Tris{2-[(5-fluorosalicylidene)amino]ethyl}amine and its manganese(iii) complex: Synthesis, characterization, crystal structures, and catalytic property

Article abstract of DOI:10.1080/15533174.2016.1212215

A tris-Schiff base tris{2-[(5-fluorosalicylidene)amino]ethyl}amine (H₃L) was prepared by the reaction of 1:3 molar ratio of tris(2-aminoethy1)amine with 5-fluorosalicylaldehyde in methanol. The Schiff base reacted with manganese perchlorate to

Full text of DOI:10.1080/15533174.2016.1212215

Inorganic and Nano-Metal Chemistry
ISSN: 2470-1556 (Print) 2470-1564 (Online) Journal homepage: http://www.tandfonline.com/loi/lsrt21
Tris{2-[(5-fluorosalicylidene)amino]ethyl}amine
and its manganese(III) complex: Synthesis,
characterization, crystal structures, and catalytic
property
Fen-Yan Wei
To cite this article: Fen-Yan Wei (2017) Tris{2-[(5-fluorosalicylidene)amino]ethyl}amine and its
manganese(III) complex: Synthesis, characterization, crystal structures, and catalytic property,
Inorganic and Nano-Metal Chemistry, 47:4, 603-607, DOI: 10.1080/15533174.2016.1212215
To link to this article: http://dx.doi.org/10.1080/15533174.2016.1212215
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Aug 2016.
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Date: 06 January 2017, At: 17:01

INORGANIC AND NANO-METAL CHEMISTRY
017, VOL. 47, NO. 4, 603–607
2
http://dx.doi.org/10.1080/15533174.2016.1212215
Tris{2-[(5-fluorosalicylidene)amino]ethyl}amine and its manganese(III) complex:
Synthesis, characterization, crystal structures, and catalytic property
Fen-Yan Wei
Department of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji, China
ABSTRACT
ARTICLE HISTORY
A tris-Schiff base tris{2-[(5-fluorosalicylidene)amino]ethyl}amine (H
3
L) was prepared by the reaction of 1:3
Received 30 May 2015
Accepted 30 January 2016
molar ratio of tris(2-aminoethy1)amine with 5-fluorosalicylaldehyde in methanol. The Schiff base reacted with
manganese perchlorate to give a mononuclear manganese(III) complex, [MnL]. The Schiff base and the
complex were characterized by elemental analysis, IR spectra, and single-crystal X-ray determination. The
KEYWORDS
ꢀ
ꢀ
Manganese complex;
mononuclear complex; Schiff
base; crystal structure;
catalytic property
Schiff base crystallized in triclinic space group P1, with unit cell dimensions a D 10.191(2) A, b D 10.778(2) A,
ꢀ
ꢀ
3
ꢀ
ꢀ
ꢀ
c D 13.353(2) A, a D 79.727(2) , b D 81.986(2) , g D 64.717(2) , V D 1301.6(3) A , Z D 2, R
1
D 0.0522, wR
2
D
0
.1155. The complex crystallized in cubic space group Ia-3, with unit cell dimensions a D b D c D 21.6266(5)
ꢀ
ꢀ
3
A, V D 10115.0(4) A , Z D 16, R
1
D 0.0779, wR D 0.2442. The Mn atom in the complex is in octahedral coordi-
2
nation. The complex has good catalytic capability in the oxidation of selected olefins to the corresponding
epoxides.
1
13
Introduction
KBr disc. H and C NMR were performed with a Bruker
00 MHz NMR instrument. GC analyses were carried out using
3
Due to increasing demand for green technologies in chemical
process engineering, considerable attention has been paid to
catalytic processes, which include removal of toxic and expen-
sive reagents, minimization of by-products, and simplification
a Shimadzu GC-2014C gas chromatograph. The X-ray diffrac-
tion was carried out on a Bruker SMART 1000 CCD area dif-
fractometer at 298(2) K.
[
1,2]
of workup procedures.
Olefin oxidation is an important
transformation in the production of fine and pharmaceutical Synthesis of the Schiff base
grade chemicals. Metal-catalyzed oxidation of olefins can give
5
-Fluorosalicylaldehyde (4.20 g, 0.01 mol) was dissolved in
rise to a whole variety of organic products. Thus, to explore
methanol (20 mL), to which a methanol solution (30 mL) con-
taining tris(2-aminoethy1)amine (1.46 g, 0.01 mol) was added
dropwise. The mixture was stirred at room temperature for 1 h
and filtered. The yellow precipitate was obtained by filtration.
Yield: 83%. Elemental analysis calcd (%) for C H F N O : C
efficient catalysts is a growing subject in organic, coordination,
[
3–7]
and catalytic chemistry.
plexes with transition metal centers have shown various cata-
To date, a great number of com-
[8–12]
lytic properties on organic reactions.
Among the
2
7
27
3
4
3
complexes, manganese complexes with Schiff bases are effective
6
3.3, H 5.3, N 10.9%; found: C 63.1, H 5.4, N 11.0%. IR (KBr,
[13–15]
catalysts for aerobic oxidation of olefins.
In search of new
¡1
cm ): 3445 (m, O-H), 3027–2805 (w, C-H of aliphatic and
catalysts for the oxidation of olefins, in this article, a new Schiff
1
aromatic), 1636 (s, CHN). H NMR data (300 MHz, DMSO) d
base tris{2-[(5-fluorosalicylidene)amino]ethyl}amine (H L)
3
1
4
6
3.06 (s, 3H), 7.86 (s, 3H), 6.80 (m, 3H), 6.53 (dd, J D 9.1,
and its manganese complex [MnL], are presented.
.5 Hz, 3H), 6.33 (dd, J D 8.9, 3.2 Hz, 3H), 3.27 (t, 6H), 2.50 (t,
1
3
H). C NMR data (300 MHz, DMSO) d 156.9, 156.0, 152.9,
Experimental
119.2, 118.9, 118.3, 118.2, 56.8, 54.5.
Materials and measurements
Synthesis of the manganese complex
5
-Fluorosalicylaldehyde and tris(2-aminoethy1)amine were
purchased from Fluka and used as received. Manganese per- H L (2.56 g, 0.005 mol) and manganese perchlorate (1.81 g,
3
chlorate was prepared by the reaction of manganese carbon in 0.005 mol) were dissolved and stirred in methanol (30 mL).
water, followed by recrystallization. The solvents used were of The mixture was stirred at room temperature for 1 h and fil-
reagent grade. Elemental analyses were carried out using a Per- tered. The filtrate was kept still at room temperature for sev-
kinElmer 2400 II elemental analyzer. Infrared spectra were eral days, to give deep brown block-like single crystals. Yield:
recorded on a PerkinElmer FT-IR spectrophotometer with a 40%. Elemental analysis calcd (%) for C H F MnN O :
2
7
24
3
4
3
CONTACT Fen-Yan Wei
weifenyan78@163.com
Department of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721013, China.
CCDC—1008306 for H L and 1008307 for [MnL] contains the supplementary crystallographic data for this article. These data can be obtained free of charge at
3
http://www.ccdc.cam.ac.uk/const/retrieving.html or from the Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: C44(0)1223-
336033 or e-mail: deposit@ccdc.cam.ac.uk.
©
2017 Taylor & Francis Group, LLC

6
04
F.-Y. WEI
Table 1. Crystallographic data for the Schiff base and the complex.
X-ray crystallography
H
3
L
[MnL]
Single crystals of the Schiff base and the complex were
mounted on the top of glass fibers. Graphite-monochromat-
Empirical formula
FW
C
27
H
27
F
3
N
4
O
3
C
27
H
24
F
3
MnN
564.4
Block/brown
4
O
3
ꢀ
512.5
Block/yellow
0.23 £ 0.20 £ 0.17 0.35 £ 0.27 £ 0.23
ized Mo-Ka radiation (λ D 0.71073 A) and the v scan tech-
[16]
Crystal shape/color
Crystal size (mm)
Crystal system
Space grouꢀp
λ (MoKa) (A)
T (K)
nique were used to collect the diffraction data. Absorption
correction was applied with SADABS.
The structures of
Triclinic
P1
0.71073
298(2)
0.101
Cubic
Ia-3
the Schiff base and the complex were solved with direct
0.71073
298(2)
0.581
method and refined with a full-matrix least-squares tech-
[17]
¡
1
nique with SHELXTL.
Anisotropic thermal parameters
m (mm ) (Mo-Ka)
Unit cell dimensions
a (Aꢀ )
were applied to all non-hydrogen atoms. Hydrogen atoms
were generated geometrically. The crystallographic data and
the details of the data collection and refinement for the com-
pounds are listed in Table 1. Selected bond lengths and
angles are given in Table 2.
ꢀ
10.191(2)
10.778(2)
13.353(2)
79.727(2)
81.986(2)
64.717(2)
1301.6(3)
2
21.6266(5)
21.6266(5)
21.6266(5)
90
b (A)
ꢀ
c (A)
ꢀ
a ( )
ꢀ
b ( )
90
90
ꢀ
g ( )
ꢀ
3
V (A )
10115.0(4)
16
Z
T
T
min
0.9771
0.9830
0.8224
0.8779
Catalytic epoxidation of olefins
max
No. of measured reflections
No. of unique reflections
11901
4585
2326
4585/0/337
0.0348
536
0.995
0.0522, 0.1155
0.1309, 0.1493
42851
1582
1216
1582/0/115
0.0498
4640
1.189
0.0779, 0.2442
0.0978, 0.2802
To a solution of olefins (0.28 mmol), NaHCO (0.11 mmol)
3
¡4
and catalyst (9.4 £ 10 mmol) in MeCN (0.5 mL) was added
No. of observed reflections [I ꢀ 2s(I)]
Data/restraints/parameters
H O (1.1 mmol, 30% H O solution) as oxidant. After the reac-
2
2
2
R
int
tion was over, for the products analysis, the solution was sub-
jected to multiple ether extraction, and the extract was also
F(000)
Goodness of fit on F
2
3
R
R
1
, wR
, wR
2
[I ꢀ 2s(I)]
concentrated down to 0.5 cm by distillation in a rotary evapo-
1
2
(all data)
rator at room temperature, and then, a sample (2 mL) was taken
from the solution and analyzed by GC. The retention times of
the peaks were compared with those of commercial standards,
and chlorobenzene was used as an internal standard for GC
yield calculation.
ꢀ
ꢀ
Table 2. Selected bond lengths (A) and angles ( ) for the Schiff base and the
complex.
H
3
L
C7-N1
1.268(3)
1.266(3)
1.455(3)
119.0(3)
118.6(2)
110.5(2)
C14-N2
C23-N4
C27-N4
C14-N2-C24
C23-N4-C25
C23-N4-C27
1.266(3)
1.462(3)
1.464(3)
119.6(3)
112.3(2)
110.6(2)
C21-N3
C25-N4
C7-N1-C22
C21-N3-C26
C25-N4-C27
Results and discussion
Synthesis
[
MnL]
C7-N1
Mn1-O1
The Schiff base tris{2-[(5-fluorosalicylidene)amino]ethyl}amine
1.289(6)
1.950(4)
115.6(4)
92.6(1)
87.0(1)
96.3(1)
C9-N2
Mn1-N1
C9-N2-C9A
O1-Mn1-N1A
O1-Mn1-N1B
1.452(5)
2.144(4)
118.6(1)
84.2(2)
(H L) was prepared by the reaction of 1:3 molar ratio of tris(2-
3
C7-N1-C8
aminoethy1)amine with 5-fluorosalicylaldehyde in methanol
(
O1-Mn1-O1A
O1-Mn1-N1
N1-Mn1-N1A
Scheme 1). The Schiff base reacted with manganese perchlo-
rate to give a mononuclear manganese(III) complex, [MnL]
Scheme 2). It should be noted that although no problem
occurred, perchlorate salts are potential explosive. Only small
C 57.5, H 4.3, N 9.9%; found: C 57.6, H 4.2, N 10.1%. IR quantities of such chemicals should be handled with great care.
KBr, cm ): 3020–2810 (w, C-H of aliphatic and aromatic), Elemental analyses of the complex are in good agreement with
616 (s, CHN).
expected values.
176.7(2)
(
¡1
(
1
Scheme 1. The synthesis of the Schiff base.

INORGANIC AND NANO-METAL CHEMISTRY
605
Scheme 2. The synthesis of the complex.
Structure description of the Schiff base and the complex
The molecular structure of the Schiff base is shown in Figure 1.
The bond lengths and angles around N4 atom indicate that it is
3
sp -hybridized. The bond lengths of C7-N1, C14-N2, and C21-
ꢀ
N3 are about 1.27 A, which are within the values of typical
CHN double bonds. The intramolecular O–H¢¢¢N hydrogen
[
21]
bonds (Table 3) in the Schiff base make S(6) ring motifs.
The angles of the apical atom to the neighboring carbon atoms
ꢀ
range from 110.5(2) to 112.3(2) , thus severely deviating from
an aminic trigonal pyramid.
The molecular structure of the complex is shown in Figure 2.
The molecule possesses a crystallographic threefold rotation
axis symmetry, with the axis passing through N2 and Mn1
atoms. The Mn atom in the complex is in octahedral coordina-
tion, with two imino N and two phenolate O atoms defining
the equatorial plane, and with one imino N and one phenolate
O atoms located at the axial positions. The distortion of the
coordination can be observed from the bond angles related to
the Mn atoms. The cis and trans angles range from 84.2(2) to
ꢀ
ꢀ
9
2.6(2) , and 176.7(2) , respectively. The Mn-O and Mn-N
bond lengths in the complex are comparable to those observed
[21–23]
in similar manganese complexes.
The apical nitrogen
atom N2 is not involved in coordination and has long distance
ꢀ
to the metal atom of 3.30 A. The angles of the apical atom to
the neighboring carbon atoms are 118.6(1) , thus slightly devi-
Figure 1. Molecular structure of the Schiff base with 30% probability level. Hydro-
gen bonds are shown as dashed lines.
ꢀ
ating from an aminic trigonal pyramid. It is considered that the
apical N atom is being repelled by the metal atom. The CHN
bond lengths in the complex are much longer than those in the
Infrared spectra
¡1
The medium and broad absorption centered at 3445 cm for free Schiff base, which is caused by the coordination to the
the Schiff base can be assigned to the O-H stretching vibrations Mn atom.
of the hydroxyl groups. The weak absorptions in the region
¡1
3
020–2805 cm are resulted from the C-H vibrations of the
aliphatic and aromatic groups. The intense absorptions at 1636
¡1
and 1616 cm for the spectra of the free Schiff base and the
complex, respectively, can be assigned to the vibration of CHN
[
18-20]
groups.
The lower shift in the complex compared to the
free Schiff base indicates the coordination via the N atoms of
the CHN groups.
ꢀ
ꢀ
Table 3. Hydrogen-bonding geometry for the Schiff base (A, ).
D–H¢¢¢A
D–H
H¢¢¢A
D¢¢¢A
D–H¢¢¢A
O1–H1¢¢¢N1
O2–H2¢¢¢N2
O3–H3¢¢¢N3
0.82
0.82
0.82
1.85
1.85
1.85
2.579(3)
2.583(3)
2.577(2)
148
148
147
Figure 2. Molecular structure of the complex with 30% probability level.

6
06
F.-Y. WEI
b
Table 4. Catalytic oxidation results .
c
d
e
Substrate
Product
Conversion (%) (TON)
Conversion (%)
19
7
3 (166)
85 (171)
23
8
8
9 (213)
2 (195)
35
27
b
3 2 2 3 2 2
The molar ratios for catalyst: substrate:NaHCO :H O are 1:300:120:1200. The reactions were performed in (80:20) mixture of CH OH/CH Cl at ambient conditions.
c
The GC conversion was measured relative to the starting olefin after 75 min.
TON D (mmol of product)/mmol of catalyst.
d
e
The conversion without the addition of sodium bicarbonate.
Catalytic property
3. Amini, M.; Haghdoost, M. M.; Bagherzadeh, M. Monomeric and
dimeric oxido-peroxido tungsten(VI) complexes in catalytic and stoi-
chiometric epoxidation. Coord. Chem. Rev. 2014, 268, 83–100.
4. Wang, F.; Lu, C.-H.; Willner, I. From cascaded catalytic nucleic acids
to enzyme-DNA nanostructures: Controlling reactivity, sensing, logic
operations, and assembly of complex structures. Chem. Rev. 2014,
The catalytic oxidation results are listed in Table 4. The com-
plex has good catalytic capability in the oxidation of selected
olefins to the corresponding epoxides. When H O was used as
2
2
a sole oxidant, the catalytic efficiency is not good, but when
114, 2881–2941.
NaHCO was added as a co-catalyst, the efficiency of the sys-
3
5
. Martins, L. M. D. R. S.; Pombeiro, A. J. L. Tris(pyrazol-1-yl)methane
metal complexes for catalytic mild oxidative functionalizations of
alkanes, alkenes and ketones. Coord. Chem. Rev. 2014, 265, 74–88.
. Arevalo, A.; Tlahuext-Aca, A.; Flores-Alamo, M.; Garcia, J. J. On the
catalytic hydrodefluorination of fluoroaromatics using nickel com-
plexes: The true role of the phosphine. J. Am. Chem. Soc. 2014, 136,
tem increases sharply. The H O and hydrogen carbonate may
2
2
react in an equilibrium process to produce peroxymonocarbon-
¡
6
ate, HCO , which is a more reactive nucleophile than H O
4
2
2
and speeds up the epoxidation reaction.
4
634–4639.
7
8
9
. Haldon, E.; Delgado-Rebollo, M.; Prieto, A.; Alvarez, E.; Maya, C.;
Nicasio, M. C.; Perez, P. J. Synthesis, structural characterization, reac-
tivity, and catalytic properties of copper(I) complexes with a series of
tetradentate tripodal tris(pyrazolylmethyl)amine ligands. Inorg. Chem.
2014, 53, 4192–4201.
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Funding
The authors acknowledge the Education Office of Shanxi Province (project
No. 11JK0601) and the Natural Science Foundation of China (project No.
21173003) for supporting this work.
44, 590–597.
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