Reaction of TiCl4 with diethyl ether. Experimental and quantum-chemical study

Article abstract of DOI:10.1134/S1070363216010035

The reaction of titanium tetrachloride with diethyl ether at various ratios of components and temperatures was studied by the NMR and mass spectrometry methods. The TiCl₄·2Et₂O complex does not pass in the gas phase. Formation of ethoxytrichlorotitanium among reaction products was established by the X-ray structure analysis. The model of conversion from initial components to titanium dioxide was suggested on the basis of the obtained experimental data and quantum-chemical calculations (B3LYP/def2-SVP level of theory).

Full text of DOI:10.1134/S1070363216010035

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 1, pp. 9–17. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © N.V. Shugurova, E.I. Davydova, T.N. Sevast’yanova, A.D. Misharev, M. Bodensteiner, M. Scheer, 2016, published in Zhurnal
Obshchei Khimii, 2016, Vol. 86, No. 1, pp. 11–19.
Reaction of TiCl with Diethyl Ether.
4
Experimental and Quantum-Chemical Study
a
a
a
N. V. Shugurova , E. I. Davydova , T. N. Sevast’yanova ,
a
b
b
A. D. Misharev , M. Bodensteiner , and M. Scheer
a
St. Petersburg State University, Universitetskaya nab. 7–9, St. Petersburg, 199034 Russia
e-mail: tns6@yandex.ru
b
Institute of Inorganic Chemistry, University of Regensburg, Germany
Received June 26, 2015
Abstract—The reaction of titanium tetrachloride with diethyl ether at various ratios of components and
temperatures was studied by the NMR and mass spectrometry methods. The TiCl ·2Et O complex does not
4
2
pass in the gas phase. Formation of ethoxytrichlorotitanium among reaction products was established by the
X-ray structure analysis. The model of conversion from initial components to titanium dioxide was suggested
on the basis of the obtained experimental data and quantum-chemical calculations (B3LYP/def2-SVP level of
theory).
Keywords: titanium tetrachloride, diethyl ether, donor-acceptor complexes, ethoxytrichlorotitanium, titanium
dioxide
DOI: 10.1134/S1070363216010035
The use of titanium complexes as Ziegler–Natta
catalysts [1–3], reagents for a number of organic
syntheses [4–6], and precursors for obtaining titanium
was shown by the NMR method (a solution in SO2,
–84°C) that 1 : 1 and 1 : 2 complexes (cis- and trans-
isomers) are formed in the case of dimethyl ether [18].
In a CH Cl –CD Cl solution at 175 K only the cis-
dioxide [7–10] has attrached much interest to their
behavior at elevated temperatures.
2
2
2
2
form of the 1 : 2 complex with Me O was detected by
2
the methods of vibrational spectroscopy (Raman and
IR) and NMR spectroscopy [19, 20].
Titanium tetrachloride, being a typical Lewis acid,
forms 1 : 1 and 1 : 2 complexes with N- and O-
containing bases (amines, ethers, ketones, and
haloketones) [11–15]. Their vaporization is defined by
a competition between ruptures of intra- and inter-
molecular bonds [11]. Three types of reactions of these
compounds proceeding on heating can be distinguished:
With diethyl ether TiCl forms the complex TiCl ·
4
4
2
Et O of cis-structure, unstable at room temperature
2
[6, 17, 21–23, 25].
On the basis of the data of UV photoelectronic
spectroscopy (UVPES) and electron energy loss
spectroscopy (EELS) [21] it was found that the 1 : 2
complex is formed in the gas phase at 70°С. At the
ratios of components TiCl –Et O 1 : 1 and 2 : 1 only
(
1) vaporization of complexes in the gas phase
possible for saturated molecular structures with strong
donor–acceptor bonds);
(
4
2
the signals corresponding to titanium tetrachloride
were recorded, which testifies that no forms of gaseous
(
2) stepwise or complete dissociation with donor–
complexes other than TiCl ·2Et O are present. It was
acceptor bond rupture;
4
2
shown in [2] that the reaction of TiCl with diethyl
4
(
3) decomposition similar to hydrolysis or ammo-
ether leads to the formation of the 1 : 1 complex.
nolysis with evolution of hydrogen chloride or organo-
chlorine compounds.
To refine the composition of complex compounds
formed in the TiCl –Et O system and to make clear
4
2
Titanium tetrachloride forms donor–acceptor com-
plexes with dimethyl and diethyl ethers [6, 16–25]. It
their thermal behavior, in the present work we have
studied the reaction of TiCl with diethyl ether.
4
9

1
0
SHUGUROVA et al.
1
13
13
Table 1. Chemical shifts of signals in H and С NMR
The signal of the CH group in the С NMR
2
spectra of Et
Substance
Et
2
O and TiCl
4
·2Et
2
O
spectrum of the complex is shifted downfield, whereas
the position of the CH group signal practically does
3
δ
Н
,
Δδ,
ppm
δ
ppm
С
,
Δδ,
ppm
not change with respect to the pure ether, i.e., as in the
ppm
1
case of the H NMR spectra, the coordination affects
2
O
3.46 q (2H, CH
J = 7.1 Hz),
2
,
–
66.2 (CH
2
)
–
the CH group much more strongly than the CH
2
3
group. Values of chemical shifts of the ether and
complex are presented in Table 1 together with Δδ =
δcomplex – δligand values. The Δδ values are smaller than
the published data [25]. These distinctions are
connected with the fact that measurements in [25] were
carried out in a titanium tetrachloride excess, which
suppresses dissociation of the complex.
1
.17 t (3H, CH
3
,
15.6(CH
0.28 67.5(CH
3
2
)
J = 7.1 Hz)
3.74 q (2H, CH
J = 7.0 Hz),
4 2
TiCl ·2Et O
2
,
)
1.3
1
.28 t (3H, CH
3
,
0.11 15.3 (CH
3
)
–0.3
J = 7.0 Hz)
Mass spectra of vapor over TiCl ·2Et O taken in the
4
2
Reaction products were studied by the mass
spectrometry, NMR spectroscopy, and X-ray structure
analysis methods. Thermodynamic characteristics of
the processes occurring in the titanium tetrachloride-
diethyl ether system were calculated by a quantum-
chemical method.
temperature interval 120–380°С in the range of m/z =
1
2
6–430 are presented in Fig. 1. In the mass spectrum
of vapor over the TiCl ·2Et O complex there are no
4
2
peaks of molecular and fragmental ions of 1 : 1 and
: 2 complexes containing a Ti–O bond.
1
Comparison of the mass spectra of vapor over the
To elucidate the composition of complexes forming
in the TiCl –Et O system, reactions were carried out in
TiCl ·2Et O complex with the mass spectra of the pure
4
2
4
2
components, and also of chlorine derivatives and
alcohols as most probable products of the thermal
decomposition shows that at 120°С peaks of ions
characteristic of diethyl ether (m/z = 31, 47, 74) and
peaks of the ions related to titanium tetrachloride are
present in the spectra. Furthermore, characteristic
peaks of chloroethane EtCl (m/z = 64, 66) are observed
in the spectrum. Their intensity decreases as tempera-
ture increases: at 220°С the peak of EtCl is absent in
the spectrum. The peak with m/z = 28 corresponding to
a vacuum at various ratios of components: almost
twofold excess of the ether (1.00 : 1.98, 1.00 : 1.92),
equimolar ratio (1.00 : 1.02), and at tetrachloride
excess (1.00 : 0.62). At the 1.00 : 1.98 and 1.00 : 1.92
ratios of the TiCl –Et O components right after mixing
4
2
reagents the crystalline complex TiCl ·2Et O is
4
2
formed, which, as it is known [17, 22], is unstable at
room temperature. Therefore, to avoid decomposition,
the substance was stored at a low temperature (–30°C).
At the ratio of TiCl –Et O components 1.00 : 1.02 a
+
4
2
4
2
the C H ion, which appears either as a result of
2
two-phase liquid system consisting of solid complex
TiCl ·2Et O and its solution in titanium tetrachloride is
proceeding reactions or as a result of dissociative
ionization of organic compounds, has the maximum
intensity at 120°С. Its intensity decreases with
temperature increase. Ethanol signals are absent in the
spectrum.
4
2
formed. In the case of the synthesis in the tetrachloride
excess with the ratio TiCl : Et O = 1.00 : 0.62 a
4
2
homogeneous yellow solution of the TiCl ·2Et O
4
2
complex in TiCl was obtained. Thus at any ratio of
4
In the mass spectrum taken at 120°С a high intensity
of peaks of titanium-containing ions is observed,
which sharply decreases on keeping the complex at
this temperature within 10 min. As temperature
increases, intensity of peaks of these ions increases,
and at 330°С starts to decrease again. In the range
components the crystalline product of the synthesis
was the 1 : 2 adduct.
When studying the TiCl ·2Et O complex by the
4
2
NMR spectroscopy and mass spectrometry methods,
spectra were measured directly after synthesis in order
1
to avoid its decomposition. The general view of the H
+
m/z = 184–192 at 120°С peaks of TiCl OCH
3
2
NMR spectrum of the adduct is the same as for the
non-coordinated ether, but signals are shifted down-
field, which is characteristic of complex formation [19,
1
2
In Fig. 1 the m/z range is presented up to 240, because there are
no peaks in the region of higher values.
2
0, 24, 25]. The displacement of the group CH2
chemical shift is 2.5 times greater than that of the CH3
group.
The elemental composition of the ion with m/z = 28 was found
by measuring the exact weight in a high voltage mode.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

REACTION OF TiCl
4
WITH DIETHYL ETHER
a)
11
(
(
b)
(
c)
(
d)
(
e)
(
f)
m/z
4 2
Fig. 1. Mass spectra of vapor over TiCl ·2Et O taken at temperature: 120 (a) at once; (b) 10 min later, (c) 220, (d) 270, (e) 330, and
(f) 380°С.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

1
2
SHUGUROVA et al.
3
Fig. 2. General view of the TiCl OEt molecule.
(
titanium is detected by the isotope distribution) are
the complex. Signals at 1.48 and 3.61 ppm point to the
formation of chloroethane [27]. The range of chemical
shifts from 4.90 to 5.82 ppm is characteristic of
alkenes [27]. A weak signal in the region of δ ~ 5 ppm
is present in this spectrum, which is attributable to the
presence of alkenes in the adduct decomposition
products. Hence, even at room temperature, reactions
leading to the occurrence of chloroethane, unsaturated
hydrocarbons, and also products of their polymeriza-
tion proceed in the system.
observed in addition to TiCl4.
Relative intensities of peaks of ions corresponding
to titanium tetrachloride and chloroethane agree well
with experimental data for titanium tetrachloride and
with published data for pure EtCl [26].
To study thermal behavior of the complex in more
detail, we have fulfilled an experiment with time
exposure (100 min), normalizing mass spectra by a
standard substance (C F ) N. In the region of the initial
temperature increase (up to 120°С) peaks of ions
corresponding to Et O, TiCl , C H , EtCl, and HCl
ionization were detected in the mass spectrum. Their
intensity quickly decreases to background level on
exposure within 35 min. At further temperature rise up
to 170°С the intensities of peaks of the ions corres-
ponding to TiCl , C H , and HCl increase. Exposure at
this temperature within 10 min also leads to the
decrease in the intensity of peaks of ions to the back-
ground value. At 220 and 270°С only peaks of ions
corresponding to titanium tetrachloride and hydrogen
chloride are present in the spectrum, their intensity
decreasing to the background level on keeping the
sample at 220° within 10 min and at 270°С within 15 min.
4
9 3
On keeping an evacuated ampule with a solution of
the complex in titanium tetrachloride at room tempera-
ture within several months colorless crystals of ethoxytri-
2
4
2
4
chlorotitanium TiCl OEt were grown. Its structure was
3
confirmed by X-ray structure analysis (Fig. 2).
The obtained alkoxide is a polymer, where titanium
atoms are in a pseudo-octahedral environment formed
by the ethoxy-group oxygen and four bridging and one
terminal chlorine atoms. As it is seen from Table 2
4
2
4
1
1
1
3
bridging Ti –Cl and Ti –Cl bonds are longer than
1
2
terminal Ti –Cl bonds, but they both are much longer
than the Ti–Cl distance in the TiCl molecule (2.19 Å
4
1
1
1
[28]). The Ti O C angle is almost right (Table 3). Our
data, as seen from Tables 2 and 3, agree well with
structural characteristics of [TiCl OEt] available in
3
n
Thus, we can conclude that the TiCl ·2Et O
4
2
the literature [29]. However ethoxytrichlorotitanium in
29] was obtained by the reaction of Ti(OEt) with
complex decomposes on heating to liberate diethyl
ether, titanium tetrachloride, chloroethane, and
ethylene. Moreover, this process begins even at room
temperature, as demonstrated by the NMR data.
[
4
SiCl , whereas we obtained it by the decomposition of
4
the ether complex of titanium tetrachloride. The
association of TiCl OEt molecules proceeds with
3
The singlet with chemical shift of 1.25 ppm cor-
participation of chlorine atoms instead of oxygen
atoms of alkoxy group, as in similar TiCl (OR) and
responding to the CH group is the most intensive in
2
2
2
1
the H NMR spectrum of decomposition products of
TiCl(OR) dimers [30–37].
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

REACTION OF TiCl
4
WITH DIETHYL ETHER
Bond
13
Table 2. Bond lengths in the TiCl
3
OEt molecule
d, Å
d, Å
published data [29]
Bond
experiment
published data [29]
experiment
1
1
1
3
3
Ti –O
1.709(3)
1.704(7)
2.406(4)
2.522(3)
2.235(3)
Ti –Cl
2.3689(14)
2.6096(13)
1.425(6)
2.361(4)
2.602(3)
1.43(1)
1.51(2)
1
1
1
2
1
Ti –Cl
2.4062(14)
2.5211(13)
2.2346(13)
Ti –Cl
1
1
1
Ti –Cl
O –C
1
1
2
Ti –Cl
C –C
1.497(7)
3
Table 3. Bond angles in the TiCl OEt molecule
ω, deg
ω, deg
Angle
Angle
experiment
published data [29]
experiment
published data [29]
1
1
1
1
2
1
1
Cl Ti O
98.24(12)
90.32(12)
80.85(4)
92.61(5)
169.57(5)
160.99(5)
84.03(4)
86.27(4)
83.28(4)
97.7(3)
90.0(3)
80.8(1)
92.3(1)
169.7(1)
161.9(1)
84.4(1)
86.5(1)
83.5(1)
Cl Ti O
98.69(12)
88.00(4)
97.96(5)
95.74(12)
172.80(12)
80.61(4)
174.9(3)
99.15(4)
99.39(5)
98.6(3)
88.2(1)
98.2(1)
95.2(3)
172.8(3)
81.3(1)
176.3(7)
99.2(1)
99.2(1)
1
1
2
1
3
3
Cl Ti O
Cl Ti Cl
1
1
1
2
2
3
3
3
3
2
1
Cl Ti Cl
Cl Ti Cl
1
1
3
1
1
Cl Ti Cl
Cl Ti O
1
1
3
1
1
Cl Ti Cl
Cl Ti O
1
1
3
1
3
Cl Ti Cl
Cl Ti Cl
1
1
1
1
1
Cl Ti Cl
Ti O C
1
1
1
1
1
1
Cl Ti Cl
Ti Cl Ti
1
1
1
3
Cl Ti Cl
Ti Cl Ti
+
A peak of the fragment ion TiCl OCH is observed
On the basis of published data and experimental
results of the present work, we have simulated the
processes proceeding in the TiCl –Et O system on
3
2
in the mass spectrum of vapor over ethoxytrichloro-
titanium (Fig. 3) at 120–170°С. Its relative intensity is
4
2
1
6% at 120°С, which points to the fact that in the gase
heating. The 1 : 2 complexes, easily formed in the
condensed phase, are unstable even at room
temperature. The mass spectrometry data allow us to
conclude that the dissociation into components and the
HCl elimination proceed in parallel on heating. It
results in the formation of ethoxytrichlorotitanium,
which decomposes to form chloroethane, hydrogen
chloride, ethylene, and titanium oxochloride. TiOCl2
disproportionates into highly volatile titanium tetra-
chloride and poorly volatile titanium dioxide [38, 39].
phase the alkoxide exists as а monomer. At 170–270°С
peaks of chloroethane, hydrogen chloride, and ethylene
ions are detected in the spectra. The peaks of ions
corresponding to titanium tetrachloride appear in
insignificant quantities only at 270°С. It is connected
with the fact that alkoxide seems to convert to
nonvolatile titanium oxochloride on heating, which
disproportionates on the further temperature increase
to form titanium tetrachloride and dioxide.
TiCl 2Et O(cr.)
TiCl OEt(cr.) + EtCl(gas) + Et O(gas)
4
2
3
2
o
o
t
t
TiCl (gas) + 2Et O(gas) 0.5EtCl(gas) + 0.5HCl(gas) + 0.5C H (gas) + TiOCl (gas)
4
2
2
4
2
o
t
0
.5TiO (s.) + 0.5TiCl (gas)
2 4
To check the offered model, we have fulfilled quan-
tum-chemical calculations of competing homogeneous
gas-phase reactions of the complex decomposition into
components or up to ethoxytrichlorotitanium with its
subsequent decomposition to titanium oxochloride and
dioxide.
The calculations of thermodynamics of the gas-
phase processes were carried out by the B3LYP/def2-
SVP method. Quantum-chemical calculations are suc-
cessfully applied to predict the energy of titanium
tetrachloride complex formation and to interpret the
mechanism of transition from TiCl to TiO [40–44].
4
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

1
4
SHUGUROVA et al.
(
a)
1
1
1
00
8
6
4
2
0
0
0
0
(
b)
00
8
6
4
2
0
0
0
0
(
c)
00
8
6
4
2
0
0
0
0
(
d)
1
00
8
6
4
2
0
0
0
0
2
0
40
60
80
100
120
m/z
140
160
180
200
3
Fig. 3. Mass spectra of vapor over TiCl OEt taken at temperatures: (a) 120, (b) 170, (c) 220, and (d) 270°С.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

REACTION OF TiCl
4
WITH DIETHYL ETHER
15
Table 4. Energy and thermodynamic characteristics of gas-phase processes (B3LYP/def2-SVP)
0
0
0
0
0
ΔE ,
ΔH298
,
ΔS298
,
ΔG298
,
ΔG573
,
Process
–
1
–1
kJ/mol kJ/mol J mol K
kJ/mol
kJ/mol
1
2
cis-TiCl
4
4
·2Et
2
2
O = TiCl
4
+ 2Et
2
O
49
18
34
1
341
392
–68
–162
–223
cis-TiCl
·2Et
O = TiCl
3
OEt + EtCl + Et
2
O
–116
3
4
TiCl
3
3
OEt = TiOCl
2
+ 0.5EtCl + 0.5HCl + 0.5C
2
H
4
296
360
280
344
219
189
205
278
135
217
TiCl
OEt = 0.5TiO
2
+ 0.5TiCl + 0.5EtCl + 0.5HCl + 0.5C H
4
2 4
Results of the fulfilled calculations are presented in
Table 4.
If a substituent R in compounds of the type ROTiCl is
3
a secondary or tertiary alkyl, disintegration of such
compounds proceeds instantly even at low
temperatures with the formation of hydrogen chloride,
olefins, alkyl chlorides, and polymeric titanium oxo-
chlorides [46].
Comparison of the thermodynamics of processes 1
and 2 testifies that the decomposition of the complex
with alkoxide formation (process 2) is much more
favorable than the process of TiCl ·2Et O dissociation
4
2
into components (process 1). The decomposition of
ethoxytrichlorotitanium with the formation of both
gaseous TiOCl2 (process 3) and gaseous TiO2
EXPERIMENTAL
As titanium tetrachloride is easily hydrolyzed in air,
all operations of purification, taking sample weights,
and synthesis were carried out in vacuum-sealed glass
systems completely excluding contact of substances
with atmosphere. In the synthesis we used chemically-
pure grade titanium tetrachloride and diethyl ether
additionally dried and purified according to standard
techniques.
(process 4) is thermodynamically unfavorable.
Condensation of titanium dioxide decreases the
endothermicity of this reaction. Using characteristics
of titanium dioxide sublimation calculated on the basis
0
of the reference data [45], ∆H = 619.17 kJ/mol and
0
–1
–1
∆
S = 205.07 J mol K , we obtain for the hetero-
geneous reaction
1
13
TiCl OEt(gas) = 0.5TiO
3
2
(s.) + 0.5TiCl
4
(gas) + 0.5HCl(gas)
The H and С NMR spectra were recorded on a
+
0.5EtCl(gas) + 0.5C H (gas),
2 4
Bruker DX 300 instrument at room temperature using
CDCl as a solvent. The mass spectra were taken on an
MCh-1321 instrument using a system of direct sample
input at ionizing energy of 70 eV in the mode of
stepwise heating sample at temperatures 120–380°С.
0
0
–1 –1
∆
H
∆
298 = 34.4 kJ/mol, ∆S 298 = 86.5 J mol K ,
298 = 8.6 kJ/mol, ∆G 573 = −15.2 kJ/mol.
3
0
0
G
The process is favorable thermodynamically, its
exothermal effect increases as temperature increases.
The single-crystal X-ray structural analysis was
carried out on an Oxford Diffraction Gemini Ultra
Thus, our calculations point to the preferential
occurring of process 2 yielding ethoxytrichlorotita-
nium with its further decomposition yielding titanium
dioxide.
diffractometer with CuK radiation (λ = 1.54178 Å) in
α
the range of angles 5.19° < θ < 62.69°. The structure
was solved by the direct method with the program
2
In summary it may be said that the similar model of
decomposition of titanium tetrachloride ether com-
plexes was considered for analogous systems with
ethers [16, 24, 46]. For example, titanium tetrachloride
complex with dimethyl ether on heating to 50–60°С
converts to chloromethane and titanium methoxide,
which further passes into titanium oxochloride and
MeCl [24]. The synthesis of the product of diisopropyl
ether addition to titanium tetrachloride completely
unsuccessful, but TiCl [OCH(CH ) ] was isolated [16].
SHELXS-97 [47]; refinements on F was carried out
by the least squares method using SHELXL-97 [48].
Positions of hydrogen atoms were calculated
geometrically and refined in the rigid group
approximation. Crystals of C H Cl OTi are of the
2
5
3
triclinic system, unit cell parameters at 123 K are as
follows: a = 5.9723(5), b = 7.1932(8), c = 8.7000(9) Å,
α = 93.988(9)°, β = 98.826(8)°, γ = 110.687(10)°, V =
3
3
342.40(7) Å , M = 199.28, Z = 2, d = 1.933 g/cm ,
space group P-1. The full data are deposited in the
3
3 2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 1 2016

1
6
SHUGUROVA et al.
Cambridge Crystallographic Data Center (CCDC
12. Gur’yanova, E.N., Gol’dshtein, I.P, and Romm, I.P.,
Donor–Acceptor Bond, New York: Halsted, 1975.
1
407825).
1
1
1
1
3. Davydova, E.I., Sevast’yanova, T.N., and Shugurova, N.V.,
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using GAUSSIAN 09 program package [49] by the
density-functional method B3LYP with Becke
exchange functional В3 [50] and Lee–Yang–Parr
correlation functional [51]. A def2-SVP basic set was
used for all atoms [52]. Geometrical parameters of all
compounds were fully optimized with the following
vibrational analysis. All structures correspond to the
minima on the respective potential energy surfaces.
1
0.1134/S1070363214010241.
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