Journal of Inorganic and Organometallic Polymers, Vol. 13, No.

1, March 2003 ( 2003)

Complexation of Titanium Alkoxides with

Cis-2-butene-1,4-diol and Hydrolysis of
Their Products
Asgar Kayan 1
Received July 18, 2002; revised November 8, 2002
Reaction of Ti(OEt)4 and Ti(OBu n )4 with cis-2-butene-1,4-diol (B.diol-2H) in
1:1 molar ratio was studied at room temperature using the sol-gel process.
13
C{ 1 H}- and 1 H-NMR data showed that all the B.diol-2H completely reacted
with both titanium alkoxides. Each of the products was hydrolyzed by water.
The new hydrolyzed products were characterized by 13C- and 1 H-NMR spectroscopy and KarlFischer Titration. Thermogravimetric and differential
thermal analyses (TGA-DTA) of the hydrolyzed-products were also studied.
KEY WORDS: Sol-gel; titanium alkoxides; cis-2-butene-1,4-diol; hydrolysis of
metal alkoxides.

INTRODUCTION
Metal alkoxides and their organic derivatives have been used in the synthesis of glasses, ceramics and organic-inorganic hybrid materials [13].
The complexing of metal alkoxides with appropriate organic acids, diketones or glycols influences the functionality of the precursors and controls
the degree of polycondensation of the reaction products [46].
The first group of complexing ligands that contains unsaturated bonds
for metal alkoxides complexes are organic acids such as acrylic and
methacrylic acid (McOH) [4, 7]. The second group of complexing organic
compounds contains unsaturated bonds and involves b-ketoesters such as
allyl acetoacetate [6, 8] and methacryloxyethyl acetoacetate [6, 9]. When
organic acids or b-ketoesters are added to the metal alkoxide solution,

Department of Chemistry, Kocaeli University, zmit, Turkey. E-mail: akayan@kou.edu.tr

29
1053-0495/03/0300-0029/0 2003 Plenum Publishing Corporation

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Kayan

some of the alkoxy groups in the starting material are replaced with the
chelated organic groups [e.g., Eq. (1)].
Zr(OPr n )4 +2McOH |||Q
[Zr(OPr n )2 (OMc)2 ]n
2Pr nOH

(1)

In hydrolysis reactions of organic-modified metal alkoxide complexes,

only the alkoxide group undergoes substitution while chelated organic
groups remain bonded to the metal [Eq. (2)] [4, 5, 10, 11]. This observation is a result of chelate bond formation and steric hindrance effects [6, 8,
10, 12]. The other complexing organic compounds include glycols
+H O

2
[Zr(OPr n )2 (OMc)2 ]n |||Q
[ZrO(OMc)2 ]n
2Pr nOH

(2)

[Equation (3)]. The reaction between glycols and metal alkoxides results
in the formation of glycolates complexes (G:alkyl or G:alkylene) [1316].
Furthermore, addition of cis-2-butene-1,4-diol to Ti(OPr i )4 in a 1:1
stoichiometry produces [Ti4 (OPr i )8 (m,g 2-OCH 2 CH=CHCH 2 O)2 -(m3 ,g 2OCH 2 CH=CHCH 2 O)2 ] or simply [Ti(OPr i )2 (OCH 2 CH=CHCH 2 O)]n
[17].
OH
M(OR)4 +nG

|Q (RO)4 2n M
OH

O
G
O

+2nROH)n

(3)

In order to explore further this chemistry, we undertook a study of the

reactions of the metal alkoxides, Ti(OEt)4 and Ti(OBu n )4 , with the chelated
alcohol cis-2-butene-1,4-diol (B.diol-2H). The hydrolytic stability of the
ligand on the metal alkoxide complexes was also investigated.

EXPERIMENTAL
Methods and Materials
13

C- and 1 H-NMR spectra were recorded on a Bruker AC200 spectrometer. The amount of water in the hydrolysates was determined by
KarlFischer (KF) titration using a Mettler DL 18. Thermogravimetric
analysis (TGA) and differential thermal analysis (DTA) measurements
were carried out on a Bahr-Thermoanalyse Type STA 501 thermal
analyzer. The chemicals, Ti(OEt)4 (92%), Ti(OBu n )4 (90.6%), B.diol-2H
(95%) and ethyl methyl ketone were used in the experiments without
further purification.

Complexation of Titanium Alkoxides with Cis-2-butene-1,4-diol

31

Preparation of [Ti(OEt)2 (B.diol)]n (1)

Ti(OEt)4 (3.7 mmol) in methyl ethyl ketone (15 ml) was stirred for 10
minutes. B.diol-2H (3.7 mmol) was added to the solution. The mixture was
stirred for two hours at room temperature. The solvent and liberated
ethanol were removed from the gel under vacuum at about 60C. 13C{ 1 H}NMR (in CDCl3 ), ppm (assignment): 19.10 (CH 3 , OEt); 64.03 (Ti-OCH 2 b
b
CH=); 71.36 (OCH 2 , OEt); 131.32 (Ti-OCH 2 -CH=). 1 H-NMR (in
b
b
CDCl3 ), ppm (multiplicity, assignment): 1.2 (t, CH 3 , OEt); 4.4 (m, CH 2 ,
OEt); 4.93 (brs, CH 2 , from Ti-OCH 2 -CH=); 5.83 (brs, CH, from Ti-OCH 2 CH=).
Hydrolysis of [Ti(OEt)2 (B.diol)]n (2)
The hydrolysis of the [Ti(OEt)2 (B.diol)]n complex was carried out
with a water/methyl ethyl ketone solution at room temperature for 30 min.
The hydrolysis ratios of H 2 O/Ti(OEt)4 for these experiments were 2:1, 3:1,
and 4:1. The amount of unreacted water was determined by KF-titrations
[18]. The consumed water was found to be 1.79 mol (4H 2 O/Ti ethoxide)
by subtracting unreacted water from the added water. Only transparent
solutions were examined by 13C- and 1 H-NMR spectroscopy. These solutions included hydrolyzed product, released ethanol, and dissociated B.diol2H as shown in Fig. 1. The intensity ratio of CH 2 protons of dissociated
B.diol-2H to CH 2 protons of B.diol that is bonded to the titanium

H
C

HOH2C

C
CH 2OH

+Ti(OEt)2 -EtOH

[ Ti(OEt)0.9 (OH)1 .28(OCH2 CH=CHCH2 O) ]n

+4H2O

-1.1EtOH
-0.6B.diol-2H

[ Ti(OEt)0.9 (OH)1 .28(B.diol)0 .4(O) 0 .51 ]n

Fig. 1. Scheme for the complexation of Ti(OEt)4 with B.diol-2H and the hydrolysis of the
complex.

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Kayan

(product) indicated that 0.6 mol of B.diol-2H dissociated from starting

complex 1. 1 H-NMR (in CDCl3 ), ppm (multiplicity, assignment): 1.2
(t, CH 3 , Ti-OEt, EtOH); 3.64 (m, CH 2 , EtOH); 3.91 (s, OH, from TiOH,
EtOH and B.diol-2H); 4.14 (brs, CH 2 , B.diol-2H); 4.26 (brs, CH 2 , TiOEt);
4.88 (brs, CH 2 , Ti-OCH 2 CH=); 5.69 (m, CH, Ti-OCH 2 CH=, B.diol-2H).
13
C{ 1 H}-NMR (in CDCl3 ), ppm (assignment): 18.04 (CH 3 , EtOH); 57.73
b
(HO-CH 2 -CH=, B.diol-2H); 64.10 (CH 2 , EtOH); 130.7 (HO-CH 2 -CH=,
b
b
b
13
B.diol-2H). The same data were obtained for the C- and 1 H-NMR
spectra using ethanol as a solvent.

TGA-DTA of Hydrolyzed-Product of [Ti(OEt)2 (B.diol)]n

After the hydrolyzed product was dried under vacuum at 60C, the
product (50 mg) was used for TGA and DTA measurements. The thermograms are shown in Fig. 2. The TGA of the hydrolyzed product resulted in
a weight loss of 50.7% up to 800C. It is assumed that all the organic
groups are removed at this temperature. In other words, hydrolyzed
product contained 49.3% TiO2 , (or 29.6% Ti). Two exothermic peaks in
DTA of the hydrolyzed product appear at 215 and 510C and are
attributed to the removal of the organic groups.

Fig. 2. TGA and DTA curves of the hydrolyzed product of [Ti(OEt)2 (B.diol)]n .

Complexation of Titanium Alkoxides with Cis-2-butene-1,4-diol

33

Preparation of [Ti(OBu n)2 (B.diol)]n (3)

A preparative procedure for 3, which was analogous to the above for 1,
was performed [Eq. (4)]. 13C{ 1 H}-NMR (in CDCl3 ), ppm (assignment):
14.01 ( 4CH3, OBu n=); 19.18 ( 3CH 2 , OBu n ); 35.19 ( 2CH 2 , OBu n ); 62.84
b
b
b
(Ti-OCH 2 -CH=); 75.79 ( 1CH 2 , OBu n ); 131.4 (Ti-OCH 2 -CH=); (Fig. 3).
b
b
b
1
H-NMR (in CDCl3 ), ppm (multiplicity, assignment): 1.0 (t, 4CH 3 ,
n
3
n
1
2
OBu ); 1.31.6 (m, CH 2 CH 2 , OBu ); 4.25 (m, CH 2 , OBu n ); 4.90 (brs,

Fig. 3.

C-NMR spectra of Ti(OBu n )4 (1), B.diol-2H (2), and [Ti(OBu n )2 (B.diol)]n (3).

13

34

Kayan

CH 2 , from Ti-OCH 2 -CH=); 5.83 (brs, CH, from Ti-OCH 2 -CH=). ( 4CH 3 3
CH 2 - 2CH 2 - 1CH 2 -OTi).
Ti(OBu n )4 +B.diol-2H |||Q
[Ti(OBu n )2 (B.diol)]n
2Bu nOH

(4)

Hydrolysis of [Ti(OBu n )2 (B.diol)]n (4)

A preparative procedure for 4, which was analogous to the above
for 1, was performed. 1 H-NMR (in CDCl3 ), ppm (multiplicity, assignment): 0.92 (t, 4CH 3 , TiOBu n and Bu n OH); 1.271.60 (m, 3CH 2 2CH 2 ,
b
TiOBu n and Bu n OH); 3.57 (m, 1CH 2 , Bu n OH); 3.97 (s, OH, from TiOH,
Bu n OH and B.diol-2H); 4.14 (brs, CH 2 , B.diol-2H); 4.48 (brs, CH 2 ,
TiOBu n ); 5.05 (brs, CH 2 , TiOCH 2 CH=); 5.69 (t, CH, TiOCH 2 CH=, and
B.diol-2H); (Fig. 4). 13C{ 1 H}-NMR (in CDCl3 ), ppm (assignment): 13.95
( 4CH 3 , Bu n OH); 19.13 ( 3CH 2 , Bu n OH); 34.85 ( 2CH 2 , Bu n OH); 57.70 (HOb
b
b
CH 2 -CH=, B.diol-2H); 62.13 ( 1CH 2 , Bu n OH); 130.8 (HO-CH 2 -CH=,
b
b
b
B.diol-2H). ( 4CH 3 - 3CH 2 - 2CH 2 - 1CH 2 -OH, from hydrolysis of complex 3).

Fig. 4.

H-NMR spectrum of the hydrolyzed product of [Ti(OBu n )2 (B.diol)]n .

Complexation of Titanium Alkoxides with Cis-2-butene-1,4-diol

35

Table I. KarlFischer Titration of the Hydrolysis of [Ti(OBu n )2 (B.diol)]n

Added water/Ti(OBu n )4 , mole

Consumed water, mole

2/1
3/1
4/1

1.30
1.38
1.42

The consumed water was found to be 1.42 mole (4H 2 O/Ti butoxides)
by KF titration (Table I). The amount of dissociated B.diol-2H from the
starting complex 3 was found to be approximately 0.6 mole from the
1
H-NMR data [Eq. (5)].
+4H2 O
|||Q [Ti(OBu n )0.9 (OH)0.54 (B.diol)0.4 (O)0.88 ]n
[Ti(OBu n )2 (B.diol)]n ||
1.1Bu nOH
0.6B.diol-2H
(5)

TGA-DTA of the Hydrolyzed Product of [Ti(OBu n )2 (B.diol)]n

After the hydrolyzed product of [Ti(OBu n )2 (B.diol)]n was dried at
60C, TGA and DTA measurements were obtained. The TGA of the
hydrolyzed product showed a weight loss of 56.2% up to 800C. By the
time that temperature is reached, all the organic groups are removed. The
hydrolyzed product, therefore, contained 43.8% TiO2 (or 263% Ti). As
shown in Fig. 5, the DTA of the hydrolyzed product included two
exothermic peaks at 208 and 516C, which is consistent with the removal of
the organic groups.

Fig. 5. TGA-DTA curves of the hydrolyzed product of [Ti(OBu n )2 (B.diol)]n .

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Kayan

RESULTS AND DISCUSSION

The 13C{ 1 H}-NMR spectrum of uncoordinated cis-2-butene-1,4-diol
exhibits two peaks at 57.66 (HO-CH 2 -CH=) and 130.6 ppm (HO-CH 2 b
CH=). When cis-2-butene-1,4-diol is coordinated to Ti(OEt)4 , the CH 2 and
b
CH carbons of organic ligand are shifted to 64.0 and 131.3 ppm, respectively. The 1 H-NMR spectrum of the uncoordinated B.diol-2H also shows
three peaks at 3.00, 4.20, and 5.73 ppm, which are characteristic of
hydroxyl, CH 2 and CH protons, respectively. Upon addition of cis-2butene-1,4-diol to titanium ethoxide, the CH 2 protons of the diol are
shifted downfield to 4.93 ppm. Furthermore, the signal for the OH proton
in the 1 H-NMR spectrum is absent. Lack of an OH proton signal indicates
that the B.diol is quantitatively coordinated to titanium.
Characteristic 1 H- and 13C-NMR data were obtained for complex 3.
For example, the 1 H-NMR spectrum 3 is consistent with that of
[Ti(OEt)2 (B.diol)]n . Hence, the presence of the -OCH 2 CH=CHCH 2 Oligand is evident by the appearance of a broad singlet at 4.90 ppm for the
CH 2 protons and at 5.83 ppm for the CH proton. It is proposed, therefore,
that cis-2-butene-1,4-diolate is bonded to the titanium alkoxide as a chelating bridge ligand, as suggested by HubertPfalzgraf [17]. For instance,
[Ti(OPr i )2 (B.diol)]4 was determined to be an open-shell, tetranuclear
polyhedron and, therefore, n should be 4.
The hydrolysis reactions for compounds 1 and 3 were investigated by
13
C- and 1 H-NMR spectroscopy and KarlFischer titration. The unsaturated organic ligand; i.e., cis-2-butene-1,4-diolate, in compounds 1 and 3
is stable toward hydrolysis for a several hours in a 1:4 Ti-alkoxide/H 2 O
ratio. 1 H- and 13C-NMR spectra of the hydrolyzed product were taken
without removal of the dissociated B.diol-2H and the released alkoxides.
Thus, the 1 H-NMR spectra of the transparent solutions of hydrolyzed
products 2 and 4 in CDCl3 show that almost 60% of the cis-2-butene-1,4diol are dissociated from the starting complexes 1 and 3. The CH 2 protons
of the dissociated B.diol-2H from compounds 2 and 4 appear at 4.14 ppm
(see Fig. 4 for compound 4). The 1 H-NMR spectra of the hydrolyzed
compounds of 2 and 4 show CH 2 proton signals for the B.diol at 4.88 and
5.05 ppm, respectively. These signals are evidence for the formation of both
2 and 4. The 1 H-NMR spectra of both 2 and 4 exhibited an OH signal for
Ti-OH, CH 3 CH 2 OH, and HOCH 2 CH=CHCH 2 OH at 3.91 ppm. The shift
in this signal suggests that the OH protons of ethanol and B.diol-2H are
weakly bonded to titanium in the mixture. In contrast, the 13C-NMR
spectra of hydrolyzed products 2 and 4 indicate that ethanol and B.diol-2H
are dissociated from titanium. Because the data collection for 13C-NMR
spectra took a long time, the hydrolyzed product decomposed to titanium

Complexation of Titanium Alkoxides with Cis-2-butene-1,4-diol

Fig. 6.

37

C-NMR spectrum of the hydrolyzed product of [Ti(OBu n )2 (B.diol)]n .

13

hydroxides, ethanol and cis-2-buten-1,4-diol in the presence of water

(i.e., 4:1 H 2 O/Ti). The 13C-NMR spectrum of the hydrolyzed product of
[Ti(OBu n )2 (B.diol)]n (Fig. 6) reveals two characteristic peaks for the dissociated cis-2-butene-1,4-diol at 57.70 (OCH 2 ) and 130.8 (CH=) ppm,
respectively.
The KarlFischer titration measurement indicates that [Ti(OEt)2
(B.diol)]n and [Ti(OBu n )2 (B.diol)]n consume 1.79 and 1.42 moles H 2 O,
respectively. If both the KarlFischer titrations and the NMR spectroscopy
results are considered, the formula of hydrolyzed products is [Ti(OEt)0.9
(OH)1.28 (B.diol)0.4 (O)0.51 ]n (2) and [Ti(OBu n )0.9 (OH)0.54 (B.diol)0.4 (O)0.88 ]n (4).
The oxo ligand stems from a condensation reaction between the alkoxyl
and hydroxyl groups bonded to titanium. The calculated percentage Ti for

38

Kayan

complexes 2 and 4 is 31.35 and 27.95%, respectively. These values are very
close to thermogravimetric analysis result, which gives 29.59% Ti for 2 and
26.25% Ti for 4.
CONCLUSION
In summary, inorganic-organic hybrid compounds 1 and 3 were
synthesized by the sol-gel process and characterized by 13C{ 1 H}- and
1
H-NMR spectroscopy. These compounds can be used as a source of
titania to obtain low density, microcellular, doped organic materials [17].
Compounds 1 and 3 contain a double bond, which is suitable for addition
and polymerization reactions. The hydrolysis of 1 and 3 was also studied.
The hydrolysis products, 2 and 4, were characterized by 13C{ 1 H}- and
1
H-NMR spectroscopy and KarlFischer titration. Both compounds were
stable for several hours in water.
ACKNOWLEDGMENTS
The author thanks Inonu University where the KarlFischer titration
measurements were carried out, and the Institut fur neue Materialien
(INM) in Saarbruken, Germany, for providing the 13C- and 1 H-NMR
spectra and the TGA-DTA measurements.
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Complexation of Titanium Alkoxides with Cis-2-butene-1,4-diol

39

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