Synthesis, structures, and catalytic property of manganese(III) complexes derived from N,N′-bis(5-fluoro-2-hydroxybenzylidene)ethane-1,2-diamine

Article abstract of DOI:10.1134/S1070328415020062

Two mononuclear manganese(III) complexes, [Mn(L)(NCS)] (I) and [Mn(L)(OH₂)₂] · Hfac · H₂O (II), where L is the deprotonated form of N,N′-bis(5-fluoro-2-hydroxybenzylidene)ethane-1,2-diamine, Hfac is hexafluoroacetylacetona

Full text of DOI:10.1134/S1070328415020062

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2015, Vol. 41, No. 2, pp. 142–148. © Pleiades Publishing, Ltd., 2015.
Synthesis, Structures, and Catalytic Property of Manganese(III)
Complexes Derived from N,N'ꢀBis(5ꢀFluoroꢀ2ꢀ
1
Hydroxybenzylidene)ethaneꢀ1,2ꢀDiamine
G. S. Li* and H. L. Zhang
Key Laboratory of Surface & Interface Science of Henan, School of Material & Chemical Engineering,
Zhengzhou University of Light Industry, Zhengzhou, 450002 P.R. China
*
eꢀmail: gangsen_li@126.com
Received June 19, 2014
Abstract—Two mononuclear manganese(III) complexes, [Mn(L)(NCS)] (
H O (II), where L is the deprotonated form of 'ꢀbis(5ꢀfluoroꢀ2ꢀhydroxybenzylidene)ethaneꢀ1,2ꢀ
diamine, Hfac is hexafluoroacetylacetonate, were prepared and characterized by elemental analysis, IR specꢀ
tra and single crystal Xꢀray determination (CIF files CCDC nos. 1008309 ( ), 1008310 (II)). The Mn atoms
in both complexes are in octahedral coordination. Complex crystallized in orthorhombic space group Pbca
with unit cell dimensions = 12.4090(4), = 13.5432(5),
I
) and [Mn(L)(OH ) ]
⋅
Hfac
⋅
2
2
N,N
2
I
I
3
a
b
c
= 19.4637(7) Å,
V
= 3271.0(2) Å ,
Z
= 8, R1
=
0
7
1
.0423, wR2 = 0.0922. Complex II crystallized in triclinic space group P1 with unit cell dimensions
.6845(3), = 88.984(2), = 13.5522(7) Å, = 78.369(1) = 88.984(2) = 83.835(1)
237.63(9) Å , = 2, R1 = 0.0526, wR2 = 0.1421. In the crystal structure of
axis. In the crystal structure of II, the molecules are linked through intermoꢀ
a
, V
=
=
b
c
α
°
,
β
°
,
γ
°
3
Z
I, the complex molecules are stack
via π⋅⋅⋅π interactions along the
lecular O–H⋅⋅⋅O hydrogen bonds, to form chains along the x axis. The catalytic oxidation on olefins of the
y
complexes was studied.
DOI: 10.1134/S1070328415020062
1
INTRODUCTION
The solvents used were of reagent grade. The Schiff
base H L was prepared according to the literature
2
Exploration of new and efficient catalysts is imporꢀ
method [14, 15]. Elemental analyses were carried out
using a PerkinElmer 2400 II elemental analyser. Infraꢀ
red spectra were recorded on a PerkinElmer FTꢀIR
spectrophotometer with a KBr disc. GC analyses were
carried out using a Shimadzu GCꢀ2014C gas chroꢀ
matograph. The Xꢀray diffraction was carried out on a
Bruker SMART 1000 CCD area diffractometer at
tant for organic industry and related fields [1–4]. In
recent years, much work indicated that metal comꢀ
plexes with various ligands have shown interesting catꢀ
alytic properties on many organic reactions [5–10].
Schiff bases are readily coordinate to transition metal
complexes. Manganese complexes with Schiff bases
are effective catalysts for aerobic oxidation of olefins
298(2) K.
[
11–13]. So as to explore new catalysts for the oxidaꢀ
tion of olefins, in the present work, two new mononuꢀ
clear manganese(III) complexes, [Mn(L)(NCS)] (
and [Mn(L)(OH ) ] Hfac H O (II), where L is the
deprotonated form of
Synthesis of I. H L (3.04 g, 0.01 mol), ammonium
2
I)
thiocyanate (0.760 g, 0.01 mol) and manganese perꢀ
chlorate (3.62 g, 0.01 mol) were dissolved and stirred
in methanol (50 mL). The mixture was stirred at room
temperature for 1 h and filtered. The filtrate was kept
still at room temperature for several days to give deep
brown blockꢀlike single crystals. The yield was 53%.
⋅
⋅
2
2
2
N,N'ꢀbis(5ꢀfluoroꢀ2ꢀhydroxyꢀ
benzylidene)ethaneꢀ1,2ꢀdiamine (H L), Hfac is
2
hexafluoroacetylacetonate, are presented.
EXPERIMENTAL
For C H N O F SMn
1
7
12
3 2 2
Materials and measurements. 5ꢀFluorosalicylaldeꢀ
hyde, ethyleneꢀ1,2ꢀdiamine, ammonium thiocyanate anal. calcd., %: C, 49.17;
H, 2.91;
H, 3.02;
N, 10.12.
N, 10.27.
and bis(hexafluoroacetylacetonato)manganese were
purchased from Fluka and used as received. Mangaꢀ
nese perchlorate was prepared by the reaction of manꢀ
ganese carbon in water, followed by recrystallization.
Found, %:
C, 49.03;
–1
IR (KBr; ν, cm ): 3020–2820 w (C–H of aliꢀ
phatic and aromatic), 2033 s (NCS), 1613 s (C=N),
1580–1500 s (C=C), 1218 m (C–O).
1
The article is published in the original.
142

SYNTHESIS, STRUCTURES, AND CATALYTIC PROPERTY
143
Table 1. Crystallographic data and experimental details for compound
I
and II
Values
Parameters
I
II
Fw
415.3
618.3
Crystal shape; color
Crystal size, mm
Crystal system
Block; brown
Block; brown
0.22
×
0.19
×
0.17
0.32
×
0.30
×
0.27
Orthorhombic
Triclinic
Space group
Pbca
P1
T
, K
298(2)
0.974
298(2)
0.639
μ
(MoK
), mm–1
α
Unit cell dimensions:
a
, Å
, Å
12.4090(4)
13.5432(5)
19.4637(7)
90
7.6845(3)
b
12.2039(5)
13.5522(7)
78.369(1)
88.984(2)
83.835(1)
1237.63(9)
2
c
, Å
, deg
, deg
, deg
α
β
90
γ
90
V
Z
, Å3
3271.0(2)
8
Tmin
/
Tmax
0.8143/0.8519
31823
0.8217/0.8465
11580
Number of measured reflections
Number of unique reflections (Rint
Number of observed reflections
)
3749 (0.0388)
2853
4557 (0.0185)
3894
(
I
> 2
Data/restraints/parameters
(000)
Goodness of fit on F2
σ
(I))
3749/0/235
1680
4557/9/370
624
F
1.053
1.020
R1
,
,
wR2
(
I
> 2
σ
(
I
))
0.0423, 0.0922
0.0649, 0.1009
0.493/–0.270
0.0526, 0.1421
0.0611, 0.1518
1.037/–0.618
R1
wR2 (all data)
Δρmax/Δρmin),
e
Å–3
Synthesis of II. H L (3.04 g, 0.01 mol) and iteꢀmonochromatized Mo
K
radiation
scan technique were used to colꢀ
.01 mol) were dissolved and stirred in methanol lect the diffraction data. Absorption correction was
50 mL). The mixture was stirred at room temperature applied with SADABS [16]. The structures of the
(
λ
=
2
α
bis(hexafluoroacetylacetonato)manganese (4.69 g, 0.71073 Å) and the
ω
0
(
for 1 h and filtered. The filtrate was kept still at room complexes were solved with direct method and refined
temperature for several days to give deep brown blockꢀ
like single crystals. The yield was 36%.
with a fullꢀmatrix leastꢀsquares technique with
SHELXTL [17]. Anisotropic thermal parameters were
applied to all nonꢀhydrogen atoms. The hydrogen
atoms of the water and methanol molecules were
located from electronic density maps, with O–H and
For C H N O F Mn
21
19
2 7 8
anal. calcd., %: C, 40.79;
Found, %: C, 40.96;
H, 3.10;
H, 3.22;
N, 4.53.
N, 4.40.
H
⋅⋅⋅H distances restrained to 0.85(1) and 1.37(2) Å,
respectively. The other hydrogen atoms were generated
geometrically. The crystallographic data and the
details of the data collection and refinement for the
complex are listed in Table 1. Selected bond lengths
and angles are given in Table 2. Hydrogen bonding
–1
IR (KBr;
ν
, cm ): 3413 w (O–H), 3027–2812 w
(
C–H of aliphatic and aromatic), 1615 s (C=N),
580–1500 s (C=C), 1215 m (C–O).
1
Xꢀray crystallography. Single crystals of the comꢀ information is given in Table 3. Crystallographic data
plexes were mounted on the top of glass fibers. Graphꢀ for the complexes have been deposited with the Camꢀ
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144
LI, ZHANG
Table 2. Selected bond lengths (Å) and angles (deg) for complexes
I
and II
Bond
Bond
d
, Å
d , Å
I
Mn(1)–O(1)
Mn(1)–N(1)
Mn(1)–N(3)
1.8874(17)
1.9924(19)
2.133(2)
Mn(1)–O(2)
Mn(1)–N(2)
1.8652(16)
1.9706(19)
II
Mn(1)–O(1)
Mn(1)–N(1)
Mn(1)–O(3)
1.876(2)
1.973(3)
2.245(2)
Mn(1)–O(2)
Mn(1)–N(2)
Mn(1)–O(4)
1.876(2)
1.987(3)
2.241(2)
Angle
ω
, deg
Angle
ω
, deg
I
O(2)Mn(1)O(1)
O(1)Mn(1)N(2)
O(1)Mn(1)N(1)
O(2)Mn(1)N(3)
N(2)Mn(1)N(3)
93.89(7)
164.92(8)
89.60(8)
100.54(9)
93.75(9)
O(2)Mn(1)N(2)
O(2)Mn(1)N(1)
N(2)Mn(1)N(1)
O(1)Mn(1)N(3)
N(1)Mn(1)N(3)
91.47(7)
167.97(8)
82.45(8)
99.10(9)
90.25(9)
II
O(2)Mn(1)O(1)
O(1)Mn(1)N(1)
O(1)Mn(1)N(2)
O(2)Mn(1)O(4)
N(1)Mn(1)O(4)
O(2)Mn(1)O(3)
N(1)Mn(1)O(3)
O(4)Mn(1)O(3)
93.25(9)
91.60(10)
174.23(10)
89.78(9)
O(2)Mn(1)N(1)
O(2)Mn(1)N(2)
N(1)Mn(1)N(2)
O(1)Mn(1)O(4)
N(2)Mn(1)O(4)
O(1)Mn(1)O(3)
N(2)Mn(1)O(3)
175.11(10)
92.52(10)
82.64(11)
94.45(10)
85.41(10)
90.08(10)
89.87(10)
90.51(10)
92.12(10)
87.20(10)
174.99(8)
Table 3. Geometric parameters of hydrogen bonds for II
Distance, Å
⋅⋅⋅
*
Angle
.
..
D−
H A
D–H
H
A
D⋅⋅⋅A
D–H⋅⋅⋅A, deg
O(7)–H(7
O(3)–H(3
O(4)–H(4
O(4)–H(4
O(3)–H(3
O(7)–H(7
O(7)–H(7
B
)
⋅⋅⋅O(5)i
⋅⋅⋅O(7)ii
⋅⋅⋅O(7)
⋅⋅⋅O(1)iii
⋅⋅⋅O(2)iv
0.89(2)
0.88(3)
0.85(1)
0.85(1)
0.87(2)
0.92(4)
0.92(4)
1.99(3)
1.92(3)
2.07(6)
1.96(4)
1.93(3)
1.92(8)
2.51(11)
2.875(3)
2.774(3)
2.881(3)
2.784(3)
2.794(3)
2.752(4)
3.144(3)
175(15)
163(16)
160(15)
163(15)
174(15)
150(13)
127(11)
A
A
)
)
B
B
)
)
A
A
)
⋅⋅⋅O(6)v
)
⋅⋅⋅O(5)v
i
; ii –1 +
; iii 1 –
; iv
; v 1 –
*
Symmetry codes: 1 +
x,
y,
z
x,
y,
z
x, 1 –
y, 1 –
z
–x, 1 –
y, 1 –
z
x, –y, 1 –
z.
bridge Crystallographic Data Centre (CCDC the reaction was over, for the products analysis, the
nos. 1008309 (
I
) and 1008310 (II); deposit@ccdc. solution was subjected to multiple ether extraction,
cam.ac.uk or http://www.ccdc.cam.ac.uk).
3
and the extract was also concentrated down to 0.5 cm
by distillation in a rotary evaporator at room temperaꢀ
ture and then a sample (2 L) was taken from the soluꢀ
Catalytic epoxidation of olefins. H O (1.1 mmol,
2
2
μ
3
0% H O solution) as oxidant was added to a solution
2
of olefins (0.28 mmol), NaHCO (0.11 mmol) and tion and analyzed by GC. The retention times of the
3
–4
catalyst (9.4
×
10 mmol) in MeCN (0.5 mL). After peaks were compared with those of commercial stanꢀ
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SYNTHESIS, STRUCTURES, AND CATALYTIC PROPERTY
a)
C(8)
145
(
C(7)
N(1)
C(9)
C(10)
C(11)
C(1)
N(2)
Mn(1)
C(12)
C(16)
C(15)
C(6)
C(5)
C(2)
F(2)
O(1)
F(1)
N(3)
C(3)
O(2)
C(14)
C(4)
C(17)
S(1)
C(13)
(
b)
O(6)
C(20)
C(6)
F(5)
O(5)
C(18)
F(1)
C(5)
C(7)
N(1)
C(1)
C(2)
C(21)
F(3)
O(7)
C(8)
C(19)
F(7)
C(4)
O(4)
C(9)
N(2)
C(17) F(4)
F(6)
C(3)
O(1)
F(8)
Mn(1)
C(12)
O(3)
O(2)
C(10)
C(11)
C(16)
C(13)
C(15)
C(14)
F(2)
Fig. 1. Molecular structure of complex I (a) and II (b) with 30% probability level.
dards, and chlorobenzene was used as an internal stanꢀ C=N groups. The intense absorption indicative of the
–
1
dard for GC yield calculation.
thiocyanate ligand is observed at 2033 cm .
The molecular structure of complex is shown in
Fig. 1a. The Mn atom in complex is in a square pyraꢀ
I
I
RESULTS AND DISCUSSION
midal coordination with two imino N and two phenoꢀ
late O atoms of the Schiff base ligand defining the
basal plane and with one thiocyanate N atom located
at the apical position. The Mn atom deviates from the
leastꢀsquares plane defined by the basal donor atoms
by 0.206(2) Å. The distortion of the coordination can
be observed from the bond angles related to the Mn
atoms. Due to the strain created from the fiveꢀmemꢀ
bered chelated ring Mn(1)–N(1)–C(8)–C(9)–N(2),
the angle N(1)Mn(1)N(2) is much small. The Mn–O
The two complexes were readily prepared by the
reaction of equimolar quantities of the Schiff base
ligand with manganese salts in methanol. It should be
noted that even though no problem occurred, perchloꢀ
rate salts are potential explosive. Only small quantities
of such chemicals should be handled and with great
care. Elemental analyses of the complexes are in good
agreement with expected values.
The medium and broad absorption centered at and Mn–N bond lengths in the present complex are
–1
3
413 cm for II can be assigned to the O–H stretchꢀ comparable to those observed in similar manganese
ing vibrations of the water molecules. The weak complexes [18, 19]. The dihedral angles between the
–1
absorptions in the region 3030–2810 cm are resulted two benzene rings of the Schiff base ligand is 2.9(5) Å.
from the C–H vibrations of the aliphatic and aromatic In the crystal structure of complex , the molecules are
axis by π⋅⋅⋅π interactions (Fig. 2a,
I
–
1
groups. The intense absorptions at 1613 cm for
I
and stack along the
y
–1
1
615 cm for II can be assigned to the vibration of Table 4).
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146
LI, ZHANG
a)
(
x
0
z
y
(
b)
x
0
z
y
Fig. 2. Molecular packing of complex I (a) and II (b), viewed along the y axis. Hydrogen bonds are shown as dashed lines.
The molecular structure of complex II is shown in atoms defining the equatorial plane and with two water
Fig. 1b. The asymmetric unit of complex II contains a O atoms located at the axial positions. The distortion
mononuclear manganese(III) complex cation, a of the coordination can be observed from the bond
hexafluoroacetylacetate anion, and a water molecule. angles related to the Mn atoms. Due to the strain creꢀ
The Mn atom in the complex cation is in octahedral ated from the fiveꢀmembered chelated ring Mn(1)–
coordination with two imino N and two phenolate O N(1)–C(8)–C(9)–N(2), the angle N(1)Mn(1)N(2) is
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SYNTHESIS, STRUCTURES, AND CATALYTIC PROPERTY
147
Table 4. Parameters between the planes for complexes I and II*
Distance between ring
Perpendicular distance Perpendicular distance
Cg
Dihedral angle, deg
centroids, Å
of Cg
(I
) on Cg
(J
) (Å) of Cg
(J
) on Cg(I) (Å)
I
86
87
90
8
Cg(1)–Cg(3)
Cg(1)–Cg(4)
Cg(2)–Cg(1)vi
Cg(2)–Cg(3)vi
Cg(3)–Cg(v)vi
3.876
4.888
2.997
3.507
3.560
–1.079
–2.026
1.223
2.020
–3.558
–1.755
–3.314
–3.277
–3.141
–3.283
3
II
10
10
Cg(5)–Cg(6)iv
Cg(5)–Cg(6)iii
3.896
4.233
–3.712
3.854
–3.485
3.869
*
Symmetry codes: vi
O(2)–C(12)–C(11)–C(10)–N(2), C(1)–C(2)–C(3)–C(4)–C(5)–C(6), and C(11)–C(12)–C(13)–C(14)–C(15)–C(16), respecꢀ
tively. For II Cg(5) and Cg(6) are the centroids of C(1)–C(2)–C(3)–C(4)–C(5)–C(6) and C(11)–C(12)–C(13)–C(14)–C(15)–
C(16), respectively.
–x, –y, –z. For I: Cg(1), Cg(2), Cg(3) and Cg(4) are the centroids of Mn(1)–O(1)–Mn(1A)–O(1A), Mn(1)–
:
Table 5. Catalytic oxidation results*
Substrate
Product
Conversion, % (TON) **
Conversion, % ***
7
7 (165) (
I
)
27
25
O
72 (154) (II
)
)
O
83 (202) (
I
)
32
29
87 (195) (II
O
9
2 (190) (
I
)
35
31
95 (213) (II
)
Cl
Cl
O
6
7 (177) (
I
)
18
23
73 (163) (II
)
MeO
MeO
*
The molar ratios for catalyst : substrate : NaHCO : H O are 1 : 300 : 120 : 1200. The reactions were performed in (80 : 20) mixture
3
2 2
of CH OH–CH Cl at ambient conditions.
3
2
2
** The GC conversion was measured relative to the starting olefin after 75 min. TON = (mmol of product)/mmol of catalyst.
*** The conversion without the addition of sodium bicarbonate.
much small. The cis and trans angles are range from addition, there are also π⋅⋅⋅π interactions among the
2.6(1) to 94.4(1) , and 174.2(1) to 175.1(1)
. The molecules (Table 4).
8
°
°
°
°
Mn–O and Mn–N bond lengths in the present comꢀ
plex are comparable to those observed in similar manꢀ
ganese complexes [20–22]. The dihedral angle among
The catalytic oxidation results are listed in Table 5.
The complexes have good catalytic capability in the
oxidation of selected olefins to the corresponding
epoxides. Both complexes have similar catalytic propꢀ
the benzene rings of the Schiff base ligand is 9.4(3) .
°
In the crystal structure of complex II, the molecules erty. When H O was used as a sole oxidant the cataꢀ
2
2
are linked through intermolecular O–H⋅⋅⋅O hydrogen lytic efficiency is not good, but when NaHCO was
3
bonds to form chains along the
x axis (Fig. 2b). In added as a coꢀcatalyst the efficiency of the system
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 41
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148
LI, ZHANG
increases sharply. The H O and hydrogen carbonate 10. McGuirk, C.M., Stern, C.L., and Mirkin, C.A., J. Am.
2
2
Chem. Soc., 2014, vol. 136, no. 12, p. 4689.
11. Durak, D., Delikanli, A., Demetgul, C., et al., Transiꢀ
tion Met. Chem., 2013, vol. 38, no. 2, p. 199.
may react in an equilibrium process to produce perꢀ
–
oxymonocarbonate, HCO , which is a more reactive
nucleophile than H O and speeds up the epoxidation
4
2
2
12. SalavatiꢀNiassari, M., Davar, F., and Bazarganiꢀ
reaction.
pour, M., Dalton Trans., 2010, vol. 39, no. 31, p. 7330.
1
3. Louloudi, M., Nastopoulos, V., Gourbatsis, S., et al.,
Inorg. Chem. Commun., 1999, vol. 2, no. 10, p. 479.
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