Synthesis, characterization, structures, and catalytic property of oxovanadium(V) complexes with hydrazone ligands

Article abstract of DOI:10.1134/S1070328413120087

The reaction of [VO(Acac)₂] with 4-methyl-N'-[(2-hydroxy-1- naphthyl)methylidene]benzohy- drazide (H₂L¹) and 4-methyl-N'-[1-(2-hydroxynaphthyl)ethyiidene]benzohydrazide (H₂L ²), respectively, in metha

Full text of DOI:10.1134/S1070328413120087

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2013, Vol. 39, No. 12, pp. 891–895. © Pleiades Publishing, Ltd., 2013.
Synthesis, Characterization, Structures, and Catalytic Property
1
of Oxovanadium(V) Complexes with Hydrazone Ligands
N. Wang*, J. Y. Guo, and J. Y. Hu
Department of Chemical Engineering, Henan University of Urban Construction, Pingdingshan, 467044 P.R. China
*
eꢀmail: wangning7903@yahoo.com.cn
Received January 9, 2013
Abstract—The reaction of [VO(Acac) ] with 4ꢀmethylꢀN'ꢀ[(2ꢀhydroxyꢀ1ꢀnaphthyl)methylidene]benzohyꢀ
2
1
2
drazide (H L ) and 4ꢀmethylꢀN'ꢀ[1ꢀ(2ꢀhydroxynaphthyl)ethyiidene]benzohydrazide (H L ), respectively, in
2
2
1
2
methanol, affords two new oxovanadium(V) complexes [VO(OMe)L ] (
I
) and [VO(OMe)L ] (II). Both
complexes have been characterized by elemental analysis, IR, and single crystal Xꢀray diffraction methods.
Complex is a methoxideꢀbridged dinuclear oxovanadium(V) compound, while complex II is a mononuclear
oxovanadium(V) compound. The dinegative hydrazone ligands coordinate to the metal atoms through pheꢀ
nolate, imine, and deprotonated amide donor atoms. The geometry around vanadium atom in is a distorted
2
I
I
VNO octahedron, while that in II is a VNO square pyramid. Both complexes have effective catalytic propꢀ
5
4
erty for the sulfoxidation reaction.
DOI: 10.1134/S1070328413120087
1
INTRODUCTION
EXPERIMENTAL
Materials and methods. 2ꢀAcetylꢀ1ꢀnaphthol,
Oxovanadium(V) complexes with Nꢀ and Oꢀconꢀ
2ꢀhydroxyꢀ1ꢀnaphthaldehyde, and 4ꢀmethylbenzhyꢀ
taining ligands have been extensively investigated in
recent years with respect to their remarkable efficiency
as insulin mimetic compounds [1–3]. The interaction
drazide were purchased from Aldrich Chemical Co.
All other reagentꢀgrade chemicals and reagents were
purchased commercially and used without further
of simple vanadium species with ligands having pharꢀ purification. Elemental analyses (C, H, N) were
macological activity is of particular interest. Hydraꢀ obtained with a PerkinElmer model 240C instrument.
IR spectra were recorded in KBr discs on a Nicolet 170SX
zone compounds have been widely used as versatile
ligands in coordination chemistry [4–6], and they
have shown interesting biological properties, such as
antibacterial, antitumor, and antifungi activities [7–9]
as well as catalytic properties [10–12]. Recently, we
have reported a few vanadium complexes [13]. As an
extension of the work on such complexes, in the
1
spectrophotometer. The H NMR spectra with tetꢀ
ramethylsilane (TMS) as an internal standard were
obtained using a Bruker Avance III 400MHz spectroꢀ
photometer.
1
Synthesis of H L . A mixture of 2ꢀhydroxyꢀ1ꢀ
2
naphthaldehyde (1.72 g, 10 mmol) and 4ꢀmethylbenzꢀ
hydrazide (1.50 g, 10 mmol) in 100 mL of methanol
present paper, we describe the synthesis, spectroscopic was refhrxed for 1 h. After reducing the solvent to
characterization, crystal structure determination, 20 mL by distillation and cooling to room temperaꢀ
ture, the precipitated white solid was filtered off,
washed with methanol and dried in air. Recrystallizaꢀ
and catalytic property of two new oxovanadium(V)
complexes with similar tridentate hydrazone ligands
1
tion from methanol yielded pure product of H L . The
2
4
ꢀmethylꢀN'ꢀ(2ꢀhydroxyꢀ1ꢀnaphthyl)methylidene]benꢀ
yield was 2.32 g (76%).
1
zohydrazide (H L ) and 4ꢀmethylꢀN'ꢀ[1ꢀ(2ꢀhydroxyꢀ
2
2
naphthyl)ethylidene]benzohydrazide (H L ).
2
For C H N O
19
16
2 2
anal. caicd., %: C, 74.98;
H, 5.30;
H, 5.41;
N, 9.20.
N, 9.15.
R
H
Found, %:
C, 74.73;
N
N
–1
O
IR (KBr; , cm ): 3217 w, 1645 s, 1627 m, 1601 w,
ν
OH
1
582 m, 1558 w, 1472 m, 1415 w, 1397 w, 1355 w,
1335 m, 1297 s, 1237 w, 1215 m, 1189 m, 1138 w,
113 w, 1026 w, 960 m, 855 w, 823 m, 799 m, 745 s,
692 w, 673 w, 551 w.
1
2
H L : R = H; H L : R = Me.
2
2
1
1
The article is published in the original.
891

892
WANG et al.
Table 1. Crystallographic data and structure refinement for added dropwise to a methanol solution (10 mL) of
complexes
Parameter
Formula
I
and II
1
H L (0.304 g, 1.0 mmol) with stirring, and then the
2
mixture was heated at reflux with stirring for 1 h and
cooled to room temperature. When the solution was
allowed to stand at room temperature for a few days to
slow evaporation of the solvent, Xꢀray quality brown
blockꢀshaped single crystals were collected by filtraꢀ
tion. The crystals were washed with methanol and
Value
I
II
C H N O V
C H N O V
4
0
34
4
8
2
21 19
2 4
M
800.6
0.25
414.3
0.30
Monoclinic
2 /
Crystal size, mm
Crystal system
Space group
0.27
×
×
0.23 0.32
×
×
0.27 dried in air. The yield was 0.230 g (58%).
Monoclinic
2 /
For C H N O V
4 8 2
40
34
P
n
P
n
1
1
anal. calcd. %: C, 60.01;
Found, %: C, 59.80;
H, 4.28;
H, 4.37;
N, 7.00.
N, 7.12.
a
, Å
, Å
9.105(2)
20.085(2)
9.931(2)
98.849(2)
1794.5(5)
2
9.898(1)
14.634(2)
13.213(2)
91.842(2)
1913.0(5)
4
b
c
, Å
–1
IR (KBr; cm ): 1659 m, 1604 s, 1549 m, 1501 w,
β
V
Z
ρ
μ
F
, deg
1
8
453 m, 1404 s, 1328 w, 1280 w, 1183 w, 1017 m, 983 s,
17 w, 742 w, 603 m, 534 w, 466 w.
, Å
2
Synthesis of [VO(OMe)L ] (II). This complex was
, g/cm3
1.482
1.439
calcd
, mm–1
prepared by following the same procedure outlined for
1
2
0.582
0.548
I
, but with H L replaced by H L (0.318 g, 1.0 mmol).
2 2
(000)
824
856
The Xꢀray quality brown blockꢀshaped single crystals
were obtained. The yield was 0.203 g (49%).
Temperature, K
Tmin Tmax
298(2)
298(2)
/
0.8587/0.8778
10176
0.8441/0.8661
10942
For C H N O V
21
19
2 4
Reflections measured
anal. calcd., %: C, 60.88;
H, 4.62;
H, 4.55;
N, 6.76.
N, 6.85.
Independent reflecꢀ
tions, Rint
3900
4133
Found, %:
C, 60.97;
Observed reflections
Goodness of fit on F2
2860
2658
–
1
IR (KBr;
1
1
ν
, cm ): 1657 m, 1601 s, 1546 m, 1508 s,
1.031
1.024
455 m, 1417 m, 1382 m, 1366 w, 1321 m, 1282 m,
217w, 1199 w, 1156 w, 1078 w, 1045 s, 1016 m, 972 s,
865 m, 828 m, 751 s, 723 m, 630 m, 583 s, 523 w, 436 w.
Final
R
indices,
R1 = 0.0392
wR2 = 0.0960
R1 = 0.0591
wR2 = 0.1074
R1 = 0.0444
wR2 = 0.1058
R1 = 0.0785
wR2 = 0.1222
I
≥
2σ(I)*
R
indices, all data*
Xꢀray structure determination I and II. The crystal
and instrumental parameters used in the unit cell
determination and data collection are summarized in
Table 1. Diffraction measurements were made at room
temperature on a Bruker SMART APEX II Xꢀray difꢀ
2
2 1/2
2
o
2
o
2
c
*
R1
=
Σ
||Fo| – |Fc||/
Σ
|Fo|, wR2
=
[Σw(F – F ) /Σw(F ) ]
.
2
Synthesis of H L . This compound was prepared by fractometer using graphiteꢀmonochromated Mo
K
2
α
1
following the same procedure outlined for H L , but radiation and co scan mode. Unitꢀcell dimensions
2
with 2ꢀhydroxyꢀ1ꢀnaphthaldehyde replaced by were determined and refined in the range 2.03
ꢀacetylꢀlꢀnaphthol (1.86 g, 10 mmol). The pure 27.00
for and 2.08 26.99 for II. Both structures
product was obtained as a white solid. The yield was were solved by the direct methods using SHELXSꢀ97
.70 g (85%).
and refined by fullꢀmatrix leastꢀsquares techniques on
°
–
2
°
I
°
⎯
°
2
2
F
with SHELXLꢀ97 [14]. The empirical absorption
corrections were applied by the multiꢀscan method
15]. All nonꢀhydrogen atoms were refined with anisoꢀ
tropic displacement parameters. Hydrogen atoms
were included in their idealized positions and refined
isotropically. Selected bond distances and angles for
and II are listed in Table 2.
Supplementary material for structures
been deposited with the Cambridge Crystallographic
Data Centre (nos. 917365 ( ) and 858860 (II);
For C H N O
2 2
20
18
[
anal. calcd., %: C, 75.45;
H, 5.70;
H, 5.78;
N, 8.80.
N, 8.92.
Found, %:
C, 75.21;
–1
IR (KBr;
ν
, cm ): 3225 w, 1640 s, 1612 m, 1605 w, the complexes
I
1
1
9
583 m, 1560 w, 1470 m, 1414 w, 1395 w, 1360 w,
333 m, 1293 s, 1238 w, 1213 m, 1182 m, 1146 w,
65 m, 841 w, 833 m, 787 m, 745 s, 670 w, 653 w.
I
and II has
I
Synthesis of [VO(OMe)L1]2 (I). [VO(Acac)2] deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.
0.263 g, 1.0 mmol) dissolved in 20 mL methanol was uk).
(
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 12
2013

SYNTHESIS, CHARACTERIZATION, STRUCTURES, AND CATALYTIC PROPERTY
893
RESULTS AND DISCUSSION
Table 2. Selected bond lengths (Å) and bond angles (deg)
for complex
I
and II*
The hydrazone compounds were prepared by the
condensation of similar carbonylꢀcontaining comꢀ
pounds with 4ꢀmethylbenzhydrazide in methanol.
Each of them has two dissociable protons at the pheꢀ
nolicꢀOH and the amide functionality. The reaction of
bis(acetylacetonato)oxovanadium(IV) with stoichioꢀ V(1)–O(3)
metric amounts of the hydrazone ligands in methanol
in air afforded the two vanadium(V) complexes as
brown crystalline solids. It should be pointed out that
the vanadium in the starting materials is in V(IV) oxiꢀ
dation state, but it appears to be V(V) in both comꢀ V(1)–O(3)
plexes, indicating that it was oxidized by air during the
Bond
d
, Å
Bond
d, Å
I
V(1)–O(1)
1.836(2) V(1)–O(2)
1.580(2) V(1)–O(4)
1.922(2)
1.823(2)
2.409(2)
V(1)–N(1)
2.094(2) V(1)–O(4
A)
II
V(1)–O(1)
1.825(2) V(1)–O(2)
1.756(2) V(1)–O(4)
2.086(2)
1.899(2)
1.576(2)
V(1)–N(1)
reaction procedures. Elemental analyses of the comꢀ
plexes are satisfactory with the empirical formulae.
Angle
ω
, deg
Angle
ω
, deg
The IR spectra of the ligands exhibit two bands in
I
–1
the regions 3215–3230 and 1640–1645 cm due to
the (N–H) and (C=O) stretches [16]. The absence
O(3)V(1)O(4)
O(4)V(1)O(1)
O(4)V(1)O(2)
103.4(1) O(3)V(1)O(1)
105.7(1) O(3)V(1)O(2)
89.4(1) O(1)V(1)O(2)
100.4(1)
100.5(1)
150.5(1)
ν
ν
of these bands in the spectra of the complexes is conꢀ
sistent with the enolisation of the amide functionality
and subsequent proton replacement by the vanadium O(3)V(1)N(1)
96.8(1) O(4)V(1)N(1) 156.3(1)
–1
atom. The bands appearing at about 1280 cm range
are assigned to the (C–O)(enolic) mode. The strong
bands at 1604 and 1601 cm in
with shoulders are assigned to the conjugate C=N–
O(1)V(1)N(1)
82.5(1) O(2)V(1)N(1)
74.6(1)
74.2(1)
79.1(1)
ν
–1
O(3)V(1)O(4
A
)
177.5(1) O(4)V(1)O(4A)
I
and II, respectively,
O(1)V(1)O(4
A
)
80.8(1) O(2)V(1)O(4A)
N=C moieties [17]. The bands observed at 983 and N(1)V(1)O(4
A)
85.5(1)
–1
9
72 cm for I and II, respectively, are assigned to the
II
V=O stretching [16, 18].
O(4)V(1)O(3)
O(3)V(1)O(1)
O(3)V(1)O(2)
105.7(1) O(4)V(1)O(1)
100.4(1) O(4)V(1)O(2)
87.1(1) O(1)V(1)O(2)
107.4(1)
111.4(1)
136.7(1)
The molecular structure of
complex is a bisꢀmethoxide oxygenꢀbridged cenꢀ
trosymmetric dinuclear vanadium(V) compound. The
I
is shown in Fig. 1. The
V
⋅⋅⋅V distance is 3.393(2) Å. The dianionic tridentate O(4)V(1)N(1)
hydrazone ligand binds the metal atom through the
phenolate O, imine N and deprotonated amide
atoms, forming a sixꢀ and a fivemembered chelate
rings, which are inclined to each other by 11.5(3)
97.0(1) O(3)V(1)N(1) 154.9(1)
82.5(1) O(2)V(1)N(1) 74.6(1)
O(1)V(1)N(1)
−
−
−
O
*
Symmetry code for A: 2 – x, –y, 1 – z.
°
.
Each V atom is in a distorted NO octahedral coordiꢀ
5
ation of the four equatorial donor atoms from the
leastꢀsquares plane is 0.133(3) Å. The displacement of
the V atom towards the oxo group from the plane is
nation with the three donor atoms of the hydrazone
ligand and one methoxide O atom defining the equaꢀ
torial plane, and with one oxo O and one symmetryꢀ
related methoxide O atom occupying the axial posiꢀ
tions. The mean deviation of the four equatorial donor
atoms from the leastꢀsquares plane is 0.008(3) Å. The
displacement of the V atom towards the oxo group
from the plane is 0.348(2) Å. The distances of V=O
0.501(2) Å. The value for complexes II is 0.42, indiꢀ
τ
cating the coordination is a distorted square pyramid
instead of trigonal bipyramid [21]. The distances of
V=O and other coordination bonds in complex II are
within the range of similar vanadium(V) complexes
[
22–24].
and other coordination bonds in complex I are within
the range of similar vanadium(V) complexes [19, 20].
In both complexes, the N–C and C–O bond
lengths in the fivemembered chelate rings are consisꢀ
tent with the enolate form of the amide functionality.
The corresponding bond values are comparable to
each other. The difference in the molecular structures
of the two complexes in solid state may arise due to the
crystal packing forces or bulk solid state effects mediꢀ
ated by the differing substitute groups.
The molecular structure of II is shown in Fig. 2.
The methoxide ligand lies trans to the imineꢀN atom.
The dianionic tridentate hydrazone ligand binds the
metal atom through the phenolate
deprotonated amide O atoms, forming a sixꢀ and a
fivemembered chelate rings, which are inclined to
each other by 18.3(3) . The V atom is in a distorted
NO square pyramidal coordination, with the three
−
O, imine
−
N and
−
°
The complexes were tested for their ability to cataꢀ
4
donor atoms of the hydrazone ligand, and the methoxꢀ lyze the oxidation of prochiral sulfides, using methyl
ide O atom defining the basal plane, and with the oxo phenyl sulfide PhSMe (thioanisol) and benzyl phenyl
O atom occupying the apical position. The mean deviꢀ sulfide PhSBz as model substrates [25].
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 12
2013

894
WANG et al.
C(17)
C(16)
C(18)
C(8)
C(5)
C(19)
C(7)
C(9)
C(10)
N(2)
C(11)
N(1)
C(12)
C(15)
C(14)
C(13)
O(2)
O(3)
C(6)
C(1)
V(1)
O(4)
C(2)
O(1)
C(20)
C(4)
C(3)
O(4A)
V(1A)
Fig. 1. Molecular structure of I with 30% thermal ellipsoids. Unlabelled atoms are related to the symmetry operation 2 – x, –y,
1
– z.
C(8)
C(7)
C(6)
C(12)
C(11)
C(19)
C(18)
C(17)
C(9)
C(10)
C(20)
N(2)
C(13)
C(1)
N(1)
C(16)
C(14)
C(5)
C(4)
C(15)
C(2)
O(2)
C(3)
O(1)
V(1)
O(3)
O(4)
C(21)
Fig. 2. Molecular structure of II with 30% thermal ellipsoids.
sulfide, but with CHPO as the oxidant, a lower yield
85%) and 9% ee of the Sꢀconfigured sulfoxide were
O
(
S
S
Complex
H O or CHPO
R
R
observed. When benzyl phenyl sulfide was used as the
substrate with a more bulky substituent, an increase of
reaction time to 48 h is noticed. Moreover, the yields
of conversion are much smaller and the enantioselecꢀ
tivity decreases to value of 5 and 2% with H O and
2
2
The results are summarized in Table 3. A 1.25ꢀfold
excess, based on the sulfide substrate, of H O or
cumene hydroperoxide (CHPO) as oxidants was used.
For all the reactions performed, no sulfone formation
as a side product was observed. The best results have
been obtained for II as a catalyst in the oxidation of
methyl phenyl sulfide with H O as the oxidant. In this
2
2
2
2
CHPO as oxidants, respectively. As for
alytic activity on comparison to II is observed. With
H O as the oxidant in the sulfoxidation reaction, for
I, reduced catꢀ
2
2
methyl phenyl sulfide 87% was converted within 24 h
2
2
case an overall yield of 91% within 24 h reaction time and with 11% ee of the Sꢀconfigured sulfoxide,
and a 15% ee of the Sꢀconfigured sulfoxide were whereas with CHPO as the oxidant, 82% conversion
obtained. For the same time of reaction, catalyst and was observed with 7% ee of the Sꢀconfigured sulfoxide.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 12
2013

SYNTHESIS, CHARACTERIZATION, STRUCTURES, AND CATALYTIC PROPERTY
895
Table 3. Catalytic results of complexes
I
and II
8. Patole, J., Sandbhor, U., Padhye, S., et al., Bioorg.
Med. Chem. Lett., 2003, vol. 13, no. 1, p. 51.
Comꢀ
plex
Subꢀ
strate
Oxidant Yield, % Time, h ee, %
9. Fan, C.D., Su, H., Zhao, J., et al., Eur. J. Med. Chem.
,
2010, vol. 45, no. 4, p. 1438.
1
0. Grivani, G., Bruno, G., Rudbari, H.A., et al., Inorg.
Chem. Commun., 2012, vol. 18, no. 1, p. 15.
1. da Silva, J.A.L., da Silva, J.J.R.F., and
Pombeiro, A.J.L., Coord. Chem. Rev., 2011, vol. 255,
nos. 19–20, p. 2232.
I
PhSMe H O2
87
82
75
70
91
85
82
73
24
24
48
48
24
24
48
48
11 (S)
7 (S)
3
2
PhSMe CHPO
1
2
PhSBz H O2
PhSBz CHPO
2
12. Monfared, H.H., Kheirabadi, S., Lalami, N.A., et al.,
II
PhSMe H O2
15 (S)
9 (S)
5 (S)
2 (S)
2
Polyhedron, 2011, vol. 30, no. 8, p. 1375.
PhSMe CHPO
13. Wang, N., Synth. React. Inorg. Met.ꢀOrg. NanoꢀMet.
Chem., 2011, vol. 41, no. 4, p. 378.
2
PhSBz H O2
PhSBz CHPO
14. Sheldrick, G.M., Acta Crystallogr., Sect. A: Found.
Crystallogr., 2008, vol. 64, no. 1, p. 112.
1
5. Sheldrick, G.M., SADABS, Göttingen (Germany):
In the case of benzyl phenyl sulfide, after a 48 h reacꢀ
tion time, with H O and CHPO as oxidants, overall
yields of 75 and 70% were obtained, respectively.
Univ. of Göttingen, 1996.
2
2
16. Maurya, M.R., Khurana, S., Zhang, W., et al.,
Dalton
Trans., 2002, no. 15, p. 3015.
1
1
1
2
2
7. ElꢀSayed, L. and Iskander, M.F., J. Inorg. Nucl. Chem.
,
1971, vol. 33, no. 2, p. 435.
REFERENCES
8. Sangeetha, N.R., Kavita, V., Wocadlo, S., et al.,
1
2
3
4
. Xie, M.ꢀJ., Yang, X.ꢀD., Liu, W.ꢀP., et al., J. Inorg. Bioꢀ
chem., 2010, vol. 104, no. 8, p. 851.
. Sanna, D., Micera, G., and Garribba, E., Inorg. Chem.
010, vol. 49, no. 1, p. 174.
. Mendes, I.C., Botion, L.M., Ferreira, A.V.M., et al.,
Inorg. Chim. Acta, 2009, vol. 362, no. 2, p. 414.
. Calinescu, M., Emandi, A., Serban, I., et al., Synth.
J. Coord. Chem., 2000, vol. 51, no. 1, p. 55.
9. Zhang, J.ꢀC., Li, H.ꢀH., Xian, D.ꢀM., et al., Chin. J.
Inorg. Chem., 2012, vol. 28, no. 9, p. 1959.
0. You, Z.ꢀL., Shi, D.ꢀH., Zhang, J.ꢀC., et al., Inorg.
Chim. Acta, 2012, vol. 384, p. 54.
1. Addison, A.W., Rao, T.N., Reedijk, J., et al., Dalton
Trans., 1984, no. 7, p. 1349.
,
2
React. Inorg. Met.ꢀOrg. NanoꢀMet. Chem., 2003, 22. Rath, S.P., Rajak, K.K., Mondal, S., et al., Dalton
vol. 33, no. 10, p. 1927.
Trans., 1998, no. 12, p. 2097.
. Seena, E.B., Mathew, N., Kuriakose, M., et al., Polyheꢀ 23. Rath, S.P., Mondal, S., and Chakravorty, A., Inorg.
dron, 2008, vol. 27, no. 5, p. 1455.
Chim. Acta, 1997, vol. 263, nos. 1–2, p. 247.
. Banerjee, S., Sen, S., Chakraborty, J., et al., Aust. J. 24. Kwiatkowski, E., Romanowski, G., Nowicki, W., et al.,
Chem., 2009, vol. 62, no. 12, p. 1614.
Polyhedron, 2003, vol. 22, no. 5, p. 1009.
. Wang, B.ꢀD., Yang, Z.ꢀY., Crewdson, P., et al., J. Inorg. 25. Romanowski, G. and Wera, M., Polyhedron, 2010,
Biochem., 2007, vol. 101, no. 10, p. 1492.
vol. 29, no. 13, p. 2747.
5
6
7
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 12
2013