Fluoro functional groups substituted cobalt(II), iron(II) phthalocyanines and their catalytic properties on benzyl alcohol oxidation

Article abstract of DOI:10.1007/s10847-016-0650-z

In this study, phthalocyanine complexes (Co and Fe) bearing (2-{2-[3-(trifluoromethyl)phenoxy]ethoxy}ethoxy) groups at peripheral position were synthesized using the phthalonitrile derivative and characterized by IR, ¹H-NMR, UV–Vis and mass spe

Full text of DOI:10.1007/s10847-016-0650-z

J Incl Phenom Macrocycl Chem
DOI 10.1007/s10847-016-0650-z
ORIGINAL ARTICLE
Fluoro functional groups substituted cobalt(II), iron(II)
phthalocyanines and their catalytic properties on benzyl alcohol
oxidation
2
1
•
Ays¸e Aktas¸1 Irfan Acar Ece Tugba Saka Zekeriya Biyiklioglu1
˙
•
•
•
˘
Halit Kantekin1
Received: 30 May 2016 / Accepted: 11 August 2016
Ó Springer Science+Business Media Dordrecht 2016
Abstract In this study, phthalocyanine complexes (Co and
Fe) bearing (2-{2-[3-(trifluoromethyl)phenoxy]ethoxy}ethoxy)
groups at peripheral position were synthesized using the
porphyrazines, don’t occur in nature as they are completely
synthetic compounds which synthesize a lot of application
areas such as electrochromism [2], chemical sensors [3],
liquid crystals [4], photovoltaic cells [5], catalysts [6–12]
and particularly in photodynamic therapy [13–15].
1
phthalonitrile derivative and characterized by IR, H-NMR,
UV–Vis and mass spectrometry. Catalytic activity of Co(II)
and Fe(II) phthalocyanines were investigated in the oxidation
of benzyl alcohol with different oxygen sources. Determination
of the optimal conditions for oxidation of benzyl alcohol, the
catalytic reactions were carried out change the reaction tem-
perature, oxidant/cat ratio, types of oxidants and subst./catalyst
ratio.
One of the main disadvantages in applications of the
phthalocyanine compounds is their low solubility in com-
mon organic solvent or aqueous media. While increasing
the solubility of Pcs in water by adding sulfo [16], car-
boxylic [17] and quaternized ammonium groups [18], some
substituents such as crown ethers [19, 20], alkyl [21],
alkoxy [22], alkylthio groups [23] should be added to
peripheral or non-peripheral positions to benzene rings for
the solubility in organic solvents.
Keywords Phthalocyanine Á Iron Á Cobalt Á Benzyl
alcohol Á Catalytic activity Á Oxidation
The selective oxidation of alcohols to the corresponding
carbonyl compounds is one of the most important and
challenging functional group transformations in organic
synthesis, both for fundamental research and industrial
manufacturing [24]. Especially, the selective oxidation of
benzyl alcohol to higher-value added product benzalde-
hyde has received increasing attention, because the ben-
zaldehyde has tremendous application in perfumery,
pharmaceutical, dyestuff and agrochemical industries
[25–27]. Commercially, the benzaldehyde is synthesized
by the hydrolysis of the benzal chloride and the vapor/
liquid phase oxidation of toluene [28–30]. However, in the
former process, traces of chlorine inevitably exist in the
product benzaldehyde, and in the latter, the selectivity to
benzaldehyde is very poor. Alternatively, direct oxidation
of benzyl alcohol in liquid phase is a promising route for
the manufacture of benzaldehyde, because it completely
overcomes the major drawbacks of as above mentioned.
In this work, benzyl alcohol is converted to benzalde-
hyde (as major product) and the other products by metal-
lophthalocyanine complexes with an oxygen source.
Introduction
Phthalocyanines (Pcs), having 18-p electron system that
the p electrons are delocalized over carbon and nitrogen
atoms like porphyrin and porphyrazine system and struc-
turally similar chlorophyl a and vitamin B12, appear blue-
green color tone [1]. Pcs, unlike porphyrins and
Electronic supplementary material The online version of this
article (doi:10.1007/s10847-016-0650-z) contains supplementary
material, which is available to authorized users.
˙
& Irfan Acar
acar_irfan_2000@yahoo.com
1
Department of Chemistry, Faculty of Sciences, Karadeniz
Technical University, 61080 Trabzon, Turkey
2
Department of Energy Systems Engineering, Faculty of
Technology, Karadeniz Technical University,
61830 Trabzon, Turkey
123

J Incl Phenom Macrocycl Chem
Halogenated substituents of metallophthalocyanine com-
plexes become important in several fields of science and
industry. Halogen substituents can participate in inter-
molecular interactions and control molecular recognition
processes [31]. Due to these electron withdrawing sub-
stituents, Co(II) and Fe(II) phthalocyanine complexes
employee the active catalysts during the benzyl alcohol
oxidation reactions.
7.42 (m, 16H, Ar–H), 6.99–6.92 (m, 12H, Ar–H), 4.14 (m,
16H, –CH2–O), 3.99 (m, 16H, –CH2–O). UV–Vis (THF):
k
max, nm (log e): 707 (4.79), 593 (4.26), 359 (4.80).
MALDI-TOF–MS m/z: 1562.1 [M ? H]?.
Results and discussion
Synthesis and characterization
Experimental
Materials
The synthetic pathways and structure of metallophthalo-
cyanine 2, 3 were shown in Fig. 1. In this work, cyclote-
tramerization of the phthalonitrile derivative 1 [32] to the
peripherally tetra substituted cobalt(II) and iron(II) Pcs 2, 3
were accomplished with corresponding metal salts CoCl2
and Fe(CH3COO)2 in n-pentanol and DBU. Phthalocyanine
complexes 2, 3 were purified with column chromatography.
The characterizations of all new compounds were carried
out by the combination of several methods such as UV–
The used materials, equipments and the general procedure
for the oxidation of benzyl alcohol were supplied as sup-
plementary information.
Synthesis
1
Vis, IR, H-NMR spectra and mass (MALDI-TOF tech-
Cobalt(II) phthalocyanine (2)
nique) spectrometries. All spectral data support the pro-
posed structures as shown in ‘‘Experimental’’ section.
The tetra substituted Co(II) and Fe(II) Pcs 2, 3 were
achieved by cyclotetramerization of the dinitrile derivative
1. The IR spectrum of Co(II) and Fe(II) Pcs 2 and 3 were
confirmed by the disappearance of the C:N vibration at
2233 cm-1. The NMR measurements of the cobalt(II)
phthalocyanine 2 was not be able to take into precluded
4-(2-{2-[3-(Trifluoromethyl)phenoxy]ethoxy}ethoxy)ph-
thalonitrile 1 (0.5 g, 1.33 mmol), anhydrous CoCl2
(0.086 g 0.66 mmol) and 1 mL of n-pentanol were
placed in a standart Schlenk tube in the presence of 1.8-
diazabicyclo[5.4.0]undec-7-ene (DBU) (five drops)
under N2 gas atmosphere and was heated at 160 °C for
24. After cooling to room temperature the reaction
mixture refluxed with ethanol to precipitate the product
which was filtered off. The crude product was collected
by filtration and washed with hot ethanol, diethyl ether
and dried in vacuo. The obtained green solid product was
purified with column chromotography over the alu-
minium oxide by using chloroform:methanol (100:12) as
1
owing to its paramagnetic nature [33]. H NMR spectrum
of iron(II) phthalocyanine 3 showed the aromatic protons
appeared at 7.42–6.92 ppm and aliphatic group at
4.14–3.99 ppm. In the mass spectrum of cobalt and iron
Pcs 2 and 3, which show a molecular ion peak at
m/z = 1563.8 [M ? H]? (Fig. S1) and 1562.1 [M ? H]?
(Fig. S2) respectively, confirmed the proposed structures.
The electronic spectra of the metallophthalocyanines
have two strong absorption bands which are characteristic
Q and B bands, one of them in the UV region at about
300–350 nm (B band) and the other in the visible part of
the spectrum around 600–700 nm (Q band). The electronic
absoption spectra of cobalt and iron Pcs 2 and 3 were
studied in THF at room temperature (Fig. 2). UV–Vis
spectra of cobalt and iron Pcs intense single Q band
absorptions appeared at 664 nm for 2, 707 nm for 3 with
the shoulders around at 604 nm for 2, 593 nm for 3 and the
B bands were observed at 331–359 nm, respectively.
eluents. Yield: 0.168 g (32 %). IR (KBr tablet), m/cm-1
:
3072 (Ar–H), 2930–2875 (Aliph. C–H), 1608 (C=C),
1523, 1490, 1448, 1325 (C–F), 1283, 1236, 1163, 1115
(C–O), 1092, 1061, 998, 946, 859, 823, 821, 783, 749,
696. UV–Vis (THF): kmax, nm (log e): 664 (5.04), 604
(4.53), 331 (4.94). MALDI-TOF–MS m/z: 1563.8
[M ? H]?.
Iron(II) phthalocyanine (3)
This compound was synthesized similarly to 2 from 1 by
using anhydrous Fe(CH3COO)2. The pure green solid
product was obtained by column chromatography on silica
gel with chloroform:methanol (100:10) as a solvent system.
Yield: 0.176 g (28 %). IR (KBr tablet), m/cm-1: 3072 (Ar–
H), 2920–2870 (Aliph. C–H), 1605 (C=C), 1489, 1447,
1397, 1325 (C–F), 1283, 1231, 1162, 1115 (C–O), 1095,
1060, 947, 860, 784, 746, 696. 1H-NMR (CDCl3), (d:ppm):
Catalytic studies
Oxidation of benzyl alcohol with 2 and 3
The catalytic activities of the phthalocyanine complexes
were explored for the oxidation of benzyl alcohol. All the
123

J Incl Phenom Macrocycl Chem
Fig. 1 Synthetic route of
phthalocyanine compounds (2,
3). (i) n-pentanol, DBU, 160 °C
F
F
CN
CN
F
O
O
O
1
CoCl2
Fe(CH3COO)2
i
i
RO
RO
OR
OR
N
N
N
N
N
N
N
N
N
Co
N
Fe
N
N
N
N
N
N
RO
RO
OR
OR
3
2
F
F
F
O
R =
O
2
3
fragments (benzaldehyde as major product, benzoquinone
and benzoic acid as minor products) were determined due
to the attack by catalytically active species (Fig. 3).
Besides, the by-product also included a small amount of
benzyl benzoate in the reaction products. In the blank
reactions (using no catalysts or oxidants) there were no
product detectable (Tables 1, 2). It is proved that presence
of the catalyst and oxidant are essential for the oxidation.
The conversion of benzyl alcohol and the selectivity to
benzaldehyde with Co(II) and Fe(II) Pcs at 50 °C are
shown in Table 1, which indicated that the conversion of
benzyl alcohol increased with the reaction processing and
reached the high conversion of 98 % with complex 2 and
90 % with complex 3 after reaction for 180 min, and then
remained stable with a slight increased. On the other hand,
the obvious decrease in selectivity to benzaldehyde is due
to a further oxidation of benzaldehyde to benzoic acid.
Based on the results of conversion and selectivity, 180 min
was selected as the optimal reaction time.
1,4
1,2
1
0,8
0,6
0,4
0,2
0
300
400
500
600
700
800
Wavelength(nm)
Fig. 2 UV–Vis absorption spectra of compounds 2 and 3 in THF at
1 9 10-5 mol dm-3
oxidation reactions data were given in Tables 1, 2, and 3
and Table S1, S2. In experiments maintained 3 h oxidant
and auxiliary chemicals on the conversion and yields were
investigated.
Table 1 shows the changes in the conversion of benzyl
alcohol by varing the substrat/catalyst molar ratio from 600
to 1600 at 90 °C. The results indicate that the conversion of
benzyl alcohol decreased with an increasing subs/cat ratio.
Lower conversion of benzyl alcohol with higher mass of
Benzyl alcohol can be turned into various organic
compounds in oxidation reactions. In this work, three
123

J Incl Phenom Macrocycl Chem
Table 1 Amount of substrate
effect of benzyl alcohol
oxidation with complex 2 and 3
Catalyst
Subs./catalyst Aldehydea Quinoneb Acidc Tot. conv. (%) TONd TOFe (h-1
)
2
600/1
800/1
1000/1
1200/1
1600/1
–
86
4.7
8.0
2.1
7.0
2.0
6.5
1.8
5.6
1.5
3.9
–
6.22
6.0
5.8
5.1
4.9
4.6
3.8
3.2
3.5
3.0
–
98
588
540
704
632
770
680
864
744
880
768
–
196
180
234
210
256
226
288
248
293
256
–
3
72
90
2
80.1
66.9
70.1
56.9
66.5
53.4
50.3
41.8
–
88
3
79
2
77
3
68
2
72.1
62.2
55.3
48.7
–
3
2
3
Without catalysts
a
Yield of benzaldehyde
Yield of benzoquinone
Yield of benzoic acid
b
c
d
e
TON = mole of product/mole of catalyst
TOF = mole of product/mole of catalyst 9 time
Conversion was determined by GC
Table 2 Amount of oxidant
effect of benzyl alcohol
oxidation with complex 2 and 3
Catalyst Oxidant/catayst
Aldehydea Quinoneb Acidc Tot. conv. (%) TONd TOFe (h-1
)
2
3
2
3
2
3
2
3
2
3
2
3
a
500/1
87.7
80
4.0
8.8
5.2
8.9
5.8
9.1
5.8
8.2
6.2
10.2
–
6.0
6.6
7.7
6.8
8.0
7.0
7.5
6.6
7.4
7.3
–
98
588
540
456
468
360
378
318
330
288
246
–
196
180
152
156
120
126
106
110
96
90
800/1
86.9
84.2
86.1
83.7
86.6
85.0
86.2
82.3
–
76.1
78.6
60
1200/1
63.5
53
1600/1
55.7
48.1
41.9
–
2000/1
82
Without oxidant
–
–
–
–
–
–
–
Selectivity of benzaldehyde
Selectivity of benzoquinone
Selectivity of benzoic acid
b
c
d
TON = mole of product/mole of catalyst
e
TOF = mole of product/mole of catalyst 9 time
Conversion was determined by GC
substrate and lower mass of catalyst was due to the fewer
catalytic sites. This study shows that only 600 subs/cat ratio
was needed for the reaction to reach an optimum conver-
sion of benzyl alcohol (98 % for complex 2 and 90 % for
complex 3) compared the our works in previous.
presented in Table 2. The conversion of benzyl alcohol
decreases from 98 % to 55.3 % for complex 2 and
90–48.7 % for complex 3 on increasing the TBHP:benzyl
alcohol mole ratio from 0.83 to 3.3. Benzyl alcohol con-
version reaches 98 % for complex 2 and 90 % for complex
3, when the substrate to oxidant ratio is increased to 0.83
with the highest TON and TOF values (588, 196 for
complex 2 and 540, 180 for complex 3) The above result
clearly points out that an increase in the TBHP content
The amount of oxidant TBHP is an important factor that
influences the conversion and selectivity in selective oxi-
dation reactions. The influence of the substrate to oxidant
molar ratios was next examined and the results are
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J Incl Phenom Macrocycl Chem
Table 3 Temperature effect of
benzyl alcohol oxidation with
complex 2 and 3
Catalyst
T (°C)
Aldehydea
Quinoneb
Acidc
Tot. conv. (%)
TONd
TOFe (h-1
)
2
3
2
3
2
3
2
3
a
25
83.3
76.2
82.0
75.4
81.9
78.2
87.7
80
10.4
14.2
10.4
14.0
9.7
6.2
9.5
7.4
8.9
8.3
10.1
6.0
6.6
48
42
67
57
72
69
98
90
288
252
402
342
434
414
588
540
96
84
50
70
90
134
114
144
138
196
180
11.6
4.0
8.8
Selectivity of benzaldehyde
Selectivity of benzoquinone
Selectivity of benzoic acid
b
c
d
e
TON = mole of product/mole of catalyst
TOF = mole of product/mole of catalyst 9 time
Conversion was determined by GC
Fig. 3 Product formed through
benzyl alcohol oxidation by an
oxidant in the presence of
catalysts 2 and 3
O
H
O
O
O
OH
o
Oxidant,
Catalyst
90 C
OH
O
O
Benzyl alcohol
Benzaldehyde Benzoquinone Benzoic Acid
Benzyl Benzoate
(Trace amount)
significantly decreases the benzyl alcohol conversion [34].
The selectivity for benzaldehyde is about 86.2 % for
complex 2 and 82.3 % for complex 3 at this oxidant con-
tent. When still more oxidant is used, the selectivity
decreases at TBHP:BzOH mole ratio of 3.3. Therefore, a
molar ratio of TBHP/BzOH of 0.83 was used in further
studies presented below.
Adding H2O2 or m-CPBA in the reaction media, the
reaction color changed from green to brown. This clue
explains that complex 2 and 3 was degraded immediately
with H2O2 or m-CPBA. On the other hand, the results
clearly proved that TBHP is the best oxidant in this system
for both complexes with high conversion and benzaldehyde
selectivity. Adding TBHP in the reaction media, the reac-
tion color changed from green to light green and then dark
yellow. At the end of the reaction, the reaction color turned
to light yellow. The reaction results in the open air, there is
The effect of temperature on the oxidation of benzyl
alcohol over Co(II) and Fe(II) phthalocyanine catalysts was
examined at four different temperatures in the range
25–50 °C. The results are presented in Table 3. A signifi-
cant effect of the temperature on the conversion of benzyl
alcohol is observed. The conversion of benzyl alcohol
increases from about 48 to 98 % for complex 2 and
42–90 % for complex 3 on increasing the reaction tem-
perature from 25 to 90 °C. When the reaction temperature
is increased beyond 90 °C, the benzaldehyde selectivity
decreases slightly. This decrease in selectivity of ben-
zaldehyde can be attributed, as before, to the loss of the
inhibiting effect, due to the complete conversion of the
benzyl alcohol [35]. It therefore, appears that 50 °C is the
optimum reaction temperature for the maximum yield of
benzaldehyde.
Fig. 4 The oxidant effect on benzyl alcohol oxidation [Reaction
conditions: Benzyl alcohol (1.92 9 10-3 mol), complex
In Table S1 different oxidants were used benzyl alcohol
oxidation with catalyst 2 and 3. H2O2 and m-CPBA can
serve as an oxidant but low conversion for both complexes.
2
(3.19 9 10-6 mol), complex
3
(3.20 9 10-6 mol), TBHP
(1.60 9 10-3 mol), DMF (0.01 L), 3 h and 90 °C]
123

J Incl Phenom Macrocycl Chem
Scheme 1 Proposed
mechanism of the formation of
active species from Co(II)Pc
and Fe(II)Pc and TBHP
no sufficient oxygen in the air for oxidation was observed.
Figure 4 was summarized the effect of oxygen source on
the reaction rate benzyl alcohol oxidation with complex 2
and 3.
light brown. This observation proved that cobalt(II)
phthalocyanine can remain longer than iron(II) phthalo-
cyanine on benzyl alcohol oxidation reaction.
According to results of this work, we proposed the
reaction mechanism of the formation of active species from
cobalt(II) phthalocyanine, iron(II) phthalocyanine and
TBHP(t-butyl hydroperoxide). Phthalocyanine complexes
tend to stabilize the lower oxidation states of metal com-
pared to porphyrin complexes. High metallophthalocyani-
nes should be stronger oxidizing agents than their
porphyrin analogues in the same oxidation state. In por-
phyrin series the kind of the cleavage of O–O bond (ho-
molytic vs heterolytic) is determined by the structures of
porphyrin ligand and peroxide and the presence of axial
ligand, which favors a heterolytic O–O bond cleavage [43].
When using t-BuOOH as an oxidant one can suggest the
formation of PcMIII-OOt-Bu complex on the first step. In
general, peroxides can react with iron porphyrin complexes
via homolytic or heterolytic cleavage of the O–O bont to
form LFeIV=O or LFeV=O species (L: porphyrin ligand),
respectively. It is reasonable to assume that iron phthalo-
cyanine would be able to react with t-BuOOH in the same
way to give PcFeIV=O or PcFeV=O according to Scheme 1
[44–47].
Table S2 indicate catalytic activities towards the
homogeneously oxidation of benzyl alcohol of some pre-
viously reported catalyst. Tetraphenylporphyrin cobalt,
iron, copper ruthenium, manganese complexes, unsubsti-
tuted phthalocyanine complexes, perfluoroalkyl phthalo-
cyanine complexes were investigated on benzyl alcohol
oxidation [36–41]. Molecular oxygen, m-CPBA (m-
chloroperoxybenzoic acid), TBHP (t-butylhydroperoxide),
NaIO3 (sodium iodate), NaIO4 (sodium periodate) were
also investigated as oxygen source in these researches.
Among all of the catalysts in these literatures, complex 2
and 3 will be interesting catalysts with TBHP as an oxygen
source in benzyl alcohol oxidation. Especially, complex 2
shows the excellent activity on benzyl alcohol oxidation
process.
Additionally, when the both catalysts compared with
each other, complex 2 was determined the best catalyst
with higher conversion, TON and TOF values than com-
plex 3 in this work. Complex 2 has cobalt(II) and complex
3 has iron(II) central metal ion. Based on this catalytic
study, the activity of metallophthalocyanine is depend on
the nature of the introduced transition metals. The activity
of metallophthalocyanines in oxidation reaction follows the
order CoPc [ FePc. It is known that the catalytic perfor-
mance of transition metal species depends on the outer
d-electron density [42]. On the other hand, while the color
of reaction media included cobalt(II) phthalocyanine as
catalyst can still blue and than light blue, it included iro-
n(II) phthalocyanine unfortunately turned to brown and
Conclusion
In this study, Co(II) and Fe(II) Pcs were synthesized by
using the phthalonitrile derivative and characterized by
several spectroscopic methods. Co(II) and Fe(II) Pcs
employeed active catalysts in benzyl alcohol oxidation by
using TBHP as an oxidant. Especially, Co(II)
123

J Incl Phenom Macrocycl Chem
butylphenoxy substituted indium(III) phthalocyanines. J. Pho-
tochem. Photobiol. A 192, 179–187 (2007)
phthalocyanine shows excellent catalytic performance on
benzyl alcohol oxidation with high yield and selectivity in
3 h. It seems that this kind of catalysis system is very
active, selective and suitable for the oxidation of benzyl
alcohol. In addition, alkyl peroxides proved to be very
efficient and environmentally friendly oxidants since the
by-products were just alkyl alcohols.
14. Ogbodu, R.O., Nyokong, T.: The effect of ascorbic acid on the
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Acknowledgments This study was supported by the Research Fund
of Karadeniz Technical University, Project No: 10440.
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