Inorganica Chimica Acta 510 (2020) 119756

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Inorganica Chimica Acta

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Research paper

Mechanistic studies on the in-situ generation of furoxan ring during the T

formation of Cu(II) coordination compound from dioxime ligand:
Theoretical and experimental study
⁎ ⁎
Rahman Bikasa, , Younes Valadbeigia, , Marta Otrębab, Tadeusz Lisb
a
Department of Chemistry, Faculty of Science, Imam Khomeini International University, 34148-96818 Qazvin, Iran
b
Faculty of Chemistry, University of Wroclaw, 50-383 Wroclaw, Poland

A R T I C LE I N FO A B S T R A C T

Keywords: The copper(II) coordination compound, [Cu(Lʹ)(NO3)2] (1) where Lʹ = 3,4-di(pyridin-2-yl)-1,2,5-oxadiazole 2-

Furoxan oxide, was synthesized from the reaction of Cu(NO3)2·3H2O and dioxime ligand, (1E,2E)-1,2-di(pyridin-2-yl)
Cu(II) coordination compound ethane-1,2-dione dioxime (L), in methanol under aerial atmosphere. The dark-blue crystals of 1 were obtained
Crystal structure by solvent evaporating method and were characterized by elemental analysis, FT-IR spectroscopy and single
Ring formation
crystal X-ray studies. Structural studies indicated that in 1 a furoxan ring is generated during the formation of
Mechanism
mononuclear Cu(II) coordination compound from the in-situ intramolecular cyclization reaction of dioxime
moiety of the initial ligand. The density functional theory (DFT) along with B3LYP functional was employed to
propose a rational mechanism for cyclization of dioxime (L) and formation of the furoxan ring in 1. It was found
that the isolated ligand (L) is not an acidic compound while its acidity is enhanced dramatically in coordination
compound in the presence of NO3− anions assisting its deprotonation. Ring formation is catalyzed by Cu in the
second deprotonation step, i.e. Cu(II) accepts the negative charge of L, produced upon deprotonation, to assist
formation of the neutral aromatic furoxan ring. In the last step, Cu(I) is oxidized to Cu(II) by solvated oxygen,
O2(CH3OH)n, to retrieves its structure and oxidation state.

1. Introduction compounds [11]. Various oxidizing reagents like manganese dioxide,

1,2,5-Oxadiazole-2-oxides (Scheme 1a), known as furoxans, are a
class of important five-membered heterocyclic compounds containing
two nitrogen and one oxygen atoms [1]. They can be considered as the
oxygenated form of 1,2,5-oxadiazoles (furazanes, Scheme 1b) because
an oxygen atom is connected to one of the nitrogen atoms of the het-
erocyclic ring. The compounds containing this ring have wide range of
applications in various fields like medicine [2], biological studies [3],
coordination chemistry, organic synthesis, energetic materials [4] or
high density explosives [5]. Several effective synthetic methods like the
reaction of styrenes with nitrosonium tetrafluoroborate [6], dimeriza-
tion of nitrile oxides [7], the reaction of α-nitro-ketoximes and sulfonyl
chlorides [8], oxidation of ortho-nitro anilines [9], etc. have been re-
ported for obtaining this class of heterocyclic compounds. Among the
various methods for obtaining furoxans, the oxidative cyclization of
vicinal dioximes (Scheme 1c) [10] is one of the most popular and ac-
cessible methods because a wide range of dioximes can be easily pre-
pared by the reaction of hydroxyl amine with suitable organic
ferricyanide, nitrogen oxides, hypohalites, etc. have been employed for
this oxidative cyclization reaction [12,13]. Also, it has been reported
that the copper(II) salts can act as oxidizing agent in this reaction [14].
Although, due to the presence of nitrogen and oxygen atoms, fur-
oxan based compounds are interesting ligands in coordination chem-
istry, considering literature including Cambridge Structural Database
(CSD) [15] indicates only 7 structures related the transition metal co-
ordination compounds containing this ring have been reported until
now. Surprisingly, most of them (4 of the reported 7 structures) are the
Cu(II) complexes [16] and the remaining reports are related to Mn [17],
Zn [18] and Ag [19]. Considering the reported structures indicates the
furoxan ring in some cases is generated during the formation of co-
ordination compound. It shows that the metal ion can have effective
role in this cyclization reaction beside the other parameters. Never-
theless, because of the lack of a mechanistic study, the details of this
cyclization reaction and the influencing parameters are not clear.
(1E,2E)-1,2-Di(pyridin-2-yl)ethanedione dioxime (L, see Scheme 2a)
is structurally an interesting dioxime that has also two pyridine rings

⁎
Corresponding authors.
E-mail addresses: bikas@sci.ikiu.ac.ir, bikas_r@yahoo.com (R. Bikas), valadbeigi@sci.ikiu.ac.ir (Y. Valadbeigi).

https://doi.org/10.1016/j.ica.2020.119756
Received 29 December 2019; Received in revised form 23 April 2020; Accepted 10 May 2020
Available online 15 May 2020
0020-1693/ © 2020 Elsevier B.V. All rights reserved.
R. Bikas, et al.
a) O b) O obtained by slow solvent evaporating method during one week. The
O crystals were isolated by filtration and washed with cold methanol and
N N N N
R R' R R'
c) O
O 448 (w), 416 (w). UV–Vis in CH3OH: λmax, nm (ε, M−1cm−1): 250
HO N N OH N N
Oxidation
-2H+, -2e
R R' R R'
Scheme 1. a) General structure of 1,2,5-oxadiazole-2-oxides (furoxans), and b)
1,2,5-oxadiazoles, c) obtaining furoxans from oxidative cyclization of vicinal
dioximes.
and has high potential to form coordination compounds. It was firstly
prepared in 1970 [20] and its crystal structure was reported in 2012
[21]. Although this compound can have several configurations, struc-
tural studies reveal that the oxime moieties are located trans respect to
each other and the OH groups are involved in intermolecular OH···N
hydrogen bond interactions [21]. There is only one report on the metal
coordination compound of this ligand [22] which confirms there is not
considerable report about its coordination chemistry and structural
properties. In the reported structure [22] the ligand acts as counter ion
by protonation of the pyridine rings. Also, there are two reports con-
taining furoxan compounds [16a,23]. However, considering these re-
ports shows that the starting compound in both of them was not a di-
oxime and mentioned furoxans have been obtained by other methods.
Due to the high coordination ability of L toward the metal ions, we
were interested to employ this ligand in preparing copper(II) co-
ordination compounds. The results of the synthesis and characterization
indicated that the dioxime part of the ligand is converted to a furoxan
ring during the formation of coordination compound (see Scheme 2b).
Therefore, DFT calculations were used to investigate the mechanism of
this in-situ furoxan ring formation and determine the roles of copper
and NO3− in this process.
2. Experimental
2.1. Materials and instrumentations
Copper(II) nitrate trihydrate, 2-pyridinecarboxaldehyde, hydro-
xylamine hydrochloride, and other materials and solvents were pur-
chased from Aldrich and used without any further purification. The
oxime ligand, (1E,2E)-1,2-di(pyridin-2-yl)ethanedione dioxime or
(1E,2E)-2,2′-dipyridylglyoxime (L), was synthesized and characterized
according to previous reports [21]. FT-IR spectra in the range of
400–4000 cm−1 were recorded with KBr on a Bruker TENSOR 27 FT–IR
spectrophotometer. Elemental analyses for C, H and N were performed
on a Carlo ERBA Model EA 1108 analyzer. Cu content of the compound
was determined by atomic absorption analysis using a Varian Spectra
AA-220 equipment. The UV–Vis spectra were recorded on a thermo-
spectronic Helios Alpha spectrophotometer.
2.2. Synthesis of [Cu(Lʹ)(NO3)2] (1)
The dioxime ligand (0.242 g, 1.00 mmol) was dissolved in 20 ml of
methanol and the solution was added to a flask containing 20 ml of
methanolic solution of Cu(NO3)2·3H2O (0.241 g, 1.00 mmol) and the
resulting mixture was refluxed for 12 h under aerial atmosphere. The
obtained solution was cooled to room temperature and the undissolved
residue was removed by filtration. The dark-blue crystals of 1 were
2
Inorganica Chimica Acta 510 (2020) 119756
dried at air. Yield: 72%. Anal. Calc. for C12H8CuN6O8 (MW = 427.78 g/
mol): C, 33.69; H, 1.88; N, 19.65; Cu, 14.86%. Found: C, 33.64; H, 1.91;
N, 19.65; Cu, 14.80%. Selected FT-IR (KBr, cm−1): 3061 (m), 2923 (m),
1605 (s), 1574 (m), 1476 (s), 1448 (m), 1326 (m), 1272 (m), 1224 (m),
1183 (m), 1158 (s), 1118 (s), 1109 (s), 1085 (s), 1036 (s), 1027 (s), 954
(m), 1142 (s), 832 (s), 799 (vs), 725 (m), 647 (m), 602 (w), 534 (w),
(16800), 390 (13200), 690 nm (140).
2.3. X-ray crystallography
A summary of the crystal data and refinement details for 1 are given
in Table 1 and selected bond lengths and angles are presented in
Table 2. The dark-blue cubic crystals of compound 1 crystallize in Pbca
space group of orthorhombic system. The X-ray data were collected at
100(2) K with a Kuma-KM4 CCD diffractometer using MoKα radiation
λ = 0.71073 Å. The structure was solved by direct methods and refined
with the full-matrix least-squares method on F2 with the use of
SHELXL2013 program packages [24]. The analytical absorption cor-
rections were applied by CrysAlis package of programs [25]. The C-
bonded hydrogen atoms were calculated from geometry and were
constrained during refinement.
2.4. Componential details
Structures of all intermediates, coordination compound and ligands
were fully optimized at the B3LYP/6-31+G(d) level in the methanol as
the solvent. Tomasi’s Polarized Continuum Model (PCM) was used for
the calculations in the solvent (methanol) [26]. The frequency calcu-
lations were performed at the same level of theory to obtain thermo-
dynamic quantities at 298 K. Because of accuracy of the Atomic Polar
Tensor (APT) [27] method in calculation of charge distribution of
systems with transition metals, the partial charges were computed using
APT method. Gaussian 09 was used for all calculations [28].
3. Results and discussion
3.1. Synthesis, crystal structure and spectroscopy
The dioxime ligand, L, was synthesized from the reaction of hy-
droxylamine hydrochloride and 1,2-di(pyridin-2-yl)ethane-1,2-dione
according to previous reports [21]. The reaction of L with Cu
(NO3)2·3H2O in methanol under aerial atmosphere gave blue solution
and the dark-blue crystals were obtained by evaporating of the solvent
during one week. The structure of the obtained crystals was determined
by single crystal X-ray analysis. The molecular structure of compound 1
is shown in Fig. 1 and selected bond lengths and angles are collected in
Table 2. Diffraction studies indicated that the blue crystals are related
to a mononuclear Cu(II) coordination compound and during the for-
mation of 1 the initial dioxime ligand is converted to a new ligand
containing a furoxan ring. The furoxan ring is generated by in-situ cy-
clization reaction during the coordination of ligand to the Cu(II) ion.
This ring is disordered in two positions which is mainly due to the
symmetric character of the obtained ligand. The furoxan ring is almost
planar and the C]N and NeO bonds of the ring are in the normal range
observed in similar rings [29]. The length of external NeO bond (O2-
N3 = 1.236(3) Å) is relatively shorter than NeO bonds of the furoxan
ring (O1-N4 = 1.366(3) O1-N3 = 1.437(3) Å) which is in agreement
with the previously reported furoxan rings [29] and can be attributed to
the electrostatic interactions between O– and N+ atoms. The obtained
ligand acts as a N2-donor bidentate ligand and is coordinated to the
metal ion through two nitrogen atoms of the pyridine rings. As it is seen
in Fig. 1, a seven membered CuC4N2 ring is generated by coordination
of these nitrogen atoms to the Cu(II) ion and the N–Cu–N angle is
R. Bikas, et al. Inorganica Chimica Acta 510 (2020) 119756

Scheme 2. Synthetic pathway and structure of a) H2L and b) compound 1.

Table 1
Crystallographic data and refinement details for compound 1.
Compound 1

Net formula C12H8CuN6O8

Mr/g mol−1 427.78
crystal size/mm 0.48 × 0.34 × 0.26
T/K 100
Diffractometer Kuma-KM4
crystal system Orthorhombic
Crystal shape, color Block, dark blue
space group Pbca
a/Å 10.468(3)
b/Å 14.359(4)
c/Å 20.227(5)
V/Å3 3040.3(14)
Z 8
calc. density/g cm−3 1.869
µ/mm−1 1.50
F(0 0 0) 1720
θ range 3–36.8
h,k,l −13 → 17, −14 → 19, −26 → 26
Rint 0.029
R[F2 > 2σ(F2)] 0.038
wR(F2) 0.113
S 1.10
Hydrogen refinement Mixed Fig. 1. Molecular structure of compound 1 with atom numbering scheme, the
Measured reflections 24,177 disordered part of the furoxan ring is omitted for clarity.
Independent reflections 4412
Reflections with I > 2σ(I) 3669
Parameters, Restraints 261, 0 95.31(6)°. This ring has a twist-boat configuration (see Fig. S1). The
Max electron density/e Å−3 1.27 copper(II) ion in 1 has six coordinated CuN2O4 coordination environ-
Min electron density/e Å−3 −0.60
ment and the coordination geometry around it can be described as a
distorted octahedral geometry. The equatorial plane of the distorted
octahedral geometry is formed by coordination of two nitrogen atoms
Table 2
Selected bond lengths (Å) and angles (°) in the crystal structure of compound 1.
of pyridine ring from the ligand and two oxygen atoms from the nitrate
anions. The axial positions are occupied by two oxygen atoms of the
Bond Lengths (Å) Angles Angles (°) coordinated nitrate anions and the axial Cu–O bonds are considerably
Cu1-N2 1.9799(15) N2-Cu1-N1 95.31(6)
longer than the equatorial bonds. This matter is due to the Jahn-Teller
Cu1-N1 1.9833(14) N2-Cu1-O4 164.08(5) distortion that usually observes in octahedral Cu(II) coordination
Cu1-O4 1.9913(13) N1-Cu1-O4 90.95(5) compounds with d9 electronic configuration [30]. Although in the
Cu1-O6 2.0013(13) N2-Cu1-O6 88.02(6) structure of free dioxime ligand the pyridine groups are located trans to
Cu1-O7 2.4379(13) N1-Cu1-O6 171.06(5)
each other, they are located cis respect to each other in the structure of
O1-N4 1.366(3) O4-Cu1-O6 87.98(6)
O1-N3 1.437(3) N2-Cu1-O7 87.40(5) compound 1. This conformational change is probably another de-
O2-N3 1.236(3) N1-Cu1O7 114.39(5) terminant factor assisting the formation of furoxan ring because in this
N3-C6 1.319(3) O4-Cu1-O7 103.32(5) orientation the oxime groups will have cis orientation which is the
N4-C7 1.321(3) O6-Cu1-O7 57.37(5)
suitable orientation for the formation of furoxan ring. Two hydrogen
C6-C7 1.422(2) N4-O1-N3 107.45(16)
atoms have been eliminated from the structure of ligand during the
formation of furoxan ring. As it is reported in literature [12,13], the
furoxan ring is generated by oxidative cyclization of the dioxime group

3
R. Bikas, et al.
and the aerial oxygen is the sole oxidant in this reaction (see
Scheme 2b). We could not obtain compound 1 in the control experi-
ment in the absence of oxygen (inert atmosphere). This matter indicates
the presence of molecular oxygen as an oxidant is essential for the
formation of furoxan ring. Nevertheless, it is clear that the Cu(II) ion
can also involve in the oxidation/reduction process in this reaction and
facilitate the formation of furoxan ring. The Cu–N and Cu–O bonds in
the structure of compound 1 are in the normal range observed for Cu(II)
coordination compounds with N- and O-donor ligands [31]. By con-
sidering the presence of several oxygen atoms from nitrate anions and
furoxan ring, it is predictable that the crystal structure of 1 has several
intermolecular hydrogen bond interactions. The information of the
CeH···O interactions in the crystal structure of 1 is available in Table S1
and part of them is shown in Fig. S2. These interactions may have
significant effect on the stability of the crystal structure of 1.
Elemental analysis of compound 1 was in good agreement with the
obtained structure from single crystal X-ray analysis. FT-IR spectrum of
compound 1 shows medium and strong bands at 1605, 1574, and
1448 cm−1, which can be attributed to the C]N, C]C and nitrate
vibrations, respectively [32].
3.2. Theoretical investigation of the mechanism of in-situ furoxan ring
formation
The first required criterion for the formation of [Cu(Lʹ)(NO3)2] co-
ordination compound with a furoxan ring is chelating of the nitrogen
atoms of the pyridine rings to Cu(II) ion. Chelating of other nitrogen
atoms of ligand L, does not lead to furoxan ring formation. Chelating of
Fig. 2. Relative energies of different isomers for the [Cu(L)(NO3)2] molecule. The structures have been optimized at B3LYP/6-31+G(d) level in methanol solvent.
The energies are in kJ mol−1.
4
Inorganica Chimica Acta 510 (2020) 119756
L via different donor sites causes different structural isomers of [Cu(L)
(NO3)2] molecule. Fig. 2 compares the optimized structures and relative
energies of five possible isomers for [Cu(L)(NO3)2] molecule in me-
thanol (isomers a-e). The isomer [Cu(L)(NO3)2]-a is the most stable
structure in which the Cu(II) ion simultaneously interacts with the ni-
trogen atoms of two pyridine rings. This result is in agreement with
experiment i.e. the molecule [Cu(L)(NO3)2]-a is the true precursor of
the final compound synthesized in this work.
Formation of the furoxan ring requires dehydrogenation of the L in
[Cu(L)(NO3)2]-a. The general mechanism proposed for dehydrogena-
tion of L is deprotonation of the ligand followed by electron transfer
from [Cu(L-H)(NO3)2]− to O2 [16,33]
−H+ +O2
[Cu(L)(NO3)2] → [Cu( L− H)(NO3)2]− → [Cu( L− H)(NO3)2] + O2−
−e
(1)
Reaction (1) should be repeated twice to achieve the final [Cu(Lʹ)
(NO3)2] compound. Decreasing the pH of reaction mixture during the
formation of 1 is also an experimental evidence for the release of H+
during the reaction. The optimized structures of the intermediate mo-
lecules [Cu(L)(NO3)2], [Cu(L-H)(NO3)2]−, [Cu(L-H)(NO3)2], and [Cu
(Lʹ)(NO3)2]− are depicted in Fig. 3. To track change in the oxidation
state of copper ion during the reaction, the partial charge on the Cu in
each intermediate, computed using APT method, are also shown in
Fig. 3.
Deprotonation of L in [Cu(L)(NO3)2] depends on the acidity of the
compound. Enthalpy of deprotonation, ΔHacid, [34] was used as an
index of acidity to track the acidity enhancement of L upon chelating.
R. Bikas, et al. Inorganica Chimica Acta 510 (2020) 119756

Fig. 3. The optimized structures of the possible intermediates from [Cu(L)(NO3)2] to [Cu(Lʹ)(NO3)2] in methanol. The partial charge on the Cu atom, q, computed
using APT method, also is shown for each intermediate molecule.

Table 3 in methanol indicating the second deprotonation is thermodynamically

The calculated ΔHacid and ΔGacid values for deprotonation of L, [Cu(L)(NO3)2], more preferred than the first deprotonation. Because in the first de-
and some common acids in methanol solvent at 298 K. protonation only the electron withdrawing effect of nitrate was the
Deprotonationa ΔHacid ΔGacid inflicting factor while in the second deprotonation, change in the Cu
(kJ.mol−1) (kJ.mol−1) state from +2 to +1 (Fig. 3) and formation of furoxan ring also relieve
the produced negative charge. According to the Hückel rule of 4n + 2
L → (L-H) + H+ 1210.2 1180.1
π-electrons, the furoxan ring is aromatic only in neutral form. To fulfill
HCN → CN− + H+ 1203.4 1172.3
CH3COOH → CH3COO− + H+ 1181.4 1156.9 this rule, the negative charge of [Cu(Lʹ)(NO3)2]− is transferred to Cu,
HCOOH → HCOO− + H+ 1163.3 1132.1 and consequently, the oxidation state of Cu changes from +2 to +1 in
[Cu(L)(NO3)2] → [Cu(L-H)(NO3)2]− + H+ 1154.1 1121.9 this compound. It should be noted that the Cu(I) species are the active
HNO3 → NO3− + H+ 1091.6 1060.8 intermediates and after the formation, they immediately convert to Cu
H2SO4 → HSO4− + H+ 1068.4 1037.3
[Cu(L-H)(NO3)2] → [Cu(Lʹ)(NO3)2]− + H+ 933.6 899.9
(II) in the presence of aerial oxygen. Although the detection of such
intermediates is a difficult matter and we had limitation to detect them,
a
L = Ligand. the involvement of copper atom in the redox reactions and the forma-
tion of Cu(I) intermediates in the various aerial oxidation of organic
Calculated ΔHacid values of L, [Cu(L)(NO3)2], and [Cu(L-H)(NO3)2] are compounds have been frequently reported in literature [35]. In sum-
compared in Table 3. Smaller value of ΔHacid indicates stronger acidity mary, Cu catalyzes the cyclization of the ligand by change in its oxi-
[34]. dation state from +2 to +1 and this change materializes as a structural
Comparison of the ΔHacid values reveals that L in [Cu(L)(NO3)2] is deformation from octahedral to tetrahedral (Fig. 3).
not only more acidic than the isolated ligand but is also stronger acid It should be mentioned that in the reaction condition, we did not
than formic and acetic acid in methanol. These evidences confirm that observe furoxan ring formation in the isolated ligand L. This observa-
due to the strong acidity of [Cu(L)(NO3)2], the progress of the reaction tion may be attributed to weak acidity of the isolated L (Table 3) and its
via deprotonation is thermodynamically favored. The results of charge lower ability for deprotonation. Optimized structures and relative sta-
analysis (Fig. 3) show that the acidity enhancement is not due to pre- bilities of different isomers of L and (L-H)- have been compared in Figs.
sence of copper, as the oxidation state of Cu does not change during the S3 and S4, respectively (see Supplementary Materials).
deprotonation ([Cu(L)(NO3)2] and [Cu(L-H)(NO3)2]-). Extra acidity of According to reaction (1), after each deprotonation step, the nega-
[Cu(L)(NO3)2] is the result of existence of two strong electron with- tively charged moiety should be oxidized. Our calculations showed that
drawing nitrate groups. Interestingly, [Cu(L-H)(NO3)2] with ΔHacid oxidation of [Cu(Lʹ)(NO3)2]− is an endothermic reaction with en-
values of 933.6 kJ mol−1 is a superacid stronger than HNO3 and H2SO4 thalpies of 448.6 kJ mol−1. It has been proposed that the O2 is one of

5
R. Bikas, et al.
the potent oxidizing agent for this reaction [16,33]. The reported
electron affinity (EA) value of O2 in gas phase is 86.8 kJ mol−1 [36]
indicating that it cannot oxidize the negatively charged intermediate
molecule. However, because the reaction takes place in methanol, effect
of medium and solvation should be also considered. Hence, instead of
unsolvated O2, electron affinity values for its solvated forms,
O2(CH3OH)n, were computed. The optimized structures for the clusters
O2(CH3OH)2,4 and O2−(CH3OH)2,4 are shown in Fig. S5 and their
electron affinities are summarized in Table S2. Solvation increases EA
of O2 dramatically so that the EA values for O2, O2(CH3OH)2, and
O2(CH3OH)4 are 86.8, 418.1, and 468.5 kJ mol−1, respectively. Hence,
oxidation of [Cu(Lʹ)(NO3)2]− moiety is thermodynamically more fa-
vorable using solvated forms of O2 rather than unsolvated O2. During
oxidization of [Cu(Lʹ)(NO3)2]− to [Cu(Lʹ)(NO3)2], Cu retrieves its oxi-
dation state and the tetrahedral structure converts to octahedral
(Fig. 3).
By considering the mentioned findings based on experimental and
theoretical studies and also the previous reports in literature, it is ob-
vious that the in-situ generation of furoxan ring during the formation of
copper coordination compound is occurred by several steps. Briefly, in
the first step the pyridine rings of the ligand coordinate to the Cu(II) ion
by considering their high donor ability and higher stability of the ob-
tained compound in comparison to the other possible coordination
modes. In such condition, the orientation of the dioxime moiety
changes from trans to the cis configuration. Therefore, they are located
close to each other which this orientation is one of the important re-
quirements for the formation of furoxan ring from vicinal dioximes. The
acidity of OH groups increases by coordination of the ligand to the
metal ion and consequently, the ligand releases one H+ in the next step
which also follows by the oxidation of compound with dissolved oxygen
in the methanol. In the next step, the oxidation-deprotonation of the
compound and intramolecular cyclization takes place to form the fur-
oxan ring. The Cu(II) ion acts as an important species in the oxidation
process by changing the oxidation state from II to I which also follows
by the oxidation to Cu(II) by oxygen in the next steps. Therefore, the
combination of the coordination of ligand to the metal ion and the
catalytic effect of Cu(II) ion in oxidative cyclization reaction are the
effective parameters in the formation of furoxan ring from dioxime
group in the current case. Although the copper ion has significant role
in this process, the molecular oxygen dissolved in methanol is the
oxidant and the copper ion can be considered as a catalyst or electron
transferring intermediate that increases the rate of reaction and facil-
itates the formation of furoxan ring.
4. Conclusion
In summary, a new mononuclear Cu(II) coordination compound,
[Cu(Lʹ)(NO3)2]n (1), was synthesized in the reaction of Cu(NO3)2·3H2O
and dioxime ligand and characterized by elemental analysis, FT-IR
spectroscopy and single crystal X-ray analysis. The studies indicated the
formation of a furoxan ring from the in-situ intramolecular cyclization
reaction of dioxime group. The mechanism of in-situ formation of fur-
oxan ring from dioxime group was studied theoretically at B3LYP/6-
31+G(d) level of theory in methanol. It was found that the ring for-
mation proceeds via deprotonation of L in [Cu(L)(NO3)2] followed by
oxidation by O2(CH3OH)n. In the first deprotonation step, NO3− causes
acidity enhancement assisting more easily deprotonation while the
second deprotonation is along with ring formation so that both Cu and
NO3− groups influence the acidity of the ligand in the second depro-
tonation. During the second deprotonation, Cu, by change in its oxi-
dation state from II to I, withdraws the negative charge of the depro-
tonated ligand and induces ring formation. From the calculated values
of ΔH and ΔG, it was proposed that the unsolvated O2 cannot oxidize
the deprotonated molecule, instead the oxidation is thermodynamically
preferred to be carried out by the solvated oxygen, O2(CH3OH)n. The
isolated ligand L, does not undergo ring formation because of its low
6
Inorganica Chimica Acta 510 (2020) 119756
acidity and weak ability to be deprotonated.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors are grateful to Imam Khomeini International
University, Iran for financial support of this study.
Appendix A. Supplementary data
CCDC 1973988 contains the supplementary crystallographic data
for compound 1. This data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or e-mail: deposit@
ccdc.cam.ac.uk. Supplementary data to this article can be found online
at https://doi.org/10.1016/j.ica.2020.119756.
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