Polyoxovanadate catalysts for oxidation of 1-phenyl ethanol: From the discrete [V4O12]4- and [V10O28]6- anions to the anionic [V6O17]:N4 n - Coordination polymer

Article abstract of DOI:10.1039/c8ce01237g

Three polyoxovanadate-based hybrids {[Ru(phen)₃]₂[V₄O₁₂]}·13H₂O (1), [Ru(phen)₃]₂[V₁₀O₂₈]·15H₂O (2), and [Ru(phen)₃]₂[V₆O₁₇]Cl·11H₂O (3) (phen = 1,10-phenanthroline) were prepared under hydrothermal conditions and characterized by electron paramagnetic resonance (EPR) spectroscopy, infrared spectroscopy (IR), powder X-ray diffraction (PXRD), thermogravimetric (TG) analysis, X-ray photoelectron spectroscopy (XPS), and single crystal X-ray diffraction analysis. Although the structures of both the cyclic vanadate [V₄O₁₂]^4- and the [V₁₀O₂₈]^6- anions are well-known, interestingly, a novel 1-dimensional (1-D) coordination polymer [V₆O₁₇]_n^4n- anion was constructed from tetranuclear [V₄O₁₂]^4- and dinuclear [V₂O₇]^4- building blocks, which were linked alternately through corner-shared oxygen atoms. Furthermore, the negative charges of polyoxovanadate [V₄O₁₂]^4-, [V₁₀O₂₈]^6- and [V₆O₁₇]^4- anions were balanced by two [Ru(phen)₃]^2+/3+ complex cations. The catalytic properties of compounds 1-3 for the oxidation of 1-phenyl ethanol by tert-butyl hydroperoxide (TBHP) were investigated, and the results demonstrated that 1 and 3 exhibited excellent catalytic activities for the oxidation of 1-phenyl ethanol under mild catalytic conditions.

Full text of DOI:10.1039/c8ce01237g

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DOI: 10.1039/C8CE01237G
Journal Name
ARTICLE
Polyoxovanadate catalysts for oxidation of 1-phenyl ethanol:
From the discrete [V4O12]4− and [V10O28]6− anions, to the anionic
[V6O17]n4n− coordination polymer
Received 00th January 20xx,
Accepted 00th January 20xx
Ke Wang,a, b Qiaofei Xu, a Pengtao Ma,a Chao Zhang, a Jingping Wang,a, * and Jingyang Niua, *
DOI: 10.1039/x0xx00000x
Three polyoxovanadate-based hybrids {[Ru(phen)3]2[V4O12+-∙13H2O (1), [Ru(phen)3]2[V10O28+∙15H2O (2), and
[Ru(phen)3]2[V6O17+Cl∙11H2O (3) (phen = 1,10-phenanthroline) were prepared under hydrothermal conditions, and
characterized by electron paramagnetic resonance (EPR) spectroscopy, infrared spectroscopy (IR), powder X-ray diffraction
(PXRD), thermogravimetric (TG) analysis, X-ray photoelectron spectroscopy (XPS), and single crystal X-ray diffraction
analysis. Though, the structures of both the cyclic vanadate [V4O12]4− and the [V10O28]6− anions are well known, but
interestingly a novel 1-Dimensional (1-D) coordination polymer [V6O17]n4n− anion is constructed from tetranuclear [V4O12]4−
and dinuclear [V2O7]4− building blocks which are linked alternately through corner-shared oxygen atoms. Furthermore, the
negative charge of the polyoxovanadate [V4O12]4−, [V10O28]6− and [V6O17]4− anions are balanced by two [Ru(phen)3]2+/3+
complexes cations respectively. The catalytic properties of compounds 1–3 for the oxidation of 1-phenyl ethanol by tert-
butyl hydroperoxide (TBHP) were investigated, and the result demonstrates that 1 and 3 exhibited excellent catalytic
activity for the oxidation of 1-phenyl ethanol under mild catalytic conditions.
www.rsc.org/
[{Zn(phen)2}2V4O12]·H2O,4a [(n-C4H9)4N]2,*(η-C8H12)Ir]2(V4O12)},6
[H2pn][Mn2(C2O4)(V4O12)],7 and *,Zn(2,2’-bpy)}2V4O12] (pn =
Introduction
1,3-diaminopropane, 2,2’-bpy = 2,2’-bipyridine).8 Secondly, the
classical POV [V10O28]6− can also be isolated under
hydrothermal conditions.9 Finally, polyoxoanions with the
same elemental composition {V6O17} but different
architectures have been reported (Fig. S1). The {V6O17}
components in compound [Zn(bpy)2]2V6O17 (bpy = 2,2’-
bipyridine) consist of VO 2-D layers, which display a very
pronounced sinusoidal ruffling structure.10 Another compound
[Co4(2-pzc)4(V6O17)+∙xH2O (2-pzc = 2-pyrazinecarboxylate) is
formed by [V6O17]4− double chains which is bent to give
perpendicularly arranged 8-rings, and each chain connects four
Polyoxovanadates (POVs) have attracted increasing attention
not only because of their importance in bioinorganic and
magneto-chemistry, but also due to their potential
applications in medicine, as well as in homogeneous and
heterogeneous catalysis.1 The fully-oxidised (VV) POVs, as a
family of POVs, are constituted by a series of POV clusters
[V2O7]4−, [V3O9]3−, [V4O12]4−, [V5O14]3−, [V10O28]6−, [V12O32]4−,
[V13O34]3−, [V15O42]9−, and [V16O42]4−.2 Generally, the V5+ ions
form di-, tetra-, and decavanadate species in alkaline
medium.3 An easily prepared archetype of POV anion is
[V4O12]4− (V4), which can be hydrothermally synthesized in an
alkaline solution. In the domain of the reported V4-based
compounds, examples for the coexistence of a discrete
[V4O12]4− anion and transition-metal complexes (TMCs) are
given by compounds [Zn(bipy)3]2[V4O12+∙11H2O and
[Ni(phen)3]2[V4O12]·17.5H2O.4 The interconnection of [V4O12]4−
anion by TMCs leads to supported 0-D or 2-D network
[{Co4(2-pzc)4}n] chains to form a 3-D chiral structure.11
4n−
Nevertheless, the anionic chain of [V6O17]n
in
[{Co(phen)2}2V6O17]n is composed of alternate dinuclear
[V2O7]4− building units and tetranuclear [V4O12]4−, which is
further anchored by [Co(phen)2]2+ fragments to form a 1-D
4n−
stepped chain.12 The same [V6O17]n
chains in compound
structures, exemplified by
a
range of compounds
*(2,2’-biphen)Co]V3O8.5 (2,2’-biphen = 2,2’-biphenanthroline)
as in [{Co(phen)2}2V6O17]n are linked by bridging (2,2’-
biphen)Co units to form a 2-D neutral framework (Fig. S1).13 In
contrast, less attention was paid to the self-assembly of POVs
units and TMCs in the supramolecular network, the hybrids
assembled from phenanthrolineruthenium complexes and POV
anions via electrostatic interactions have not been explored to
our knowledge. More importantly, ruthenium shows extensive
[{Cd(phen)2}2V4O12]·5H2O,4b
5
[NBu4][Ru(C8H12)(MeCN)2(HV4O12)+∙H2O∙0.5MeCN,
application in the catalytic processes of many different
14
reaction types.
Also, all inorganic coordination polymer
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4n−
[V6O17]n
reported.
Herein
anion with 1-D chain structure has not been dark red crystals suitable for X-ray diffraction were filtered off
View Article Online
DOI: 10.1039/C8CE01237G
(0.4% yield based on V). Anal. calcd (%) for C72H78N12O43Ru2V10:
we
report
three
), [Ru(phen)3]2[V10O28+∙15H2O Synthesis of [Ru(phen)3]2[V6O17]Cl∙11H2O NH4VO3 (0.250 g,
), and [Ru(phen)3]2[V6O17+Cl∙11H2O ( ), which are assembled 2.14 mmol), RuCl3 (0.147 g, 0.71 mmol), NaH2PO4∙2H2O (0.246
through electrostatic interactions. Coordination polymer g, 1.58 mmol), phen (0.280 g, 1.41 mmol) were added to 10 ml
POV-based
hybrids C, 34.44; H, 3.13; N, 6.69. Found: C, 34.66; H, 2.94; N, 6.95.
{[Ru(phen)3]2[V4O12+-∙13H2O (
1
(2
3
4n−
[V6O17]n
anion represents the first example of an all of H2O. The resulting suspension was stirred at room
inorganic 1-D chain structure so far. In this work, much temperature for 3.0 h, and then pH value was adjusted from
attention is devoted to get a deep insight in the catalytic initial 6.00 to 7.40 with tert-butylamine liquid. The mixture
studies of POVs towards oxidation of a series of 1-phenyl was sealed in a 25 ml Teflon-lined stainless steel container,
o
ethanol derivatives.
and heated to 160 C under autogenously pressure for 96 h.
From the resulting solution, dark red crystals of 3 suitable for
X-ray diffraction were filtered off (28% yield based on V). Anal.
calcd (%) for C72H70ClN12O28Ru2V6: C, 41.28; H, 3.37; N, 8.02.
Found: C, 41.14; H, 3.41; N, 8.14.
Experimental
Materials and Methods
All chemicals were used as received from commercial sources
without further purification. C, H, N elemental analyses were
carried out on a PerkinElmer 2400-II CHNS/O elemental
analyzer (Perkin-Elmer Waltham MA USA). IR spectra were
recorded on a Bruker VERTEX 70 IR spectrometer (Nicolet,
Madison, WI, USA) using KBr as pellets in the range of 2000–
500 cm–1 region. TG analysis of the samples were performed
using a NETZSCH STA 449 F5 analyzer (Mettler-Toledo
Schwerzenbach Switzerland) heated from 33 to 1000 °C under
nitrogen at the heating rate of 10 °C·min−1. PXRD was
performed on a Bruker AXS D8 Advance diffractometer (Bruker
Karlsruhe Germany) using Cu Kα radiation (λ = 1.54056Å) in
the range 2θ = 5 – 40° at 293 K. XPS measurements were
performed on a Kratos AXIS ULTRA XPS spectrometer (Kratos
Manchester UK) with monochromated Al (1486 eV) exciting
radiation source. Electron paramagnetic resonance spectra were
performed on Bruker EMX-10/12 EPR spectrometer.
Crystallography
The crystal structures of compounds
single crystal X-ray diffraction analysis. A selected single crystal
of compound was sealed into a capillary glass tube to protect
1–3 were determined by
1
it from weathering. No evidence of crystal decay was observed
during the crystal diffraction for data collection. While single
crystals of compounds
fabric with glue. The diffraction intensity data for compounds
were collected on a Bruker APEX-II CCD diffractometer
equipped with Mo Kα radiation (λ = 0.71073 Å) at 296 K. The
structures of compounds were solved by direct methods
2 and 3 were adhered to the fine glass
1–3
1–3
and non-hydrogen atoms were refined by full-matrix least-
squares on F2 method using the SHELX program suite.15 The
hydrogen atoms of the phen ligands in the three compounds
were placed in calculated positions and then refined using a
riding model with a uniform value of Uiso = 1.2 Ueq. All H atoms
of water molecules were directly added to the molecular
formula but not included in the structural model. In the final
Synthetic procedures
refinements of compounds 1–3, Ru and V metal atoms were
Synthesis of {[Ru(phen)3]2[V4O12]}∙13H2O NH4VO3 (0.125 g,
1.07 mmol), RuCl3 (0.074 g, 0.36 mmol), Sb2O3 (0.120 g, 0.41
mmol), phen (0.140 g, 0.71 mmol), and oxalic acid dihydrate
(0.025 g, 0.20 mmol) were added to 10 ml of H2O. The
resulting suspension was stirred at room temperature for 0.5 h,
and then pH value was adjusted from initial 6.60 to 8.20 with
2M KOH solution. The mixture was sealed in a 25 ml Teflon-
refined anisotropically; the O, N and C atoms were refined
isotropically. The crystal structure refinement results revealed
that empirical formula was {[Ru(phen)3]2[V4O12+-∙26H2O
(C72H100N12O38Ru2V4) for compound
1. There was loss of some
lattice water molecules due to the severe weathering of
crystals
{[Ru(phen)3]2[V4O12+-∙13H2O
of
1
.
The
resulting
chemical
formula
was
o
(C72H74N12O25Ru2V4)
lined stainless steel container, and heated to 160 C under
determined based on CHN element analysis and TGA results.
For compound , the number of lattice water molecules was
autogenously pressure for 120 h. From the resulting solution,
orange crystals suitable for X-ray diffraction were filtered off
2
determined according to structure refinement results, which is
consistent with the CHN elemental analysis results. For
(10% yield based on V). Crystals of
1 were easily converted to
powders on exposure to air, due to weathering. Anal. calcd (%)
for C72H74N12O25Ru2V4: C, 45.20; H, 3.90; N, 8.78. Found: C,
43.21; H, 3.75; N, 8.56.
Synthesis of [Ru(phen)3]2[V10O28]∙15H2O NH4VO3 (0.250 g,
2.14 mmol), RuCl3 (0.089 g, 0.43 mmol), Sb2O3 (0.120 g, 0.41
mmol), phen (0.168 g, 0.85 mmol), and oxalic acid dihydrate
(0.05 g, 0.40 mmol) were added to 10 ml of H2O. The resulting
suspension was stirred at room temperature for 0.5 h, and
then pH value was adjusted from initial 5.80 to 6.70 with 2M
KOH solution. The mixture was sealed in a 25 ml Teflon-lined
compound
3, partial lattice water molecules were located
according to structure refinement results; the remaining lattice
water molecules were determined by CHN element analysis
and TGA results. A summary of the crystallographic data and
structure refinements for compounds 1–3 is given in Table 1.
Results and discussion
Synthesis discussion
stainless steel container, and heated to 160 oC under Compounds
1–3 were isolated under hydrothermal conditions
autogenously pressure for 120 h. From the resulting solution, by the reaction of NH4VO3, RuCl3, phen, 10 ml of water and
2 | J. Name., 2012, 00, 1-3
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Table 1 Crystal structure data for 1−3.
2
3
1
Empirical formula
C72H100N12O38Ru2V4
2147.53
C72H78N12O43Ru2V10
2511.00
monoclinic
C2/c
C72H54ClN12O20Ru2V6
1944.45
Formula weight
Crystal system
triclinic
triclinic
Space group
P-1
P-1
a/Å
12.1515(10)
13.1137(11)
16.5899(14)
98.3390(10)
105.4250(10)
104.4740(10)
2403.3(3)
1
26.468(4)
15.103(2)
23.374(3)
90
16.2890(17)
16.4760(17)
18.003(2)
104.610(2)
116.152(2)
91.609(2)
4142.6(8)
2
b/Å
c/Å
α/º
β/º
108.164(3)
90
γ/º
V/Å3
8878(2)
4
Z
ρcalc/g·cm‒3
1.484
1.879
1.559
-7≤ h ≤14
-15≤ k ≤15
-19≤ l ≤17
1100.0
-18≤ h ≤31
-18≤ k ≤17
-27≤ l ≤27
5024.0
-19≤ h ≤19
-19≤ k ≤18
-21≤ l ≤21
1934.0
Index ranges
F(000)
Reflections collected
Data/restraints/Parameters
μ/mm‒1
12269
22748
21429
8497/0/272
0.767
7909/0/309
1.432
14560/0/501
1.106
GOF on F2
1.048
1.025
1.028
R1,wR2[I>2σ(I)]
R1 = 0.0752
wR2 = 0.2037
R1 = 0.0838
wR2 = 0.2151
R1 = 0.0731
wR2 = 0.1721
R1 = 0.1342
wR2 = 0.2153
R1 = 0.0926
wR2 = 0.2562
R1 = 0.1089
wR2 = 0.2771
R1,wR2[all data]
different substances containing heteroatoms. The V/Ru/phen,
molar ratio, pH, and concentration of reactants play an important
role in the formation of compounds 1–3. As shown in Scheme 1, a
comparison of the synthetic methodology of 1–3 depicts the role of
important parameters towards reaction feasibility. Firstly, we found
that the concentration and the ratio of reactants may lead to the
construction of different crystal structures. For instance,
compounds 1 and 2 were synthesized using the same reactants,
Crystal structure of compound 1
Single-crystal X-ray diffraction analysis demonstrates that
compound
1
is constructed from [V4O12]4− anion, two
[Ru(phen)3]2+ cations and 26 crystal water molecules. The
[V4O12]4− anion contains a cyclic eight-membered [V4O4] ring
and is made up of four corner-shared {VO4} tetrahedra
(Scheme 1). The four μ2-O atoms and four vanadium atoms of
{V4O4} ring are nearly coplanar. To our knowledge, there exist
except in controlled reaction stoichiometry. Compound 1 was three types of conformations of the reported cyclic [V4O12]4−
anion, namely, coplane-, chair-, and boat- types (Fig. S2).2c, 17
prepared with a reactant molar ratio of NH4VO3/RuCl3/phen ≈ 3 : 1 :
The distances between the μ2-O atoms and vanadium have an
average value of 1.78 Å and those between vanadium and the
terminal O atoms 1.64 Å. The O–V–O angles vary from 108.0(3)
to 111.4(2)°. The oxidation states of all V centers are
calculated using the bond valence sum (BVS). The BVS values
2 to form a discrete cluster structure. Whereas the crystals of
compound 2 was obtained on increasing the molar ratio to
NH4VO3/RuCl3/phen ≈ 5 : 1 : 2 with subsequent doubling the
concentration of the reactants. Secondly, it is well known that the
stability of vanadate is concentration and pH dependent in aqueous
solution. For example, in highly alkaline conditions, only
orthovanadate [VO4]3− is formed, whereas at the lower pH range
(8−12), *V2O7]4−, and [VO3]nn− (n = 4 or 5) are the major constituents,
which are formed by a sequence of condensation and hydrolysis
reactions of the protonated [HVO4]2−.3b Thus 1-D coordination
polymeric chain of compound 3 is formed through condensation
reactions of [V2O7]4− and [V4O12]4− by elimination of water under the
above mentioned experimental conditions.3b,16
of all vanadium atoms and oxygen atoms of compound
1 were
shown in Table S1. Results indicate that vanadium is in +5
oxidation state. The only crystallographically independent
ruthenium ion is coordinated by six nitrogen atoms from three
phen molecules (Ru1−N1 2.063 Å, Ru1−N2 2.077 Å, Ru1−N3
2.062 Å, Ru1−N4 2.064 Å, Ru1−N5 2.072 Å, Ru1−N6 2.059 Å),
thus yielding octahedral {RuN6} coordination geometry. The
average Ru1−N bond length (2.066 Å) is strictly same as the
literature value of [Ru(phen)3]2+.18 The organoamine acts as a
reductive agent for reducing Ru3+ to Ru2+ under the
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Fig. 1. (a) Ball-and-stick views of the asymmetric unit {V6O17} for
{V10O29} unit in . (c) Polyhedral view of sinusoidal ruffling 1-D chain
structure of [V6O17]n4n− polyanion in
3; (b)
3
3
.
Scheme 1 Simplified Representation of the Controlling Synthesis of
1−3. Crystal water molecules are omitted for clarity.
Except for C−H∙∙∙O hydrogen bonding interactions, there are
also π∙∙∙π interactions between phen ligands from
experimental conditions.19 Additionally, XPS analysis and
charge-balance considerations also confirmed that Ru of
[Ru(phen)3]3+ complexes in compound
2 with an interplane
distance of about 4.25 Å. Thus, a 3-D supramolecular structure
was formed via the combination of C−H∙∙∙O and π∙∙∙π
interactions
compound
1 should be in the oxidation states of +2,
supporting the assignment of oxidation states of Ru1 (Fig. S3).
There are C−H∙∙∙O hydrogen bonding interactions between
carbon atoms of [Ru(phen)3]2+ and oxygen atoms of POV
anions, with C···O distances in the range of 3.1493(3)–3.3271(2)
Å. Except for C−H∙∙∙O hydrogen bonding interactions, there are
also π∙∙∙π interactions between phen ligands from
Crystal structure of compound 3
Single-crystal X-ray diffraction analysis demonstrates that the
asymmetric unit of compound
3
is composed of a [V6O17]4−
anion, one chloride ion (disordered about three sites), one
[Ru(phen)3]2+ complexes in compound
1 with an interplane
[Ru(phen)3]3+ complex cation, another [Ru(phen)3]2+ complex
distance of about 3.49 Å. Thus, a 3-D supramolecular structure
was formed via the combination of C−H∙∙∙O and π∙∙∙π
interactions.
cation, and 11 crystal water molecules (Scheme
1).
Tetranuclear [V4O12]4− and dinuclear [V2O7]4− building blocks
are linked alternately in the diagonal position of circular
[V4O12]4− cluster to form a 1-D chain structure via corner-
sharing oxygen atoms (Fig. 1c). The chain of the cluster anion is
surrounded by {Ru(phen)3} coordination complexes cations
acting as counter cations. There are six crystallographically
independent vanadium atoms in the 1-D anionic chain (Fig. 1a).
All vanadium ions show {VO4} tetrahedral configuration. Two
vanadium atoms (V2 and V5) are linked to three μ2-O (V−O =
1.734(7) to 1.843(9) Å) and a terminal oxygen (V−Ot = 1.593(7)
and 1.594(8) Å). While four vanadium atoms (V1, V6, V3, and
V4) form bonds to two μ2-O (V−O = 1.734(7) to 1.843(9) Å) and
Crystal structure of compound 2
Single-crystal X-ray diffraction analysis shows that compound
2
is constructed from the classical [V10O28]6− anion, two
[Ru(phen)3]3+ complex cations and 15 crystal water molecules
(Scheme
1
). The classical [V10O28]6− ion has a close-packed
structure constructed of ten {VO6} polyhedra fused through
sharing edges. Six such {VO6} octahedrons arranged in a 2 × 3
rectangular disposition via edge-sharing, with two {V2O10}
dimers joined from above and below. The BVS values of all
two terminal oxygen atoms (V−Ot = 1.547(12) to 1.625(11) Å)
vanadium atoms and oxygen atoms of compound
2 were
4n−
(Fig. 1b). The anionic chain [V6O17]n
of 3 can also be
described as composed solely of semicircular [V6O17]4− building
blocks each of which link to two adjacent [V6O17]4− clusters
through four V−O−V bridging bonds, leading to the formation
of an unobvious sinusoidal ruffling 1-D chain structure (Fig. 1c).
The BVS values of all vanadium atoms and oxygen atoms of
shown in Table S2. Results indicate that all V centers are in the
+5 oxidation state. The coordination geometry of Ru-
containing complex is identical to that of compound
However, the comparison of Ru–N bond distances of
compound (Ru1−N1 2.054 Å, Ru1−N2 2.073 Å, Ru1−N3 2.050
1.
2
compound
3 were shown in Table S3. Results indicate that
Å, Ru1−N4 2.053 Å, Ru1−N5 2.056 Å, Ru1−N6 2.065 Å, average
Ru1−N 2.059 Å) with the reported ones (2.066 Å) reveal that
they are very different from each other.18 The shorter average
vanadium is in the +5 oxidation state. There are two
crystallographically independent ruthenium cations which are
all coordinated by six nitrogen atoms from three phen ligands
to form a distorted {RuN6- octahedron with Ru1−N bonds from
2.059 (6) to 2.077 (7) Å (average Ru1−N 2.069 Å), Ru2−N bonds
from 2.054 (7) to 2.068 (7) Å (average Ru2−N 2.062 Å). The
Ru−N bond distance of compound
2 confirms that Ru in
compound should be in the oxidation states of +3 and not be
2
reduced, which is consistent with the assignment of oxidation
state of Ru atom based on charge-balance considerations.
Virtually, all Ru(III) complexes have the low-spin configuration
average Ru1−N bond distance of compound
3 is compatible
with the reported ones (2.066 Å) and reveal that Ru1 is in the
(S=1/2) 20. The EPR spectrum of compound
2
shows that d5
oxidation states of +2.18 The shorter average Ru2−N bond
Ru(III) coordination complex really has one unpaired electron
(Fig. S4).
distance of compound
oxidation states of +3, which is consistent with the assignment
3 confirms that Ru2 should be in the
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ARTICLE
Table 2 Results for oxygenation of 1-phenyl ethanol, its derivVaiteiwveAsr,tiaclnedOnline
of oxidation state of Ru atom based on charge-balance
considerations and the results of XPS analysis (Fig. S3). For
aliphatic alcohols with TBHP catalyzed by 1 in CH3CN.
DOI: 10.1039/C8CE01237G
compound 3
, the complexes [Ru(phen)3]2+ might be EPR-silent,
Entry
Substrate
TBHP
Yield%a
Cat./
and that [Ru(phen)3]3+ has the low-spin configuration as in
compound 2, indicating that the Ru centers in both complexes
were in the low-spin configuration. It could be assumed that
/mmol
mol%
1b
2
6
6
6
5
4
6
6
6
95
97
97
89
81
65
19
32
0.1
0.3
0.2
0.2
0.2
0.2
0.2
0.2
the EPR of the compound
3 would be like that of compound 2
because both have one unpaired electron (Fig. S4).
3
There are C−H∙∙∙O hydrogen bonding interactions between
carbon atoms of {Ru(phen)3} and oxygen atoms of POV anions,
with C···O distances in the range of 3.1519(2)–3.2862(3) Å.
Except for C−H∙∙∙O interactions, there are also π∙∙∙π
interactions between phen ligands from {Ru(phen)3}
4
5
6c
7d
8
complexes cations in compound
3 with an interplane distance
of about 3.57 Å. These complex interactions link the POVs and
metal complexes into a 3-D supramolecular structure (Fig. S5).
9
6
6
39
33
0.2
0.2
Characterization
10
The PXRD patterns for
1−3 are presented in Fig. S6. The
diffraction peaks of the experimental pattern were mainly
consistent with the simulated one, which indicates the phase
purity of the samples 1−3. The TG curve of compound 1 (Fig.
S7a) can be divided into two stages; the first stage between
33°C and 190 °C are attributed to the removal of the 13 lattice
water molecules with a mass loss of 12.1 % (calcd 11.2 %). Also
11
12
13
14
15
16
6
6
6
6
6
6
6
72
38
26
19
76
83
93
0.2
0.2
0.2
0.2
0.2
0.2
0.2
，
two weight loss stages are observed on the TGA curve of 2 (Fig.
S7b). The first stage is from room temperature to 160 °C with a
weight loss of 11.8% (calculated: 10.8%), which is due to the
release of the 15 crystallization water molecules. Similarly, two
weight loss stages are observed on the TGA curve of
3 (Fig.
S7c). The first weight loss of 9.1 % corresponds to the 11
lattice water molecules in the regions of 33−220 °C (calcd
9.5 %).
In the IR spectrum of compound
1 (Fig. S8a), the multiple
middle-strong features in the 1437–1024 cm−1 region are due
17
18
to vibrations of the phen ligands. The band corresponding to
1
is located at 937 cm−1, while the band
6
6
93
93
0.2
0.2
ν(V–Ot) of compound
associated with ν(O–V–O) are located at 847 cm−1.
For compound
, peaks in the 1437–1024 cm−1 region of the
IR spectrum of compound
19
2
a
2
are also due to vibrations of phen
Yields determined by using GC with dodecane as an internal
ligands. The absorption band located at 951 cm−1 is due to the
terminal V=O stretching vibration and it should be noted that
this peak is very strong, indicating that there are only {VVO6}
standard. The products were identified by GC-MS.
Reaction
b
conditions for the entries 1 to 5, 8 to 15: 3ml CH3CN; t, 6h; 1 mmol of
substrate; 60 °C. c Reaction conditions for the entry 6: as above, but
d
reaction temperature is 50 °C. Reaction conditions for the entry 7:
as above, but reaction temperature is 25 °C.
octahedrons in [V10O28]6− cluster of compound
2
. The strong
peak at 847 cm−1 is ascribed to ν(O–V–O) (Fig. S8b).
The IR spectrum of compound in the range of 1437–1024
cm−1 is also similar to that of compounds
and . This is mainly
3
the use of such products for fragrances and pharmaceuticals
and so on.21 The catalytic activity of compound
1 using 1-
1
2
ascribed to the similar {Ru(phen)3} complexes as counter
cations in the three compounds. The bands at 970 and 928
cm−1 are associated with the terminal V=O stretching vibration,
and strong features at 843 cm−1 and 819 cm−1 are ascribed to
ν(O–V–O) (Fig. S8c).
phenyl ethanol as a model substrate in acetonitrile (CH3CN)
system with TBHP as the oxidant was examined at room
temperature /50°C /60°C. As shown in Table 2 and Fig. 2,
dosage of catalyst (entries 1−3), TBHP dosage (entries 3−5),
reaction time (Fig. 2a), and temperature (entries 3, 6−7) were
the important factors that influence the yields of oxide
products. Under optimal conditions, 1-phenyl ethanol was
oxidized to acetophenone in good yields (97%) (entry 3).
Meanwhile, the chemical kinetics for the 1-phenyl ethanol
oxidation reaction has been demonstrated as a function of
The major difference in the IR spectra of compounds
is that two bands at 970 and 819 cm−1 are absent in compound
. The difference in their IR spectra should be ascribed to the
presence of {V2O7} building units in and their absence in
1 and 3
1
3
1.
Secondary alcohols oxidation to ketone compounds is an
important reaction in organic synthetic chemistry because of
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Table 3 Oxidation of 1-phenyl ethanol using different catalystsa
View Article Online
DOI: 10.1039/C8CE01237G
Entry
Catalyst
Substrate
Yield%b
19
1
2
3
4
5
6
c7
-
RuCl3
62
NH4VO3
21
phen
16
Compound 2
Compound 3
[(CH3)3CNH3]4[V4O12
12
97
]
97
a Reaction conditions for the entries 1 to 7: 6 mmol of TBHP; 3ml CH3CN; t,
6h; 60 °C; 1 mmol of substrate; 0.2 mmol catalyst. b Yield determined by GC
analyses based on initial substrate and the products were identified by GC-
MS.
time for catalyst 1. The yield and -ln(C0/Ct) are plotted against
the reaction time in Fig. 2a, where C0 and Ct are the initial
corresponding substrate concentration and corresponding
substrate concentration at time t, respectively. The linear fit of
reaction exhibits pseudo-first-order kinetics for the oxidation
reaction of 1-phenyl ethanol.
Catalyst
1 also catalyzed the oxidation of various 1-phenyl
ethanol bearing electron-withdrawing and electron-donating
groups on the benzene ring under the optimal conditions. The
steric hindrance effect has an obvious influence on the
oxidation of 1-phenyl ethanol bearing ortho-substituents
(Table 2, entries 12−14), affording the corresponding ketones in
lower yields. Additionally, it was found that the electronic
effect of substituents of 1-phenyl ethanol should affect the
yields of ketones and the substituent groups decreased more or
less the yields of ketones (Table 2, entries 3, 15−19).
Fig. 2. (a) Kinetic profiles of oxidation of 1-phenyl ethanol catalyzed by
1
, (black line: yield of acetophenone; red line: ln(Co/Ct)). (b) Recycling
tests of catalyst
1
.
Specifically, compound
1 exhibits extraordinary efficiency in
converting 1-(4-bromophenyl) ethanol to the corresponding
ketone with much higher yield (Table 2, entry 17, yield = 93 %)
in comparison to those reported under the similar experimental
conditions.22 Furthermore, aliphatic alcohols were converted
into corresponding aliphatic ketones with the maximum 77%
yield (Table 2, entries 8−11) under the optimal conditions,
oxidation reaction, whereas it is unlikely to happen with {VO6}
unit where V center is already coordinatively saturated.
{Ru(phen)3} complexes cations had no contribution to the
catalytic process. Similarly, compound
3 also shows excellent
catalytic activity for the oxidation of 1-phenyl ethanol to
acetophenone, which is very different from that of compound
which demonstrated moderate activity of catalyst
catalytic oxidation of aliphatic alcohols.
1
for the
2
(Table 3, entries 5, 6).
Compound could be served as a recycling catalyst. Catalyst
was separated from the reaction solution by filtration and
1
To compare the catalytic activity of compound
1
to other
1
catalysts in the oxidation of 1-phenyl ethanol, the results of
the oxidation of 1-phenyl ethanol in the presence of other
catalysts were shown in Table 3. Under the optimal conditions,
then washed with CH3CN, after that, it was dried in the air at
room temperature and reused directly without being
replenished or reconditioned. The recovered catalyst
1 was
most of the oxidation reaction could happen without catalyst 1,
successively subjected to the other 4 runs of the oxidation
under the same conditions to afford acetophenone in 97%,
97%, 97%, and 96% yield, respectively, without obvious loss of
catalytic activity (Fig. 2b). The FT-IR results showed no change
the yield of the blank experiment was just about 19% (Table 3,
entry 1). Both the vanadium starting material NH4VO3 and
phen ligands as catalysts showed bad catalytic activity towards
the oxidation of 1-phenyl ethanol (Table 3, entries 3, 4), the
in the structure of compound
reaction (Fig. S9).
1 before and after catalytic
yield of the RuCl3 as catalyst was about 61% (Table 3, entry 2).
17a
Meanwhile, the compound [(CH3)3CNH3]4[V4O12]
equally excellent catalytic activity as compound
showed
1
(Table 3,
Conclusions
entry 7). In contrast, we speculated that the catalytic activity
sites might be concentrated on {VO4} units. This might be
because {VO4} unit is coordinatively unsaturated, and this
allows substrate to get bound with V center for further
In conclusion, we have reported the syntheses, structures and
catalysis for the oxidation of alcohols of three compounds. The
6 | J. Name., 2012, 00, 1-3
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hybrids assembled from phenanthrolineruthenium
complexes and POV anions via electrostatic interactions have
not been explored previously. Among them, coordination
polymer [V6O17]n4n− anion represents the first example of an all
inorganic 1-D chain structure so far. The catalytic properties of
ARTICLE
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found that compounds
1
–
3
have been systematically investigated and we
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Acknowledgements
We gratefully acknowledge support from National Natural
Science Foundation of China (21571050; 21573056; 21771053;
21771054).
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