Synthesis, X-ray structure, characterization and catalytic activity of a polymeric manganese(II) complex with iminodiacetate

Article abstract of DOI:10.1002/aoc.1802

A polymeric manganese(II) complex with the general formula [Mn(O ₂CCH₂NH₂CH₂CO₂) ₂(H₂O)₂]_n from reaction of iminodiacetatic acid and manganese(II) perchlorate under nitrogen in water, was synthesized and characterized. The structure of the complex was determined using single-crystal X-ray diffraction, elemental analysis, IR and UV-vis spectra. This complex exhibited excellent catalytic activity and selectivity for oxidation of various alcohols and sulfides to the corresponding aldehydes/ketone and sulfoxides using urea hydrogen peroxide and oxone (2KHSO ₅·KHSO₄·K₂SO₄), respectively, as oxidants under air at room temperature. The easy preparation, mild reaction conditions, high yields of the products, short reaction time, no over-oxidation products, high selectivity and inexpensive system make this catalytic system a useful method for oxidizing various alcohols and sulfides. Copyright

Full text of DOI:10.1002/aoc.1802

Full Paper
Received: 2 May 2010
Revised: 19 March 2011
Accepted: 21 March 2011
Published online in Wiley Online Library: 31 May 2011
(wileyonlinelibrary.com) DOI 10.1002/aoc.1802
Synthesis, X-ray structure, characterization
and catalytic activity of a polymeric
manganese(II) complex with iminodiacetate
a∗
a
a
Mojtaba Bagherzadeh , Mojtaba Amini , Davar M. Boghaei ,
b
c
Mohammad Mahdi Najafpour and Vickie McKee
A polymeric manganese(II) complex with the general formula [Mn(O2CCH2NH2CH2CO2)2(H2O)2]n from reaction of iminodiac-
etatic acid and manganese(II) perchlorate under nitrogen in water, was synthesized and characterized. The structure of the
complexwasdeterminedusingsingle-crystalX-raydiffraction, elementalanalysis, IRandUV-visspectra. Thiscomplexexhibited
excellent catalytic activity and selectivity for oxidation of various alcohols and sulfides to the corresponding aldehydes/ketone
and sulfoxides using urea hydrogen peroxide and oxone (2KHSO5·KHSO4·K2SO4), respectively, as oxidants under air at room
temperature. The easy preparation, mild reaction conditions, high yields of the products, short reaction time, no over-oxidation
products, high selectivity and inexpensive system make this catalytic system a useful method for oxidizing various alcohols
and sulfides. Copyright ꢀc 2011 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: manganese(II); crystal structure; iminodiacetate; alcohol; sulfide; oxidation
Introduction
measured on a FT-IR Jasco 460 spectrophotometer with KBr pel-
lets, and electronic spectra on a Jasco 7850 spectrophotometer.
Electronic spectra were recorded using a Cary 100 Bio Varian
UV–vis spectrometer. The reaction products of oxidation were
determined and analyzed using an HP Agilent 6890 gas chro-
matograph equipped with a HP-5 capillary column (phenyl methyl
siloxane, 30 m × 320 µm × 0.25 µm) and a flame-ionization detec-
tor. The X-ray crystallography data were collected at 150(2) K on a
Bruker APEXII CCD diffractometer.
Sulfoxides and aldehydes/ketone are useful reagents in organic
synthesis and they are also valuable synthetic intermediates in the
preparation of chemically and biologically active compounds.[
Transition metal complexes are well known for their catalytic
activities, and their use as catalysts for selective and controlled
oxidation reactions has prompted extensive studies.
Research on transition metal complexes with carboxylic acids
has been the subject of numerous reports.
1–4]
[
5–9]
[
10–12]
There has been
considerable interest in the coordination chemistry of manganese
complexesbecauseofthesignificantinvolvementofmanganesein
Preparation of complex [Mn(O2CCH2NH2CH2CO2)2(H2O)2]n
[
13–21]
various biological systems.
Polymer–metal complexes have
The complex was prepared by dissolving iminodiacetatic acid
(4 mmol, 532.4 mg) and manganese(II) perchlorate (2 mmol,
736 mg) in water (20 ml); The mixture was stirred for about 10 min
at room temperature under nitrogen. Then calcium hydroxide
(1 mmol, 74 mg) was added to this solution and stirred for about
3 h at room temperature under nitrogen. This solution yielded
colourless crystals of the complex after 10 days. C8H16Mn N2O10:
anal. calcd for the complex, C 27.0, H 4.5, N 7.9; found, C 27.7, H
also been of interest to many researchers during the past three
decades, and have been successfully employed in many fields.[22]
The iminodiacetate (IDA) dianion as ligand has been used in the
preparation of metal complexes with interesting structures.[
In this paper, we selected iminodiacetatic acid and synthesized
a complex containing manganese(II) with iminodiacetate, and
investigated its catalytic ability to selectively oxidize sulfides
and alcohols using urea hydrogen peroxide (UHP) and oxone,
respectively, as oxidant.
23,24]
−
1
4.7, N 8.3. IR (cm ): 3423(b), 1584(s), 1408(s), 1323(m), 1266(m),
∗
Correspondence to: Mojtaba Bagherzadeh, Chemistry Department, Sharif
University of Technology, PO Box 11155-3615, Tehran, Iran.
E-mail: Bagherzadehm@sharif.edu
Experimental Section
Materials and Instrumentation
a Chemistry Department, Sharif University of Technology, PO Box 11155-3615,
Tehran, Iran
All reagents and materials used for synthesis were reagent grade.
They were purchased from Merck or Fluka and used without
further purification.
b Department of Chemistry, Institute for Advanced Studies in Basic Sciences,
45195-1159, Gava Zang, Zanjan, Iran
Elemental analyses were performed on a Perkin-Elmer 2400
CHNS/O elemental analyzer. IR spectra (400–4000 cm ) were
c Department of Chemistry, Loughborough University, Leicestershire LE11 3TU,
UK
−
1
Appl. Organometal. Chem. 2011, 25, 559–563
Copyright ꢀc 2011 John Wiley & Sons, Ltd.

M. Bagherzadeh et al.
1
5
123(m), 1008(w), 924(m), 874(w), 797(w), 724(w), 704(w), 596(w),
28(w). UV–vis: 197 nm (ε = 7.3 × 10 l mol cm ).
4
−1
−1
General Procedure for Sulfide Oxidation
A typical reaction using the complex [Mn(O2CCH2NH2CH2
CO2)2(H2O)2]n as a catalyst and sulfides as substrates at a 1 : 20 mo-
lar ratio is described as follows. To a solution of sulfide (0.2 mmol),
imidazole(0.1 mmol)astheaxialligand,chlorobenzene(0.2 mmol)
as the internal standard and catalyst (0.01 mmol) in a (1 : 1) mix-
ture of CH3OH–CH2Cl2 (1 ml), was added UHP (0.4 mmol) as the
oxidant. The mixture was stirred at room temperature and the
progress of the reaction was monitored by GC, by removing small
samples of the reaction mixture. To establish the identity of the
products unequivocally, the retention times and spectral data
were compared with those of commercially available compounds.
All the reactions were run at least in duplicate.
General Procedure for Alcohol Oxidation
Catalytic oxidation of alcohols to corresponding carbonyl com-
pounds by the Mn(II) complex containing iminodiacetate as ligand
was studied in the presence of oxone as the oxidant. In a typical
experiment, a solution of oxone (0.2 mmol) in H2O (5 ml) at room
temperaturewasaddedtoasolutionofalcohol(0.2 mmol),tetra-n-
butylammonium bromide, (0.1 mmol), chlorobenzene (0.2 mmol)
as the internal standard and catalyst (0.01 mmol), in CH2Cl2 (1 ml),
and the biphasic mixture was stirred vigorously. Formation of
products and consumption of substrates were monitored by gas
chromatography. Authentic samples of all oxygenated product
were used to attribute the peaks in chromatograms (compari-
son of retention times was carried out for different regimes of
GC-analysis). Blank experiments showed that, in the absence of
catalyst, only very small amounts of products were formed. Oxi-
dation product yields based on the oxidant, were quantified by
comparison with chlorobenzene. The details of the catalytic ac-
tivity of the complex with respect to oxidation of sulfides and
alcohols are recorded in the Results and Discussion section.
Figure 1. Molecular structure of the complex.
X-ray Crystallography
The determinations of unit cell parameters and data collections
were performed with Mo-Kα radiation (λ = 0.71073 Å). The struc-
ture was solved by direct methods and semi-empirical absorption
corrections were applied using the SHELXS-97 program.[ The
final refinement was performed with the SHELXL-97 program by
Figure 2. H-bonds between sheets in the polymeric complex.
25]
2
full matrix–least squares methods on F with anisotropic ther-
sulfoxides using UHP and oxone (2KHSO5·KHSO4·K2SO4) was also
studied.
Each Mn ion is 6-coordinate and is bonded to four carboxylate
[
25]
mal parameters for nonhydrogen atoms. The hydrogen atoms
were generated theoretically onto the atoms to which they were
attached and refined isotropically with fixed thermal factors.
−
oxygen atoms, each from a different (O2CCH2NH2CH2CO2)
zwitterion (the carboxylates are deprotonated but the amine is
protonated), with two water molecules trans to each other (Fig. 1).
The second carboxylate group on each ligand is coordinated
to a different Mn(II) ion, resulting in a 2D sheet perpendicular
to c. Each protonated amine is H-bonded to the uncoordinated
oxygen atoms of two different ligands. The sheets are linked by H-
bonding from the coordinated water molecules to uncoordinated
carboxylate oxygen atoms (Fig. 2). The structure is chiral and the
absolute configuration was determined unambiguously from the
diffraction data.
Results and Discussion
Complex Characterization
The complex was synthesized as reported previously.[26,27] A new
syntheticroutewithhighyieldforthecomplexisreportedhere.The
complex was prepared by reacting iminodiacetatic acid and man-
ganese(II) perchlorate in water and characterized by single-crystal
X-ray diffraction, elemental analysis, IR and UV–vis spectroscopy.
The catalytic activity of complex for oxidation of various alco-
hols and sulfides to the corresponding aldehydes/ketone and
The IR spectrum of the complex displays a medium and
−
1
broad absorption band at about 3423 cm for the stretching
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Copyright ꢀc 2011 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2011, 25, 559–563

Polymeric manganese(II) complex with iminodiacetate
Table 1. The effect of various conditions in the oxidation of methylphenylsulfide by [Mn(O2CCH2NH2CH2CO2)2(H2O)2]n – UHPa
Amount of catalyst
(mmol)
Amount of UHP
(mmol)
Amount of imidazole
(mmol)
Selectivity to sulfoxide
Conversion (%)b
(%)
c
Entry
Solvent (1 ml)
1
2
3
4
5
6
7
8
9
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.005
0.015
0.01
0.01
0.01
0.01
0.01
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.2
0.3
0.5
0.4
0.4
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0
CH2Cl2 –CH3OH
CH2Cl2
51
15
36
34
13
41
44
38
54
25
37
57
11
50
96
100
99
CH3OH
CH3CN
100
100
99
CH3COCH3
CH3COCH3 –CH3OH
CH2Cl2 –CH3CN
CH2Cl2 –CH3OH
CH2Cl2 –CH3OH
CH2Cl2 –CH3OH
CH2Cl2 –CH3OH
CH2Cl2 –CH3OH
CH2Cl2 –CH3OH
CH2Cl2 –CH3OH
98
98
87
10
11
12
13
14
100
100
78
100
91
0.2
a
b
c
Reaction conditions: methylphenylsulfide, 0.2 mmol.
The GC conversions (%) were measured relative to the methylphenylsulfide after 60 min.
Selectivity to sulfoxide = [sulfoxide %/(sulfoxide % + sulfone %)] × 100.
vibrations of coordinated water. Absorption bands at about 1590
and 1408 cm can be assigned to the antisymmetric stretching
vibrations and symmetric stretching vibrations of carboxylate
Table 2. Oxidation of sulfides catalyzed by [Mn(O2CCH2NH2CH2
−
1
CO2)2(H2O)2]na
groups.[28] Thevalueofꢀυas–s [υas(COO)−υs(COO)]is∼200 cm
−1
Turnover
,
Conversion Selectivity to Number
indicating a monodentate coordination mode of carboxylate
groups.[ This result was consistent with the crystal structure.
The electronic spectrum of the complex shows an absorption
b
c
d
e
Entry
1
Substrate
(%) (%)
sulfoxide (%)
(TON)
28]
51(6)
96
10.2
4
−1
−1
band at 197 nm (ε = 7.3 × 10 l mol cm ) for the complex,
∗
∗
[29]
attributed to π –π or n–π charger transfer of the ligand.
2
3
56(7)
55(8)
97
98
11.2
11
Catalytic Reactivity
Inordertofindtheoptimumconditionsfortheoxidationreactions,
the effects of reaction conditions including reaction time, the
amount of catalyst and oxidant were investigated.
4
5
61(6)
48(5)
98
12.2
9.6
Sulfide oxidation
Methylphenylsulfide was used as a model substrate and subjected
to different reaction conditions, as shown in Table 1. The oxidation
wasinvestigatedinvarioussolvents, suchasCH2Cl2 –CH3OH(1 : 1),
CH2Cl2, CH3OH, CH3CN, CH3COCH3, CH3COCH3 –CH3OH (1 : 1) and
CH2Cl2 –CH3CN (1 : 1) (entries 1–7).
Our findings showed CH2Cl2 –CH3OH (1 : 1) to be the optimum
solvent and it was used in subsequent optimization studies. The
conversion of methylphenylsulfide increased monotonically with
the addition of catalyst between 0.005 and 0.01 mmol. When the
amount of catalyst was increased to 0.015 mmol, the reaction
led to more sulfone and the selectivity of methylphenylsulfide
oxidation reduced from 96 to 87% (entries 8 and 9).
100
6
7
8
CH3CH2-S-CH2CH3
CH3(CH2)2-S-(CH2)2CH3
CH3(CH2)7-S-(CH2)7CH3
41(1)
36(0)
33(0)
100
100
100
8.2
7.2
6.6
a
Molar ratios for catalyst: imidazole–substrate–UHP, 1: 10 : 20 : 40. The
reactions were performed in a 1 : 1 mixture of CH2Cl2 –CH3OH (1 ml)
under air at room temperature.
b
The GC conversions (%) were measured relative to the starting sulfide
after 60 min.
c
Oxidation of sulfide was carried out in the absence of catalyst.
Selectivity to sulfoxide = [sulfoxide %/(sulfoxide % + sulfone %)] ×
d
The reaction was also monitored at different UHP concen-
trations. When the amount of UHP was increased from 0.2 to
100.
e
TON = (mmol of sulfoxide + mmol of sulfone)/mmol of catalyst.
0.4 mmol, the methylphenylsulfide conversion increased from 25
to 51%. With further increases in UHP to 0.5 mmol, the selectivity
to sulfoxide decreased from 96 to 78% (entries 10–12). According
to the literature for the manganese complex, when UHP is used
as the sole oxidant, the catalytic efficiency is poor, but when im-
idazole (ImH) is added as an additive (axial ligand), the efficiency
improves.[
To find the optimum amount of imidazole, the oxidation of
methylphenylsulfide was performed with different molar ratios
of imidazole per catalyst (entries 13 and14). As Table 1 shows,
increasing the molar ratio of ImH/catalyst up to 10 raised
30,31]
Appl. Organometal. Chem. 2011, 25, 559–563
Copyright ꢀc 2011 John Wiley & Sons, Ltd.
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M. Bagherzadeh et al.
Table 3. The effects of various conditions on the oxidation of benzyl alcohol by the [Mn(O2CCH2NH2CH2CO2)2(H2O)2]n –oxone–n-Bu4NBr catalytic
a
system
Amount of catalyst
(mmol)
Amount of oxone
(mmol)
Selectivity to
benzaldehyde (%)
Conversion (%)b
c
Entry
Time of reaction (min)
Solvent–H2O (1 : 5 ml)
1
2
3
4
5
6
7
8
9
0.01
0.01
0.01
0.01
0.01
0.005
0.015
0.01
0.01
0.01
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.1
0.3
0.2
30
30
30
30
30
30
30
30
30
60
CH2Cl2
CH3Cl
81
63
49
55
38
58
83
44
93
86
100
100
100
100
100
100
98
CH3CN
CH3COCH3
n-hexane
CH2Cl2
CH2Cl2
CH2Cl2
100
92
CH2Cl2
10
CH2Cl2
95
a
b
c
Reaction conditions: benzyl alcohol, 0.2 mmol, n-Bu4NBr 0.1 mmol.
The conversions (%) were measured at room temperature.
Selectivity to benzaldehyde = [benzaldehyde/(benzaldehyde + benzoic acid)] × 100.
the oxidation yield of catalytic system. However increasing the
amount of imidazole to 0.2 mmol decreased conversion but also
increased the amount of sulfone to 9% (entries 13 and 14). It
was also found that, without imidazole, UHP alone could not
oxidize sulfides to sulfoxides. Therefore, an optimum amount of
catalyst, oxidant and imidazole with a suitable solvent for the
sulfide oxidation is necessary. Based on the above observations
we conclude that 0.01 mmol of catalyst, 0.4 mmol of UHP,
[Mn(O2CCH2NH2CH2CO2)2(H2O)2]n as the catalyst in the pres-
ence of oxone and tetra-n-butylammonium bromide as phase
transfer agent (entries 1–5). When the reaction was carried out in
CH Cl , the conversion of benzyl alcohol was higher than in CH Cl,
2
2
3
CH CN, CH COCH or n-hexane. This illustrated that the solvent
3
3
3
had an effect on the reaction. The addition of catalyst led to an
increase in conversion to benzaldehyde (entries 6 and 7). With the
use of 0.005 and 0.01 mmol catalyst, respectively, the conversion
reached 58 and 81%. With more catalyst, there was no further
increase in the conversion and the selectivity of benzyl alcohol
oxidation reduced from 100 to 98%. The amount of oxone also
significantlyaffectedtheconversionandbenzaldehydeselectivity.
With increases in oxone to 0.2 mmol, benzaldehyde reached the
highest yield. However, excess oxone led to increased conversion
to 93% with decreased selectivity to 92% (entries 8 and 9). Further-
more, the reaction time was also optimized (entry 10). The reaction
was fast, giving 81% conversion of benzyl alcohol after 30 min.
Further increases to 60 min led to increased conversion to the
maximum value (86%), with a small decrease in selectivity to 95%
owing to the expected subsequent oxidation to carboxylic acid.
After identifying the most effective catalytic conditions,
reactions were performed at room temperature under air in
CH2Cl2 –H2O containing the catalyst, tetra-n-butylammonium
bromide, substrate and oxone in a 1 : 20 : 10 : 20 molar ratio. The
systemwasusedtooxidizeawidevarietyofprimaryandsecondary
aliphatic and benzylic alcohols to the corresponding aldehydes
or ketones (Table 4). Benzyl alcohols were oxidized to give the
corresponding aldehydes with 64–81% conversion (entries 1–4).
Substrates having electron-donating and -withdrawing
substituents on the aromatic ring were compatible with this
protocol. The nature of the substituents (methyl, methoxy and
nitro) was changed to probe the electronic effects, but this caused
no consistent in the conversion. Although it is difficult to stop
the oxidation of primary alcohols at the intermediate aldehyde
stage, this system is very useful in transforming primary alcohols
into aldehydes without over-oxidation to carboxylic acids.
Secondary alcohols, e.g. cyclohexanol, 2-methyl cyclohexanol,
0
.1 mmol of ImH and CH2Cl2 –CH3OH (1 : 1) as solvent are the
best combination for oxidation of sulfides to sulfoxides with good
selectivity.
After optimization, the oxidations of various sulfides were
investigated and the details of catalytic activity with respect to
oxidation of sulfides are recorded in Table 2.
Various types of structurally diverse substrates – arylalkyl,
diaryl, dibenzyl, benzylphenyl and dialkyl sulfides – underwent
smooth and selective oxidation to produce the corresponding
sulfoxides in good yields (Table 2). Both aliphatic and aromatic
sulfides were effectively oxidized to the corresponding sulfoxides
(in yields of 33–61%). In a few cases, minor amounts of byproducts
resulting from overoxidation to sulfone were found (entries 1–4).
The highest and lowest yields were obtained for dibenzylsulfide
and dioctylsulfide (61 and 33%), respectively (entries 4 and 8). The
replacement of one or both alkyl groups in the dialkylsulfide with
phenyl or benzyl to probe electronic effects caused an increasing
trend in the yield (entries 1–5). As shown in Table 2, the catalytic
oxidation of sulfides showed moderate efficiency in yield but
excellent selectivity.
In order to check the polymeric nature of the complex
[Mn(O2CCH2NH2CH2CO2)2(H2O)2]n in solution, under oxidative
degradation, we also compared the FT-IR spectral analysis of
complex before and after methylphenylsulfide oxidation under
the optimal reaction conditions. The obtained results indicate
that catalyst is not prone to decomposition and the polymeric
nature of catalyst is preserved throughout sulfide oxidation.
Alcohol oxidation
4-methyl cyclohexanol and 1-indanol, can be converted to the
Table 3 reflects efforts to optimize conditions for the oxi-
dation of alcohols. At first, five solvents–H2O (1 : 5) – CH2Cl2,
CH3Cl, CH3CN, CH3COCH3 and n-hexane – were tested with
corresponding ketones in 66–91% conversion (entries 5–8).
Linear secondary alcohols were less reactive in comparison
to aromatic and cyclic alcohols (entries 9 and 10). The results
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Copyright ꢀc 2011 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2011, 25, 559–563

Polymeric manganese(II) complex with iminodiacetate
Supporting Material
Table 4. Oxidation of alcohols catalyzed by [Mn(O2CCH2NH2CH2
CO2)2(H2O)2]n
a
Supporting information can be found in the online version of this
article. Tables of crystallographic data, IR spectrum of complex
and CCDC 760648 contain the supplementary crystallographic
data for this paper. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
b
c
d
e
Entry
1
Substrate
Conversion (%) (%) TON (selectivity, % )
81(31)
74(28)
16.2 (100)
14.8 (100)
2
3
4
76(30)
64(16)
15.2 (100)
12.8 (100)
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10.2
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[
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[
[
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Conclusions
We have presented the synthesis, structural character-
ization and catalytic reactivity of
a polymeric complex
[Mn(O2CCH2NH2CH2CO2)2(H2O)2]n. The complex was used in the
1
986, pp. 231–233.
oxidationofsulfidesandalcoholstotheircorrespondingsulfoxides
and aldehydes or ketones, respectively, and was very efficient in
termsofcatalysteconomy, selectivity, yieldandcost-effectiveness.
[
[
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Acknowledgments
E. Bouwman, J. G. Haasnoot, J. Reedijk, Inorg. Chem. Acta 1998, 279,
217.
We are grateful to the Research Council of Sharif University
of Technology and the Institute for Advanced Studies in Basic
Sciences for their financial support.
Appl. Organometal. Chem. 2011, 25, 559–563
Copyright ꢀc 2011 John Wiley & Sons, Ltd.
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