Oxidative coupling of 2-naphthol catalyzed by a new methoxido bridged dinuclear oxidovanadium(V) complex

Article abstract of DOI:10.1016/j.poly.2016.03.023

A new dinuclear oxidovanadium(V) complex, [(VO)₂(μ-L-κ⁴O,N,N,O)(μ-OCH₃)₂(OMe)₂]·CH₃OH (1), is synthesized by the reaction of V₂O₅ with 1,1′-((1E,1′E)-hydrazine-1,2-diylidenebis(methanylylidene))bis(naphthalen-2-ol) (H₂L) in methanol. H₂L is synthesized by two different methods: (i) from the reaction of hydrazine hydrate with 2-hydroxy-1-naphthaldehyde and (ii) from the reaction of hydrazine hydrate with 2-naphthol in the presence of formaldehyde (Mannich condensation). The ligand and its vanadium complex are characterized by elemental analysis, spectroscopic methods (FT-IR, NMR and UV-Vis) and their structures are determined by single crystal X-ray analysis. X-ray studies show that 1 is a neutral dinuclear complex of oxidovanadium(V) in which two vanadium(V) ions are connected by two methoxido bridging groups. The Schiff base ligand is coordinated to both vanadium centers by two NO-donor sets. Complex 1 is employed as initiator for oxidative coupling of 2-naphthol to produce BINOL. The effect of temperature, reaction atmosphere and solvent in catalytic reaction is studied. According to the obtained results, a mechanism is proposed for catalytic oxidative coupling reaction in the presence of complex 1.

Full text of DOI:10.1016/j.poly.2016.03.023

Accepted Manuscript
Oxidative coupling of 2-naphthol catalyzed by a new methoxido bridged dinu-
clear oxidovanadium(V) complex
Nader Noshiranzadeh, Rahman Bikas, Marzieh Emami, Milosz Siczek, Tadeusz
Lis
PII:
S0277-5387(16)30003-1
DOI:
http://dx.doi.org/10.1016/j.poly.2016.03.023
POLY 11888
Reference:
To appear in:
Polyhedron
Received Date:
Accepted Date:
21 January 2016
6 March 2016
Please cite this article as: N. Noshiranzadeh, R. Bikas, M. Emami, M. Siczek, T. Lis, Oxidative coupling of 2-
naphthol catalyzed by a new methoxido bridged dinuclear oxidovanadium(V) complex, Polyhedron (2016), doi:
http://dx.doi.org/10.1016/j.poly.2016.03.023
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Oxidative coupling of 2-naphthol catalyzed by a new
methoxido bridged dinuclear oxidovanadium(V) complex
a,*
a
a
b
Nader Noshiranzadeh, Rahman Bikas, Marzieh Emami, Milosz Siczek and
b
Tadeusz Lis
a
Department of Chemistry, Faculty of Science, University of Zanjan 45371-38791,
Zanjan, Iran
b
Faculty of Chemistry, University of Wroclaw, Joliot-Curie 14, 50-383 Wroclaw,
Poland
Abstract
4
A
new dinuclear oxidovanadium(V) complex, [(VO)
OCH (OMe) OH (1), is synthesized by the reaction of V
]·CH
(1E,1'E)-hydrazine-1,2-diylidenebis(methanylylidene))bis(naphthalen-2-ol) (H
methanol. H L is synthesized by two different methods: i) from the reaction of
2
(µ-L-κ O,N,N,O)(µ-
3
)
2
2
3
2
O
5
with 1,1'-
L) in
(
2
2
hydrazine hydrate with 2-hydroxy-1-naphthaldehyde ii) from the reaction of
hydrazine hydrate with 2-naphthol in the presence of formaldehyde (Mannich
condensation). The ligand and its vanadium complex are characterized by elemental
analysis, spectroscopic methods (FT-IR, NMR and UV-Vis) and their structures are
determined by single crystal X-ray analysis. X-ray studies show that 1 is a neutral
dinuclear complex of oxidovanadium(V) in which two vanadium(V) ions are
connected by two methoxido bridging groups. The Schiff base ligand is coordinated
to both vanadium centers by two NO-donor sets. Complex 1 is employed as initiator
for oxidative coupling of 2-naphthol to produce BINOL. The effect of temperature,
reaction atmosphere and solvent in catalytic reaction is studied. According to the
obtained results, a mechanism is proposed for catalytic oxidative coupling reaction in
the presence of complex 1.
*
Corresponding author. Tel.: +98 243 3052583; Fax: +98 243 2283203. E-mail
addresses: nadernoshiranzadeh@yahoo.com, nadernoshiranzadeh@znu.ac.ir.
1

Keywords: Dinuclear oxidovanadium(V), Schiff base ligand, Oxidative coupling,
BINOL synthesis, Catalytic coupling
Introduction
The C-C coupling reactions are one of the most important reactions in organic
1
chemistry [ ]. Therefore, developing catalytic coupling reactions which generate new
C-C bonds have continued to attract the attention of many researchers during last
2
several decades [ ]. 1,1'-bi-2-naphthol (BINOL) and its derivatives are a class of
important bis(phenol) compounds because they are used as ligands for synthesis of
3
several transition metal complexes [ ]. BINOL complexes are used as efficient
4
catalysts for a wide range of organic functional transformations [ ]. The oxidative
coupling of 2-naphthols is a useful method for synthesis of BINOL derivatives. In this
context, many reagents and a variety of methods have been reported for 2-naphthols
coupling. Catalytic oxidation coupling of 2-naphthols using transition metal
5
6
7
8 4b
complexes such as Cu [ ], Fe [ ], Ru [ ], V [ , ], etc. is one of the most important
reported methods for this reaction. Many transition metal complexes catalytically
couple 2-naphthol derivatives to BINOLs, vanadium compounds are particularly
9
useful for this process [ ]. Vanadium-mediated couplings occur via a favorable one-
electron phenolic oxidation in mild reaction conditions with the further advantage
1
0
that only water is formed as side product [ ]. Although several catalytic systems have
been reported for preparing BINOLs from 2-naphthols, development of new catalysts
1
1
and methods are gaining much attention [ ].
Vanadium plays a vital role in biological systems since the active sites of some
1
2
enzymes such as haloperoxidases consist of vanadate moieties [ ]. Vanadium
participates in many important catalytic redox processes. The utility of vanadium
2

1
3
complexes in oxidation reactions like epoxidation of olefins [ ], oxidation of sulfides
1
4
15
[
] and oxidation of alcohols [ ] is well documented. Nevertheless, the reports on
1
6
oxidative coupling reactions catalyzed by mononuclear [ ] and dinuclear vanadium
1
7
complexes [ ] are relatively low (in comparison with mentioned oxidation reactions).
According to the reported studies in the literature, the dinuclear vanadium complexes
1
8 11b
have higher reactivity in comparison with mononuclear ones [ , ]. This is mainly
attributed to the mechanism of 2-naphthol coupling in which the α-positions of two 2-
naphtholic groups approach to each other by coordinating to the two adjacent
1
9
vanadium cores [ ].
By taking the advantage of vanadium complexes toward oxidation reactions, we tried
to prepare a dinuclear vanadium complex in the aerobic oxidative coupling of 2-
naphthol. We focused on prepare a new vanadyl complex containing two vanadium
ions connected by rigid bridging groups together with monodentate ligands
susceptible to replacing by 2-naphtholate anion. In the present work, we report the
synthesis, characterization, crystal structure and catalytic reactivity of a new
methoxido bridged dinuclear oxidovanadium(V) complex bearing a tetradentate
Schiff base ONNO-type ligand.
2
. Experimental
2.1. Materials and instrumentations
Vanadium(V) oxide, V O , hydrazine hydrate, 2-hydroxy-1-naphthaldehyde, 2-
2
5
naphthol and formaldehyde were purchased from Merck and used as received.
Solvents of the highest grade commercially available (Merck) were used without
1
13
further purification. H and C NMR spectra of the ligand and complex 1 in CDCl
3
solution were measured on a Bruker 250 and 62.9 MHz spectrometer, respectively.
3

FT-IR spectra were recorded as KBr disks with a Bruker FT–IR spectrophotometer.
The vanadium content of the complex was measured by atomic absorption analysis
using Varian Spectra AA-220 equipment.
Scheme 1.
2
.2.
Synthesis
of
1,1'-((1E,1'E)-hydrazine-1,2-
L)
diylidenebis(methanylylidene))bis(naphthalen-2-ol) (H
2
Method A) A methanol solution (10 mL) of hydrazine hydrate (0.22 mL, 4.5 mmol)
was added to a methanolic solution of 2-hydroxy-1-naphthaldehyde (1.81 g, 9 mmol).
The solution was refluxed for 3 h at the 70 ˚C. The obtained yellow solid was
separated, filtered and washed with cold methanol and finally recrystallized from
ethanol. Yield 91%. Method B) Methanolic solution of formaldehyde (37%) (0.8 mL,
10 mmol) was added to methanolic solution of 2-naphthol (1.44 g. 10 mmol) and the
rapidly stirred solution was cooled to 0 °C. The mixture was stirred for 10 min, then
hydrazine hydrate (0.24 mL, 5 mmol) was added and the mixture was refluxed for 12
h. The resultant solution was evaporated on a steam bath to 5 mL and cooled to room
temperature. The resulting precipitate was separated and filtered off, washed with 20
mL of cooled methanol and re-crystallized from ethanol. Yield 85%. M.p. 316-318
˚
C. Anal. Calc. for C H N O (MW = 340.37): C, 77.63; H, 4.74; N, 8.23. Found: C,
2
2
16
2
2
-
1
7
7.71; H, 4.70; N, 8.29%. FT-IR (KBr, cm ): 3454 (w, br), 3057 (w), 2920 (w), 1621
(
vs), 1604 (s), 1580 (s), 1508 (w), 1467 (s), 1417 (m), 1385 (w), 1321 (s), 1282 (m),
242 (m), 1214 (w), 1185 (m), 1167 (m), 1142 (w), 1084 (w), 1030 (w), 962 (w), 965
1
(
w), 871 (m), 833 (s), 797 (m), 787 (s), 754 (s), 721 (w), 680 (w), 658 (w), 527 (w),
1
5
09 (w), 440(w). H NMR (250 MHz, CDCl , 25 °C, TMS): δ10.14 (s, 1H, phenolic
3
1
3
OH); 8.18 (s, 2H, CH=N); 7.75-7.57 ppm (m, 12H, aromatic). C NMR (62.90 MHz,
CDCl ): δ= 162.09 (C-OH), 151.7 (C=N), 134.2, 128.9, 128.5, 127.9, 125.9, 124.2,
3
4

-
5
-1
-
1
22.6, 119.8, 118.5 ppm. UV-Vis (in CH OH, c = 2.5×10 M, λ [nm] with ε[M cm
3
max
1
]
): 226 (48400), 279 (4760), 333 (3500).
4
2.3. Synthesis of the complex [(VO)
2 3 2 2 3
(µ-L-κ O,N,N,O)(µ-OCH ) (OMe) OH (1)
]·CH
The ligand H L (0.344 g, 1 mmol) and V O (0.182 g, 1 mmol) were placed in the
2
2
5
main arm of branched tube. Methanol was carefully added to fill the arms the tube
was sealed and the reagents containing arm immersed in an oil bath at 60 ˚C while the
other arm was kept at ambient temperature. After a week, black crystals were
appeared in the cooler arm, which were separated and washed by methanol. Yield
6
9%. Anal. Calc. for C H N O V (MW = 628.41): C, 51.60; H, 4.81; N, 4.46; V,
2
7
30
2
9
2
-
1
1
6.21. Found: C, 51.48; H, 4.74; N, 4.43; V, 16.34%. FT-IR (KBr, cm ): 3440 (m,
br), 2923 (w), 2848 (w), 1618 (s), 1598 (vs),1545 (s), 1455 (w), 1408 (w), 1384 (m),
1
1
7
335 (m), 1288 (w), 1247 (w), 1225 (w), 1198 (w), 1180 (w), 1167 (w), 1043 (w),
010 (w), 1043 (m), 955 (m), 951 (w), 927 (m), 903 (m), 874 (w), 824 (w), 749 (m),
1
13 (w), 633 (w), 596 (w), 561 (w), 510 (w), 484 (w), 462 (w). H NMR (250 MHz,
CDCl , 25 °C, TMS): δ9.28 (s, 2H, CH=N); 8.58-7.09 (m, 12H, aromatic); 5.29 (s,
3
1
2
H, OHmethanol), 3.14 (m, 9H, OCH ), 3.24 (s, 6H, OCH ) ppm. UV-Vis (in CH OH, c =
3
3
3
-
5
-1
-1
.5×10 M, λ [nm] with ε[M cm ]): 220 (70800), 327 (19700), 428 nm (7440).
max
2.4. Representative procedure for oxidative coupling of 2-naphthol catalyzed by
complex 1
Liquid phase catalytic coupling of 2-naphthol was carried out in a 25 mL round
bottom flask equipped with a magnetic stirrer. In a typical experiment, catalyst (63
mg, 0.01 mmol) was added to a flask containing the anhydrous solvent (5 mL). The
solution was stirred for 10 minutes under desired atmosphere and then treated with a
solution of 2-naphthol (2-naphthol was dissolved in the same solvent used in the
5

reaction). Temperature was kept stable during the reaction and controlled by a
thermometer and the course of the reaction was monitored by TLC (24 hours). After
checking by TLC, the reaction mixture was concentrated under reduced pressure and
the product was isolated by column chromatography (ethyl acetate: petroleum ether =
1
: 3) to give the coupling product, BINOL. M.p. 205-207 °C. Anal. Calc. for C H O
2
0
14
2
-
1
(
MW = 286.33): C, 83.90; H, 4.39%. Found: C, 83.88; H, 4.36%. FT-IR (KBr, cm ):
3
1
1
8
4.85 (m), 34.03 (m), 3051 (w), 2923 (w), 2851 (w), 1617 (s), 1590 (s), 1508 (m),
470 (m), 1461 (m), 1435 (w), 1404 (w), 1382 (vs), 1347 (w), 1322 (m), 1273 (m),
252 (m), 1217 (s), 1175 (s), 1146 (s), 1125 (m), 1023 (w), 979 (w), 960 (w), 930 (w),
64 (w), 826 (vs), 784 (w), 774 (w), 751 (vs), 723 (w), 675 (w), 665 (w), 624 (w), 585
1
(
w), 573 (m), 533 (w), 489 (w). H NMR (250.13 MHz, CDCl , 25 °C, TMS): δ= 7.97
3
(
d, J=9.0 Hz, 2H), 7.53 (d, J=7.75 Hz, 2H), 7.40-7.25 (m, 6H), 7.15 (d, J=8 Hz, 2H),
1
3
5
1
2
.03 ppm (s, 2H, OH). C NMR (62.90 MHz, CDCl ): δ= 152.73 (C-OH), 133.4,
3
31.4, 129.44, 128.4, 127.5, 124.2, 124.0, 117.7, 110.8 ppm. UV-Vis (in CH OH, c =
3
-
5
-1
-1
.5×10 M, λ [nm] with ε[M cm ]): 228 (51300), 278 (4440), 335 (3400).
max
2.4. X-ray crystallography
A summary of the crystal data and refinement details for complex 1 is given in
Table 1. Single crystal data collection for 1 were performed on Xcalibure PX
diffractometer with Onyx CCD detector, equipped with an Oxford Cryosystems open-
flow nitrogen cryostat, using ω-scan and a graphite-monochromated Mo Kα (λ=
0.71073 Å) radiation at 100 K. The structure was solved by direct methods with
2
SHELXS-97 [20], and refined with full-matrix least-squares techniques on F with
SHELXL-97 [21]. The C-bonded hydrogen atoms were calculated in idealized
geometry riding on their parent atoms. The molecular structure plot was prepared
6

using Diamond [22]. The X-ray data of pure ligand gave same results as earlier
2
3
reported [ ].
Table 1.
3
. Results and discussion
3.1. Syntheses and spectroscopy
The reaction of hydrazine hydrate with 2-hydroxy-1-naphtaldehyde gave the
desired ligand in high yield and purity. The reaction of 2-naphthol with hydrazine
hydrate in the presence of formaldehyde in methanol also produced the same
compound (Scheme 1). Spectroscopic data, elemental analysis and single crystal X-
ray studies [23] confirmed the formation of the same ligand in both methods. In the
1
H-NMR spectrum of H L, the presence of a broad singlet signal at δ 10.14 ppm was
2
assigned to the naphtholic O-H groups. The singlet peak at δ 8.18 ppm is assigned to
the hydrogen atom of azomethine (-CH=N-) group and confirms that the Schiff base
ligand is formed. The FT-IR spectrum of the H
2
L shows an absorption band at 1621
-1
24
cm which can be assigned to the imine C=N stretching frequency [ ].
Complex [V (L)(µ-OCH
2
O
2
3 2 3 2 3
) (OCH ) ]·CH OH (1) was synthesized by the
reaction of H L and V O with molar ratio 1 : 1 in methanol. Slow change in the color
2
2 5
of the reaction mixture from yellowish-brown to dark brown was the first evidence for
the complexation of ligand to the vanadium core. Single crystals of complex 1 were
obtained by thermal gradient method during one week. Comparison of the FT-IR
spectrum of complex 1 with the FT-IR spectrum of free ligand shows evidences for
the coordination of Schiff base ligand to the vanadium ion. The infrared spectrum of 1
−1
displays a band at 1618 cm which can be assigned to the C=N stretching frequency
of the coordinated Schiff base ligand and is red shifted with respect to the free ligand
7

−1
(
1621 cm ) [24]. Furthermore, in the FT-IR spectrum of complex 1 the band
−1
13a,14,15d
observed at 955 cm is assigned to the V=O stretching vibration [
]. Very
−1
broad band around 3440 cm expresses the presence of methanolic –OH group which
2
5
involved in hydrogen bonding interaction [ ].
3.2. Description of structure
The molecular structure of complex 1 is shown in Fig. 1 and selected bond distances
and angles are summarized in Table 2. Single crystal X-ray analysis indicates that 1 is
a neutral dinuclear complex of oxidovanadium(V) with a methanol molecule of
solvation. Two vanadium atoms are doubly bridged by two methoxido bridging
groups. The Schiff base ligand acts as a tetradentate dianionic compartmental donor,
with two NO-donor cavities. Both vanadium centers have similar coordination
5
environments, VNO , and the coordination geometry around them can be described as
distorted octahedral. One oxygen atom and one nitrogen atom of the Schiff base
ligand occupy two coordination sites of each vanadium core and the remaining four
sites are occupied by the two oxygen atoms provided by two methoxido bridging
groups, the oxygen atom of terminal methoxido ligand and the oxygen atom of oxido
group. The azomethine nitrogen atom, naphtholate oxygen and the oxygen atom of
methoxido ligand together with oxygen atom of bridging methoxido group form the
equatorial plan. The V–Omethoxido bonds trans to the oxido ligands are longer than V–
Omethoxido bonds in cis position, which can be attributed to the trans influence of V=O.
The V atoms are displaced by 0.275(2) Å (V1) and 0.307(2) Å (V2) from the plane
defined by the equatorial donor atoms towards the V=O. The V1···V2 distance is
2
6
3
.264(1) Å and is close to the ethoxido bridged dinuclear vanadium complexes [ ].
The dihedral angle between the V1,O1M,O2M and V2,O1M,O2M planes is 20.4(1)°.
8

The V1−O1M−V2 and V1−O2M−V2 angles are 105.9(2)°. The crystal packing of
complex 1 is stabilized by several C−H···O and C−H···π interactions. Furthermore, an
uncoordinated methanol molecule is connected to complex molecule by O−H···O and
C−H···O hydrogen bonding interactions (Fig. 2).
Fig. 1.
Fig. 2.
Table 2.
3
.3. Oxidative coupling of 2-naphthol catalyzed by complex 1
Considering the catalytic reactivity of oxidovanadium complexes in preparing
BINOLs, we were interested to employee complex 1 as catalyst in the oxidative
coupling of 2-naphthol. For this purpose, 2-naphthol was added to the reaction flask
containing complex 1 in a solvent and the reaction progress was monitored by TLC.
The reaction did not take place in the absence of molecular oxygen or catalyst. In the
presence of oxygen and complex 1, the oxidative coupling of 2-naphthol took place
and BINOL was obtained as sole product. Several parameters effects on the reaction
speed. Reaction atmosphere (O
important parameters in this reaction because they can effect on this catalytic reaction.
Firstly, the effect of solvent was studied in the coupling reaction. CCl , CH Cl
CHCl , CH CN, toluene, THF, DMSO and CH OH were examined as solvent at room
temperature. These reactions were done at aerial atmosphere. Among the used
solvents, CCl was found to be the most suitable solvent since in this solvent the
reaction was completed in a shorter time. It was observed that the catalytic activity of
2
, N
2
and air), temperature and solvent are the
4
2
2
,
3
3
3
4
2
7
the catalyst decreased with respect to CCl
dichloromethane (DN = 0) > chloroform (DN = 0) > acetonitrile (DN = 14.1 ) >
toluene (DN = 0) > THF (DN = 20) > CH OH (DN = 19) ≈ DMSO (DN = 29.8).
4
(donor number [ ] DN = 0) >
3
9

Overall, solvents with high donor ability decrease the reactivity of the catalyst, and
the lowest conversion in DMSO or CH OH is due to the highest coordinating ability
3
of these solvents. Having higher conversion in aprotic solvents is in agreement with
the previous reports for vanadium catalyzed oxidative coupling reaction of 2-
4
b,8a,18b
naphthols [
].
2
-Naphthol oxidative coupling is quite sensitive towards the reaction atmosphere.
Therefore, the reaction was studied at nitrogen, oxygen and aerial atmospheres. The
results are shown in Table 3. In oxygen atmosphere, the reaction was completed faster
than in aerial atmosphere and the product was not observed in the nitrogen
atmosphere. These results show that the presence of molecular oxygen as an oxidant
is essential parameter in the oxidation coupling of 2-naphthol. The coupling reaction
was studied at 0 °C, room temperature and 40 °C. Increase the reaction temperature
from 0 to 40 °C causes increase the catalytic activity of complex 1 since the reaction
is completed in a shorter time.
Table 3.
3
.4. Mechanism
Till now, several studies have been done and reported to understand the
possible mechanism pathways of the vanadium catalyzed oxidative couplings of 2-
naphthols. It was observed that the dinuclear vanadium complexes generate an
intermediate with two naphthoxy groups connected to the two adjacent vanadium
1
0b,18a
centers [
probably is the most important and capable intermediate in the oxidation coupling of
-naphthol by oxidovanadium complexes. The coupling occurs by intramolecular
]. Several experimental studies have been reported that this intermediate
2
manner when the conformations of 2-naphtholates change and their alpha carbons
locate near to each other. This suggestion is also supported by the fact that the
1
0

mononuclear vanadium complexes are much less catalytically active than the
2
8
dinuclear ones [ ].
Although the mechanism of this reaction was not studied here, on the basis of the
reported mechanisms for oxidative coupling of 2-naphthols catalyzed by dinuclear
vanadium complexes, it is predicted that the key step in this process is the replacing of
two monodentate terminal methoxido ligands by 2-naphthoxy groups. The proposed
catalytic pathway is shown in Scheme 2. Dinuclear vanadium(V) complex reacts with
two molecules of 2-naphthol and compound X1 is formed by replacing two
methoxido ligands. Two methanol molecules forms in this step. Consequently, the
oxidation state of vanadium core doesn’t change by replacing two methoxido groups
with two naphtholate groups. In the next step, the alpha positions of the 2-naphthol
molecules approach each other yielding X2, which is then intramolecularly coupled
2
9,4b,17,18a
by a manner similar to the reported mechanism by Gong et. al. [
]. In the next
step, one water molecule is formed by oxidation reaction and the BINOL product is
generated (X3). The oxidation by molecular oxygen is supported by the fact that the
reaction is faster in the oxygen atmosphere. The obtained BINOL molecule releases
by coordinating of two next 2-naphthol molecules to the catalytically active species
and this cycle occurs several times.
4
. Conclusion
In summary, a new methoxido bridged dinuclear complex of oxidovanadium(V) was
synthesized and characterized by spectroscopic methods and single crystal X-ray
analyses. The catalytic ability of this complex was investigated in the oxidation
coupling of 2-naphthol. The effects of temperature, solvent and reaction atmosphere
1
1

2 2
(O , N , air) have been studied. The results showed that complex 1 promotes the
preparation of BINOL from 2-naphthol in the presence of O2
Acknowledgment
The authors are thankful to the University of Zanjan for support of this study.
Appendix A. Supplementary data
CCDC 1448933 contains the supplementary crystallographic data for complex 1. This
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)
223-336-033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary data associated
with this article can be found, in the online version, at
1
http://dx.doi.org/10.1016/j.poly.2016.???.???.
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Tables/Schemes/Figures caption
Table 1. Crystallographic data of 1
Table 2. Selected geometrical parameters (Å, °) for complex 1
Table 3. Comparison the catalytic activities of complex 1 in the oxidative coupling of
2
-naphthol in different conditions
Scheme 1. The synthesis of H L
2
1
6

Scheme 2. Proposed mechanism for the oxidative coupling of 2-naphthol catalyzed by
complex 1
2 2 3 2 3 2 3
Fig. 1. Molecular structure of complex [V O (L)(µ-OCH ) (OCH ) ]·CH OH (1)
Fig. 2. O−H•••O and C−H•••O hydrogen bonding interactions in the crystal of
complex 1
Table 1. Crystallographic data of 1
Complex 1
net formula
C H N O V ·CH O
628.41
2
6
26
2
8
2
4
−1
M /g mol
r
crystal size/mm
T/K
0.16 × 0.11 × 0.04
100
Radiation
Diffractometer
crystal system
Crystal shape, color
MoKα
Xcalibur PX
Orthorhombic
Plate, brown
Pca21
space group
a/Å
b/Å
c/Å3
V/Å
Z
12.892(4)
12.717(4)
16.350(6)
2680.5(15)
4
−3
calc. density/g cm
µ/mm
1.557
0.76
−1
F(000)
θrange
h,k,l
1296
2.6–29.6
−17•8,−17•17, −10•21
0.088
0.055
0.119
Rint
R(F )
obs
2
R (F )
w
S
1.02
Absorption correction
measured reflections
independent reflections
reflections with I > 2σ(I)
Parameters
Restraints
Max electron density/e Å−
Analytical
9857
4769
2369
350
1
0.86
−
3
3
Min electron density/e Å
−0.71
Table 2. Selected geometrical parameters (Å, °) for complex 1
Bond Angle/deg Bond
Distance/Å
1
7

O3M—V1—O2M
O1M—V1—O2M
O1—V1—O2M
O3—V1—N1
O3M—V1—N1
O1M—V1—N1
O1—V1—N1
O2M—V1—N1
O4—V2—O4M
O4—V2—O2
O4M—V2—O2
O4—V2—O2M
O4M—V2—O2M
O2—V2—O2M
O4—V2—O1M
O4M—V2—O1M
O2—V2—O1M
O2M—V2—O1M
O4—V2—N2
91.0(3)
72.3(2)
89.1(2)
95.6(3)
163.1(3)
82.2(2)
80.2(2)
73.2(2)
102.5(3)
99.4(3)
95.1(3)
98.2(2)
97.4(3)
155.7(3)
164.8(2)
89.8(3)
88.2(2)
71.0(2)
95.6(3)
161.7(3)
79.5(2)
82.2(2)
72.7(2)
V1—O3
1.578(6)
1.796(6)
1.884(5)
1.908(5)
2.171(5)
2.194(7)
1.589(5)
1.788(6)
1.900(6)
1.916(5)
2.198(6)
2.218(8)
V1—O3M
V1—O1M
V1—O1
V1—O2M
V1—N1
V2—O4
V2—O4M
V2—O2
V2—O2M
V2—O1M
V2—N2
Bond
Angle/deg
105.9(2)
105.9(2)
100.9(3)
97.5(2)
99.3(3)
98.2(3)
93.6(3)
157.4(2)
V1—O1M—V2
V1—O2M—V2
O3—V1—O3M
O3—V1—O1M
O3M—V1—O1M
O3—V1—O1
O3M—V1—O1
O1M—V1—O1
O3—V1—O2M
O4M—V2—N2
O2—V2—N2
O2M—V2—N2
O1M—V2—N2
165.5(2)
Table 3. Comparison the catalytic activities of complex 1 in the oxidative coupling of
-naphthol in different conditions
2
1
8

a
Entry
Solvent
Atmosphere T/˚C
Yield (%)
1day
2day
3day 4day 5day 6day
1
2
3
4
5
6
7
8
9
CCl
CH
CHCl
4
N
Air
Air
2
RT
RT
RT
RT
RT
RT
RT
0
RT
40
40
0
RT
40
0
-
-
0
0
0
0
0
-
-
70
0
0
0
0
-
-
-
-
0
0
15
42
98<
0
0
-
-
-
-
0
0
31
78
0
2
Cl
2
23
16
-
0
0
0
-
-
80
98<
-
-
30
45
33
18
10
0
0
-
73
64
32
15
0
0
48
98
3
Toluene Air
THF Air
CH OH Air
DMSO Air
3
CCl
CCl
CCl
CCl
4
4
4
4
Air
Air
Air
-
b
10
11
12
13
14
b
O
O
2
CH
CH
CH
3
CN
CN Air
CN Air
2
-
-
-
13
18
60
-
-
-
36
54
98<
3
3
b
-
a
Isolated yield except b cases
TLC showed no signs of 2-naphthol.
b
1
9

Scheme 1. The synthesis of H L
2
2
0

N
N
CH3
OH
OH
O
O
O
OH
V
V
O
O
2
O
O
CH3
O
OH
N
N
CH3
O
N
N
2
O
CH3
O
O
O
V
O
O
V
V
O
O
V
O
O
O
O
CH3
O
O
O
CH3
2
CH OH
3
X1
X3
N
N
CH3
O
H2O
O
O
N
N
V
O
V
O
O
O
O
O
CH3
O
N
N
O
1/2O2
H
H
O
X2
Scheme 2. Proposed mechanism for the oxidative coupling of 2-naphthol catalyzed by
complex 1
2
1

2 2 3 2 3 2 3
Fig. 1. Molecular structure of complex [V O (L)(µ-OCH ) (OCH ) ]·CH OH (1)
2
2

Fig. 2. O-H•••O and C-H•••O hydrogen bonding interactions in the crystal of
complex 1
2
3

Graphical Abstract
Graphical abstract
•
Synthesis and structure of a new dinuclear oxidovanadium(V) complex with an
-donor ligand
N
2
O
2
•
Catalytic behavior of the V(V) complex for the oxidative coupling of 2-naphthol
to produce BINOL