioisomers [60].
1
6

ACCEPTED MANUSCRIPT
2
9
Additionally, Si NMR spectroscopy, like other spectroscopic methods, clearly shows
H
that the functionalization of M2 in our systems is complete; in the spectra the signal at
δ = -5.0 ppm, assigned to [(CH ) Si(O)H] units [59], is absent.
3
2
H
M
/Nap
2
H
M
/Nach
2
H
M
/Naa
2
1
0
5
0
-5
-10
-15
-20
-25
Chemical shift [ppm]
2
9
H
Fig. 6. Si NMR spectra of M modified by N-allyl compounds
2
According to elemental analysis, compositions of the final reaction products between
H
M2 and Naa or Nach are close to those calculated for the disubstituted siloxane (Table 2).
H
Discrepancies observed for M /Nap are presumably due to its incomplete purification by
2
column chromatography (section 2.3) reflected by the signals at ~-22 ppm, 0.05 ppm and 1.34
29
1
13
ppm in its Si (Fig. 6), H and C (SI, Fig. S5) NMR spectra, respectively as well as by the
H
peaks at 20.8 and 22.3 min. in the gas chromatogram of the final M /Nap product measured
2
by the longer program (SI, Fig. S3a).
1
7

ACCEPTED MANUSCRIPT
H
Table 2. Results of elemental analysis of M2 functionalized by N-allyl compounds
Contents of elements [wt. %]
Sample
C
H
N
ƩSi,O
found
found
calc.
found
calc.
found
calc.
calc.
H
M /Naa
65.66
63.75
60.88
65.94
64.01
62.43
8.92
11.65
11.61
9.05
11.73
11.53
7.83
6.63
6.92
7.82
6.78
7.28
17.57
17.97
20.59
18.01
17.48
18.76
2
H
M /Nach
2
H
M /Nap
2
To summarize, results of our experiments show that successful, direct hydrosilylation
of N-allyl amines in the presence of the Pt catalyst is possible. Reactivity of these compounds
in the process is influenced by their nucleophicity and molecular structure. Low
nucleophicity, i.e. low electron density on the nitrogen atom, as well as planar, aromatic ring
connected to the allyl group, as in Naa, are the most beneficial for hydrosilylation, possibly by
facilitating immediate coordination of >C=C< bond to Pt center in the catalyst, necessary for
the reaction to occur. Higher nucleophicity and the presence of non-planar, aliphatic rings, as
in Nach and Nap, slow down the reaction and – in the case of Nach – result in the formation
of a mixture of disubstituted regioisomers.
H
3
.2 Functionalization of M2 with N-containing vinyl compounds
Analysis of gas chromatograms recorded during hydrosilylation of 2VP and 4VP with
H
M2 (Fig. 7) leads to the conclusion that functionalization of the siloxane takes place only
H
when 2VP is applied in the reaction. Intensity of the GC peak corresponding to M2 decreases
in time and new peaks of retention times ~9 min and ~15 min, most probably due to the
monosubstituted and disubstituted products, respectively appear (Fig. 7a). In contrast,
H
intensity of the M2 peak practically does not change in the process conducted with 4VP and
no new peaks are seen in the chromatograms (Fig. 7b). This indicates stronger interaction of
4
VP than that of 2VP with Pt in Karstedt’s catalyst, most probably due to geometric reasons:
vinyl group present in the 2VP molecule close to the nitrogen atom causes that it is a less
efficient ligand than 4VP.
H
Unfortunately, as mentioned in section 2.3, we were not able to separate M /2VP
2
from the excess of 2VP. Therefore FTIR spectrum of the final reaction product (Fig. 8)
-
1
corresponds in fact to the mixture of compounds. The band at ~2100 cm (Si-H groups) is,
1
8

ACCEPTED MANUSCRIPT
H
however, distinct in it. This proves, in agreement with GC, that modification of M2 by 2VP
H
is not complete. The FTIR spectrum of M /4VP is, in turn, dominated by the bands
2
corresponding to 4VP which constitutes a large excess in the mixture. Because of these
features, we have not analyzed FTIR spectra quantitatively.
H
M2
toluene
H
M2
a)
toluene
b)
2
VP
4VP
after 24h
after 3h
after 24h
after 3h
initial reaction
mixture
initial reaction
mixture
0
2
4
6
8
10 12 14 16 18
0
2
4
6
8 10 12 14 16 18
Time [min]
Time [min]
H
Fig. 7. Gas chromatograms recorded during modification of M2 with: a) 2VP b) 4VP
H
M +2VP after 24h
2
2
VP
H
M +4VP after 24h
2
4
VP
4
000 3500 3000 2500 2000 1500 1000
500
-
1
W avenumber [cm ]
H
Fig. 8. FTIR spectra of 4VP, 2VP and final products of functionalization of M2 by both compounds
1
9

ACCEPTED MANUSCRIPT
The conclusions drawn from gas chromatograms and FTIR spectra are fully
1
29
1
corroborated by H and Si NMR spectra (not shown). The H NMR spectra of both,
H
H
M /2VP and M /4VP are dominated by the signals corresponding to 2VP and 4VP
2
2
respectively which indicates the presence of a large excess of unreacted N-containing vinyl
compounds in the final mixtures. There are signals attributed to protons of unreacted vinyl
H
groups (three doublet of doublets at δ = 6.58, 6.00, 5.22 ppm for M /2VP and at δ = 6.37,
2
H
29
5
.69, 5.20 ppm for M /4VP) and those of Si-H groups (δ = 4.56 ppm). The Si NMR
2
H
spectrum of M /2VP contains the lines due to [SiOC ] units (δ = 9.3, 8.0 and 6.0 ppm), not
2
3
H
observed in the spectrum of M /4VP mixture.
2
H
All the presented data clearly show that the reaction of M2 with 2VP does, whereas
H
with 4VP does not take place. Reactivity of 2VP towards M2 is, however, markedly lower
than that towards N-allyl compounds. This may be caused by strong deactivation of
Karstedt’s catalyst by pyridine moieties. Pyridine shows stronger affinity to platinum than
amines since in its bonding with this metal not only the lone electron pair on nitrogen atom,
but also π electrons of the ring are involved [61]. Hence, there is a strong competition
between coordination of >C=C< bonds and pyridine moieties to Pt centers in the catalyst in
these systems.
Our results are in contrast to those obtained by other groups reporting successful
hydrosilylation of 4VP with hydride-terminated polydimethylsiloxane [40] or
dimethylsiloxane-methylhydrosiloxane copolymer [41, 42]. This may be due to different
reaction conditions. Although in all the studies Karstedt’s catalyst was applied, the process
o
o
was conducted in methylene chloride at 60 C [40] or in toluene at 110 C for 2 days [41, 42].
In the former case, functionalization was quantitative but not selective yielding a 1:2 mixture
of α and β adducts, while in the latter only ~60 wt. % of Si-H groups reacted. This points to
the important role of the solvent in the hydrosilylation of 4VP. We decided, however, to
perform hydrosilylation of vinylpyridines in toluene in order to be able to directly compare
H
their reactivities with those of N-allyl compounds. Application of M2 as the hydrosilylating
agent precluded the use of higher temperatures in the processes due to its relatively low
o
boiling point (70 C).
It is also worth mentioning that the work by our group which is currently in progress
shows that polymethylhydrosiloxane, i.e. a homopolymer with a hydrogen atom attached to
H
each Si atom in the chain, like M , does not react with 4VP in the conditions used in the
2
H
present studies. Thus, M2 is a good compound to perform model investigations on reactivity
2
0

ACCEPTED MANUSCRIPT
in hydrosilylation of other low- or high-molecular-weight siloxanes containing a Si-H group
in each siloxane unit or copolymers with a block of such units in their chains under given,
mild conditions.
4
. Conclusions
Model studies conducted in the work on functionalization of 1,1,3,3-tetramethyldisiloxane by
nitrogen-containing moieties originating from N-allylaniline (Naa), N-allylcyclohexylamine
(Nach), N-allylpiperidine (Nap), 4-vinylpiridine (4VP) and 2-vinylpiridine (2VP) via
hydrosilylation in the presence of Karstedt’s catalyst show that:
1
. N-allyl compounds applied in the investigations can be used to modify siloxanes by
H
nitrogen-containing groups. Complete difunctionalization of M2 established after a 24-
hour hydrosilylation process of Naa, Nach and Nap proves that nitrogen atoms of these
compounds do not interact strongly with Pt centers in the Karstedt’s catalyst. The fastest
reaction observed for Naa can be due to its lowest nucleophicity and suggests that the
geometry of this molecule (rigid, planar aromatic ring) is more advantageous for
hydrosilylation than the geometry of Nach and Nap (aliphatic rings of chair
conformation).
2
3
. Reactions with Naa and Nap are very selective: they lead exclusively to the β
hydrosilylation product. In the case of Nach, α addition also takes place.
. Out of nitrogen-containing vinyl compounds applied in the studies, only 2VP can be
H
hydrosilylated, but M2 conversion degree in this case is significantly lower than those
found for N-allyl compounds. The reaction with 4VP does not take place at all. This
shows that Karstedt’s catalyst is deactivated by pyridine moieties which can be explained
by their strong coordinative ability towards Pt.
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50] R. Adams, J. E. Mahan, J. Am. Chem. Soc, 1942, 64, 2588-2593.
51] Calculated using Advanced Chemistry Development (ACD/Labs) Software V11.02 (©
1
994-2019 ACD/Labs).
[
[
[
52] R. Januszewski, I. Kownacki, H. Maciejewski, B. Marciniec, A. Szymańska, Eur. J.
Inorg. Chem. 2017, 851-856.
53] R. Januszewski, I. Kownacki, H. Maciejewski, B. Marciniec, J. Organometal. Chem.
2
017, 846, 263-268.
54] G. Socrates, Infrared and Raman characteristic group frequencies, Wiley, New York,
004.
2
2
4

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[
[
55] V. V. Antić, M. P. Antić, M. N. Govedarica P. R. Dvornić, J. Polym. Sci. A, 2007, 45,
2
246-2258.
56] A. Nyczyk, C. Paluszkiewicz, M. Hasik, M. Cypryk, P. Pospiech, Vib. Spectrosc, 2012,
5
9, 1-8.
1
H
H
H
57] The H NMR spectra of M /Naa, M /Nap and M /Nach were predicted directly from
2
2
2
chemical structures using free online NMR Predictor from website
https://www.nmrdb.org/.
[
[
[
[
58] R. B. Taylor, B. Parbhoo, D. Fillmore in The analytical chemistry of silicones (Eds.: A.
L. Smith), Wiley, 1991, pp 347–419.
59] H. Marsmann, in NMR basic principles and progress, Vol 17 (Eds.: P. Diehl, E. Fluck, R.
Kosfeld), Springer, 1981, pp. 65-235.
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2
018, 135, 46848/1-46848/6.
61] J. A. Davies, F. R. Hartley, Chem. Rev. 1981, 81, 79-90.
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Hydrosiloxanes react with cyclic N-allylamines in the presence of Karstedt’s complex
Aromatic ring and low nucleophicity of N-allyl amine are beneficial for the process
2-vinylpyridine is markedly less reactive than cyclic N-allylamines
Reaction with 4-vinylpyridine does not take place
Pyridine moieties deactivate the Pt catalyst which inhibits/prevents the reaction