Received: 16 October 2017 Revised: 23 November 2017 Accepted: 25 November 2017

DOI: 10.1002/aoc.4234

FULL PAPER

Catalytic activity of nickel(II), copper(II) and

oxovanadium(II)‐dihydroindolone complexes towards
homogeneous oxidation reactions

Mohamed Shaker S. Adam1,2

1
Department of Chemistry, College of
Science, King Faisal University, P.O. Box Three novel paramagnetic metal complexes (MH2ID) of Ni2+, Cu2+ and VO2+
380, Al Hufuf 31982, Al Hassa, Saudi ions with 3‐hydroxy‐3,3’‐biindoline‐2,2’‐dione (dihydroindolone, H4ID) were
Arabia
2
synthesized and characterized by different spectroscopic methods. The ligand
Department of Chemistry, Faculty of
Science, Sohag University, Sohag 82534, (H4ID) was synthesized via homocoupling reaction of isatin in presence of
Egypt phenylalanine in methanol. Complexation of low valent Ni2+, Cu2+ ions and
high valent VO2+ ions with H4ID carried out in 1: 2 molar ratios. A comparison
Correspondence
Mohamed Shaker S. Adam, Department of in the catalytic potential of paramagnetic complexes of low and high valent
Chemistry, College of Science, King Faisal metal ion was explored in the oxidation processes of cis‐cyclooctene, benzyl
University, P.O. Box 380 Al Hufuf 31982
alcohol and thiophene by an aqueous H2O2, as a green terminal oxidant, in
Al Hassa, Saudi Arabia; Department of
Chemistry, Faculty of Science, Sohag the presence and absence of acetonitrile, as an organic solvent, at 85 °C.
University, Sohag‐82534, Egypt. NiH2ID, CuH2ID and VOH2ID show good catalytic activity, i.e. good chemo‐
Email: madam@kfu.edu.sa;
and regioselectivity. VOH2ID has the highest catalytic potential compared to
shakeradam61@yahoo.com
both Ni2+‐ and Cu2+‐species in the same homogenous aerobic atmosphere.
Catalytic oxidation of other alkenes and alcohols was also studied using NiH2ID,
CuH2ID or VOH2ID as a pre‐catalyst by an aqueous H2O2. A mechanistic
pathway for those oxidation processes was proposed.

KEYWORDS
catalysis, complexes, copper(II), Dihydroindolone, hydrogen peroxide, nickel(II), oxidation,
oxovanadium(II)

1 | INTRODUCTION sterically and electronically modified, are very highlighted

for that propose.[4–8] One of the most problem facing
Redox activity of transition metal complexes towards chemists in homogenous catalytic redox processes is the
chemo‐ and regioselective oxidation of organic com- presence of toxic organic solvents, e.g. acetonitrile.
pounds as an essential issue in organic synthesis is one Recently, most of the fundamental research in catalytic
of the most challenging quest in both laboratories and redox processes carried out under organic solvent‐free
industrial applications.[1,2] The catalytic oxidation of conditions.[4–8]
alkenes, alcohols and thiols is highly applicable reaction The catalytic oxidation processes using high valent
in organic synthesis.[3] Particularly, optimization of the transition metal complexes, e.g. oxide vanadium com-
catalytic potentials in redox processes is typically plexes,[9] is more favored than that using low valent
enhanced through the structural environment of the metal, e.g. copper and nickel due to the various coordina-
metal–ligand complexes, as catalysts. Therefore, ligand tion numbers of oxide vanadium complexes. Moreover,
frameworks with O,O‐donor centers that could be the easily interchanging of high stable oxidation states of

Appl Organometal Chem. 2018;e4234. wileyonlinelibrary.com/journal/aoc Copyright © 2018 John Wiley & Sons, Ltd. 1 of 12
https://doi.org/10.1002/aoc.4234
2 of 12 ADAM

vanadium ion is observed (e.g. between V4+ and V5+). spectra were analyzed at room temperature using a multi-
The more Lewis acid character of the high valent metal nuclear FT‐NMR spectrometer Bruker ARX400 with 400.1
ion enhances its catalytic potential toward oxidation (1H) and 100.6 (13C) MHz. The 1H and 13C chemical shifts
processes. The strong bonding of the metal to oxygen, are given in ppm. Coupling constant values refer to JHH in
i.e. oxide vanadium ions O=V4+, gives more catalytic reac- 1
H and JCC in 13C NMR unless denoted otherwise. Split-
tivity toward redox processes more than other low valent ting pattern for larger and smaller coupling constants
metal‐complex catalysts.[10] are given in the same order as the J values. Molecular
An aqueous hydrogen peroxide, as a more favored oxi- electronic spectra are measured using 10 mm silica cells
dizing, is classified as green oxidant. It is significantly in the thermostatted cell holder of a Jasco UV‐Vis spectro-
cheap, safety stored, high effective oxygen donor and photometer (model V‐570). Infrared spectra (as KBr discs)
more environmentally friendly due to the only given by‐ are measured within the region of 4000‐400 cm‐1 by
product, water.[11] Shimadzu FTIR‐8101 Fourier Transform Infrared spectro-
Condensation of isatins and indolin‐2‐ones in various photometer. Conductivity measurements are accom-
reaction conditions is of interest in recent research.[12] plished using a Jenway conductivity meter model 4320,
Those reactions are directed towards yield development with an epoxy bodied conductivity cell (two electrodes,
of isoindigo derivatives due to their high applicable shiny) with cell constant calibration from 0.01 to 19.99
importance.[13,14] Moreover, isoindigo derivatives could at 25 °C. Magnetic susceptibility of the studied complexes
be synthesized by dimerization through homocoupling are measured on Gouy's balance, the diamagnetic correc-
reaction of isatins[15–17] or dihydroindolones,[18–22] which tion were made by Pascal's contents and Hg[Co(SCN)4] as
gives two main reaction products (isoindigos and a calibrant.
dihydroindolones) depending upon the reaction condi-
tions.[23,24] Synthesis and characterization of isoindigo
and its derivatives were studied in details, but those of
2.2 | Synthesis of dihydroindolone (H4ID)
dihydroindolone are so far in literatures.
To the best of our knowledge, coordination chemical H4ID was synthesized via homocoupling of isatin in an
behavior of H2ID as a dihydroindolone derivative (H4ID) attempt to prepare a dianionic tridentate ONO‐Schiff base
is not yet reported. Therefore, it is a motivation here ligand by a direct condensation of isatin with phenylala-
to study the synthetic routes and characterization of nine, as observed elsewhere.[25,26]
dihydroindolone (H4ID) and its corresponding transition The synthesis of H4ID carried out by mixing of a
metal complexes (Ni2+, Cu2+ and VO2+ ions). Applying methanolic solution (15 ml) of isatin (0.14 g, 1.0 mmol)
low and high valent transition metal complexes (MH2ID), with 20 ml of an aqueous/methanolic (1, 1) solution of
as homogeneous catalysts, in the oxidation of various phenylalanine (0.16 g, 1.0 mmol) at 25 °C.[27] The resulted
alkenes, alcohols and thiophene is considered an interest solution was heated for 2 hours at 60 °C (monitored by
study under various catalytic conditions with comparison TLC), giving of a dark‐red solution with observation of a
between their catalytic potential. It is a recent demand to white precipitate. The precipitate was filtrated out and
improve the catalytic processes environmentally using a washed with methanol and petroleum ether then dried
green oxidant, i.e. an aqueous H2O2, and under solvent‐ in an oven, as a crude product. The final product was
free conditions. Hence, the catalytic redox potential of extracted by purification with column chromatography
NiH2ID, CuH2ID or VOH2ID is investigated in acetoni- using 15% n‐hexane: 85% diethyl ester affording 84% yield.
trile and under solvent‐free conditions using an aqueous The crystals of H4ID were obtained by slow recrystalliza-
H2O2, as oxygen source. tion in methanol (Figures 1 and 2). Phenylalanine did
not inter that reaction and extracted by column chroma-
tography. Table 1 presents the hydrogen‐bond geometry
2 | EXPERIMENTAL
of H4ID, as reported before.[27]
1
H NMR (DMSO‐d6, 400 MHz): δ 3.23 (s, 1H), 4.01
2.1 | Materials and apparatus
(s, 1H), 6.26 (d, 3J = 7.12 Hz, 1H), 6.44 (s, 1H), 6.67
All required reagents and materials are supplied from (t, 3J = 7.28, 7.44 Hz, 1H), 6.77 (s, 2H), 6.99 (t, 3J = 7.28,
Sigma‐Aldrich and Acros. They are used directly without 7.40 Hz, 1H), 7.14 (t, 3J = 7.14, 7.64 Hz, 1H), 7.26
any additional purification or treatment. All experimental (t, 3J = 7.52, 7.57 Hz, 1H), 7.43 (d, 3J = 6.96 Hz, 1H),
reactions were performed under stirring and by holding 10.11 (s, 1H, NH), 10.22 ppm (s, 1H, NH).
the reaction temperature constant using oil baths. C, H 13
C NMR (100 MHz, DMSO‐d6, dept‐135): δ 51.81
and N analyses are carried out using a VarioEl GMBH (CH), 76.03 (Cq), 109.50 (CH), 110.04 (CH), 121.48 (CH),
model V2.3 CHNS machine. Nuclear magnetic resonating 121.55 (CH), 124.47 (CH), 126.29 (Cq), 126.86 (CH),
ADAM 3 of 12

128.82 (Cq), 128.89 (CH), 130.05 (CH), 143.23 (Cq), 143.82

(Cq), 174.69 (Cq, C=O), 177.51 ppm (Cq, C=O).

2.3 | Synthesis of metal‐dihydroindolone

complexes (MH2ID)
Complexes of Ni2+, Cu2+ and VO2+ ions were synthesized
by a classical method (Scheme 1). 1.0 mmol of nickel ace-
tate tetrahydrate (0.24 g), cupper acetate monohydrate
(0.19 g) or vanadyl acetylacetonate (0.26 g) in 20 ml water
was added dropwise to a suspended solution of H4ID
(0.56 g, 2.0 mmol) in methanol (50 ml). The resulted reac-
tion mixture was kept with stirring at 70 °C for 6 hours to
FIGURE 1 The molecular structure with labeling scheme and
give a precipitate of the corresponding colored MH2ID.
50% probability ellipsoids of indolyl‐indolone (H4ID). The π
The resulted precipitate of MH2ID was filtrated out and
(C―O)···π (ring) interaction is shown as a dotted line. Cg1 and Cg2
washed by water, methanol and petroleum ether, and
are, respectively, the centroids of the C1, C6, C7, C8, N1 ring and the
C10―O3 bond [27] then dried in a desiccator containing dried P2O5 awarding
good significant yield (Table 1).

2.4 | Catalytic procedure

Oxidation of alkenes, alcohols or thiophene (1.0 mmol)
was initiated by insertion of 30% an aqueous H2O2
(3.0 mmol), as the oxidizing agent, catalyzed by MH2ID
(0.02 mmol) in acetonitrile (10 ml) at the boiling point

FIGURE 2 Packing one of the N—H···O hydrogen bonded (blue SCHEME 1 The synthetic route of the metal‐dihydroindolone
dotted lines) chains of indolyl‐indolone (H4ID). [27] complexes (MH2ID)

TABLE 1 Characteristic CHN analysis, melting point, appearance and electronic spectra of MH2ID and H4ID at [MH2ID] and [H4ID] = 1 ×
10‐5 mol dm‐3 in DMSO at 25 °C

Microanalyses found %, (calc. %) Electronic spectra

MW Yield m.p.
Comp. (g mol‐1) C H N (%) App. (°C) λmax (nm) εmax (mol‐1 cm‐1) Assign.
H4ID 280.28 68.21 (68.56) 4.75 (4.32) 10.18 (9.99) 84 White 187 276 6842 n→π*
219 315 π→π*
NiH2ID 617.23 61.96 (62.27) 3.87 (3.59) 9.44 (9.08) 91 Green 274 527 vbr 14820 d→d
378 3429 LMCT
226 3386 n→π*
CuH2ID 622.09 61.95 (61.78) 3.23 (3.56) 10.37 (10.21) 87 Dark green 293 518 vbr 844 d→d
269 958 n→π*
VOH2ID 625.48 61.69 (61.45) 3.31 (3.55) 9.16 (8.96) 88 Brown 305 351 vbr 4799 LMCT
272 14266 n→π*

vbr = very broad band

4 of 12 ADAM

of acetonitrile (~ 85 °C), while the solvent‐free oxidation structure. Crystal data presents the details of structure
oxidation were performed at 85 °C, in an oil bath with refinement, which reported by Mague & Adam et al.,[27]
continuous stirring for 4 hours in an aerobic atmosphere. in which Table 2 presents the hydrogen‐bonding of H4ID.
The catalytic reactions were monitored and controlled by Figure 3 interprets the 1H NMR spectral signals of
withdrawing samples of the reaction media (ca. 1 ml in H4ID. 1H NMR spectra shows two singlet signals at
acetonitrile or one drop under solvent‐free conditions) 10.11 and 10.22 ppm, which are assigned for the two ‐
at different and interval time. The withdrawal samples NH group in two different atmospheres. Moreover, there
were treated with solid MnO2 and Na2SO4 anhydrous are two singlet signals in the aliphatic region at 3.23 and
(ca. 20 mg) to quench the excess amounts of an aqueous 4.01 ppm are assigned for the hydrogen of the chiral C‐9
H2O2. Under solvent‐free conditions the components of and the cyclic hydroxyl group (Figure 1 and supplemen-
the sample was extracted by 1 ml of acetonitrile. The tary materials of 1HNMR, 13CNMR, dept‐135). The rest
resulting slurry was filtered on celite, and then diluted of 1HNMR spectral signals are characteristic for the
by acetonitrile (1: 3) mixed in vortex. 1 μL of the diluted aromatic protons.
sample was injected in the GC‐MS to point out the
maximum reactivity of the catalyst complexes at a
diffident time. 3.2 | Synthesis and characterization of
Each sample was analyzed by Gas chromatography metal‐complexes (MH2ID)
mass spectrometer (GC‐MS) Shimadzu model QP2010 The novel complexes (MH2ID) were synthesized by com-
SE equipped with Rxi‐5 Sil MS capillary column (30 m plexation of dihydroindolone (H4ID) with Ni2+, Cu2+
length × 0.25 mm ID × 025 um film thickness). The and VO2+ ions in methanol with 2: 1 molar ratios (ligand:
analysis was performed using the gas chromatography metal) in which H4ID acted as monoanionic bidentate
parameters as follow: injector temperature, 250 °C; initial chelating agent (Scheme 1). MH2ID were obtained in
oven temperature, 40 °C (held for 1 min), increased to good yields (Table 1). NiH2ID, CuH2ID and VOH2ID were
200 °C at a rate of 10 °C min−1. The total time required characterized using elemental analysis, MS, FT‐IR and
for one GC run was 17 minutes. The inlet was operated UV–visible diffuse spectroscopies, conductivity, and mag-
in the splitless mode. The MS transfer line was held at netic measurements. The CHN microanalysis magnitudes
200 °C. The carrier gas is high‐purity helium with a flow
rate 1 ml min‐1. LabSolution software was used to control
TABLE 2 Hydrogen‐bond geometry of H4ID (Å, °) [27]
the system and to acquire the analytical data.
D—H···A D—H H···A D···A D—H···A
O2—H2A···O1 0.84 1.93 2.7575 (17) 167
3 | RESULTS AND DISCUSSION
N1—H1···O3 0.94 (2) 1.96 (2) 2.8644 (17) 161 (2)

3.1 | Synthesis and characterization of N2—H2B···O3 0.90 (3) 2.00 (3) 2.8882 (18) 173 (2)
dihydroindolone (H4ID) and its
metal‐complexes
Due to the presence of phenylalanine which did not react
with isatin in a condensation reaction as reported
previously,[25,26] promotes homocoupling or dimerization
of isatin to award dihydroindolone (H4ID) with good yield
(Table 1). Protonation of carbonyl group in isatin
increases the molecule electrophilicity by acid catalyzed
reaction using phenylalanine, as reported for the synthe-
sis of isoindigo derivatives catalyzed by ZrCl4, as Lewis
acid,[23] or by water.[24] the main role of phenylalanine
not as a reactant but as Lewis acid catalyst for the
homocoupling reaction of isatin.
H4ID was characterized by elemental analysis, NMR,
IR and UV‐Vis. spectra. The molecular structure of H4ID
has been elucidated by single crystal X‐rays diffraction
(Figures 1 and 2).[27] The single crystals of H4ID were
obtained by recrystallization in hot methanol. The FIGURE 3 1
HNMR spectral scan of indolyl‐indolone (H4ID)
dihydroindolone moieties are close to form planar ligand in DMSO‐d6 at 25 °C
ADAM 5 of 12

agree (± 0.5%) with the suggested molecular structure of TABLE 3 Structural significant infrared spectral assignments
MH2ID (Table 1). (ν, cm‐1) of the MH2ID and their corresponding ligand (H4ID)
MH2ID are soluble in N,N'‐dimethylsulfoxide (DMSO) Group
and N,N'‐dimethylformamide (DMF), and sparingly
Comp. H4ID NiH2ID CuH2ID VOH2ID
soluble in high polar solvents, e.g. methanol, acetonitrile
O―H 3523 w br
and acetone. The pH stability of MH2ID solutions
(1 × 10−4 mol dm−3) is in the neutral region from pH N―H 3342 w br 3474 br 3391 br 3364 br
~ 3.7 to 8.9. They are decomposed in strong basic and 3278 w br 3202 w br 3198 w br 3300 w br

acidic media since the decay in color takes place (pH was C―Har 3060 w 3042 w 3027 w 3041 w
controlled by using standard universal buffer solutions). C=O 1718 m 1653 m 1668 s 1650 m
Table 1 reports the characteristic maximum absorp- 1681 s 1628 s 1619 m 1601 m
tion wavelength, λmax (nm), and the calculated molar C―O 1465 m 1443 m 1438 s 1452 m
absorptivity, εmax (mol–1 cm‐1), of the all possible molecu- 1197 w 1108 w 1095 w
lar electronic transitions for ligand and its metal com- C―N 1308 w 1285 w 1277 m 1326 w
plexes (Figure 4). H4ID shows only two characteristic
M―O 486 w 558 m 489 w
bands in the ultraviolet region, at 219 and 276 nm, which
V=O 968 m
attributed to the π→π* and n→π* transitions, respec-
tively. The π→π* and n→π* transitions are overlapped br = broad intensity, s = strong intensity, m = moderate intensity, w = weak
after complexation in Ni2+, Cu2+ and VO2+‐complexes intensity, ar = aromatic ring intensity, py = pyridine ring intensity

to give an absorption band in the ultraviolet region at

226, 269 and 272 nm, respectively. One or two additional
bands are appeared in MH2ID (Table 1) at 378 and of H4ID to Ni2+, Cu2+ or VO2+ ions through the
351 nm in the visible region due L→MCT transition in deprotonated hydroxyl group of the two coordinated
NiH2ID and VOH2ID, respectively.[28] Also, the d→d ligand molecules (Scheme 1). The band at 1718 cm‐1 is
transition due to the complexation in NiH2ID and assigned for the C=O vibration which shifted to 1653,
CuH2ID are occurred at 527 and 518 nm, respectively 1668 and 1650 cm‐1 in that spectra of the Ni2+, Cu2+ or
(Figure 4 and Table 1).[29] VO2+ complexes, respectively. This observation is also
The FT‐IR spectra of H4ID and its M‐complexes resulted from the coordination of the ligand through the
(MH2ID) are presented in Table 3. In H4ID, a characteris- carbonyl group to the transition metal ion. Furthermore,
tic stretching vibrational band of ‐OH group (3523 cm‐1) is the vibrational band of C―O at 1197 cm‐1 is also influ-
completely disappeared after complexation with Ni2+, enced by the complexation and shifted to 1108 and
Cu2+ and VO2+ ions. This result is due to the coordination 1095 cm‐1 in Ni2+ and VO2+‐complexes, respectively
(Table 3). The appearance of new bands at 486, 558 and
489 cm‐1 in the spectra of Ni2+, Cu2+ or VO2+‐complexes,
3.5 respectively, are characteristic for the new formed M―O
H4ID bond. Furthermore, the additional new characteristic
NiH2ID
3.0
CuH2ID band of V=O is located at 968 cm‐1[30] (Scheme 1).
VOH2ID The high stretching vibrational of NH group in the
2.5
free ligand and its corresponding M‐ dihydroindolone
complexes (3474 and 3202 cm‐1 in NiH2ID, 3391 and
3198 cm‐1 in CuH2ID, and 3364 and 3300 cm‐1 in
2.0
Abs.

VOH2ID) is probably resulted from the intermolecular

1.5
hydrogen bonding between the complex molecules
1.0
(Figure 5).
Molar conductivities (Λm) of MH2ID were measured
0.5 in different solvents (DMF and DMSO) at 25 °C and the
results are presented in Table 4. Particularly, the results
0.0 demonstrate that MH2ID are electrolytic non‐conducting
200 250 300 350 400 450 500 550 600 650 700
compounds without any free ions in the solution.[31]
λ, nm
Magnetic susceptibilities of all MH2ID (Table 4)
FIGURE 4 Molecular electronic spectral scan of H4ID and its recommended that MH2ID are para‐magnetic in a square
corresponding M‐complexes (MH2ID), [complex] ≈ 1 × 10‐5 mol pyramidal geometrical structure, as recorded values
dm‐3 in DMSO at 25 °C 2.09, 2.75 and 1.89 B.M. for NiH2ID, CuH2ID and
6 of 12 ADAM

3.3 | Determination of thermodynamic

H parameters of MH2ID
N
O H The stoichiometric molar ratios of MH2ID were
N
O
O
determined by spectrophotometric continuous variation
O M method.[33] The continuous variation method confirms
O
N
H
O that the metal ion reacted with H4ID in 1: 2 molar ratios
N
forming MH2ID, as documented in Figure 6. The forma-
H H
N
tion constants Kf of MH2ID were obtained from the spec-
O H trophotometric measurements, by using Equation 1:[30]
N
O
O 
O M A
O Am
N
H Kf ¼  2 (1)
O
N 1−A =Am C
H H
N
O Where Am is the absorbance at the point of the most
H
O
N complete complex formation according to the continuous
O
M variation plot (Figure 6), A is the absorbance of the com-
O
O
N
H plex at the arbitrary chosen metal ion concentration C.
O
N The calculated magnitudes of Kf in Table 5 indicate
H that all prepared complexes are highly stable in the solu-
tion. The values of Kf reflect the decrease of substitution
FIGURE 5 Tentative molecular structure of intermolecular
reaction of H4ID and go in the following series: VOH2ID
hydrogen bonding of MH2ID > CuH2ID > NiH2ID.
The equilibrium formation constant for MH2ID is
measured at different temperatures, in order to derive
the thermodynamic parameters for each complex. The
TABLE 4 Characteristic magnetic moments (μ) and molar con-
thermodynamic parameters, ΔfH and ΔfS, could be
ductivity measurements (Λm) of the VO‐complexes (concentration
in electrolytic solution = 1 × 10−4 moldm‐3) in DMSO and DMF at
derived from the Gibb's–Helmholtz equation (Equation 2),
25 °C. Mass spectral data of MH2ID (electrospray ionization mass as function of (1/T) (Figure 7).
spectra) (in DMSO)
Δf G
μ Λm ¼ −RlnK f (2)
T
(Ω−1·cm2·mol−1) ESI‐MS (m/z)
Complex (B.M.) DMSO DMF [ML+1] [L‐M+1]
NiH2ID 2.09 2.2 8 616.1 280.0, 279.3
1.8
CuH2ID 2.75 2.8 13 623.0 279.0
NiH2ID
VOH2ID 1.89 1.7 12 626.2 279.3 1.6 CuH2ID
VOH2ID
1.4

1.2
VOH2ID, respectively.[32] Those derived data confirm
1.0
that there is no remarkable interaction between metal
Abs

ions (Ni2+, Cu2+ or VO2+) in their complexes in their 0.8

solutions.[30] 0.6
The molecular ion (M + 1) peak of M‐complexes indi-
0.4
cated high purity (Figures S1–S3, supporting informa-
tion). The mass spectral data match appreciably with the 0.2

tentative structure of MH2ID complexes. In addition, 0.0

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
MH2ID are mononuclear without any interaction
[L]/ [L]+[M]
between M2+ ions in the solution (Table 4). Table 1 pre-
sents the melting points of H4ID and its corresponding FIGURE 6 Plots of continuous variation method for the
Ni‐, Cu‐ and VOH2ID, which illustrate the high stability stoichiometric molar ratios in MH2ID in aqueous‐methanolic
of the synthesized complexes. medium at [MH2ID] ≈ 10‐4 mol dm‐3 and 25 °C
ADAM 7 of 12

TABLE 5 Stability constants and thermodynamic parameters of of recent research highlights on the chemoselectivity of
MH2ID, [MH2ID] ≈ 1 × 10‐4 mol dm‐3 the alcohols oxidation to their corresponding aldehydes
T Kf ×109 ΔfG ΔfH ΔfS (J and ketones by different pre‐catalyst of transition metal
Complex (°C) (L2 mol‐2) (kJ mol‐1) (kJ mol‐1) mol‐1 K‐1) complexes.[36–38] Catalytic oxidation of sulfides has been
NiH2ID 20 4.21 ‐53.98 62.90 ‐28.72 progressed recently using different oxidants.[39,40] An
25 3.93 ‐54.73 aqueous H2O2 is the most effective and less toxic oxidant,
30 2.45 ‐54.46 which used widely in such redox processes.[9,41]
35 1.67 ‐54.37 Consequently, the catalytic potential of the studied
40 0.83 ‐53.44 M‐dihydroindolone complexes (MH2ID) is investigated
CuH2ID 20 5.81 ‐54.76 38.80 ‐54.83 in the redox processes of cis‐cyclooctene, benzyl alcohol
25 4.66 ‐55.15 and thiophene using an aqueous H2O2 in acetonitrile
30 3.79 ‐55.56 or under solvent‐free conditions. NiH2ID, CuH2ID or
35 2.90 ‐55.79
VOH2ID (0.02 mmol) was mixed with the substrate
40 2.07 ‐55.82
(1.0 mmol), i.e. cis‐cyclooctene, benzyl alcohol or thio-
VOH2ID 20 5.37 ‐54.57 24.29 ‐103.52 phene in acetonitrile (10 ml) or under solvent‐free condi-
25 4.75 ‐55.20
tions. The reaction mixture was initiated with an aqueous
30 3.92 ‐55.64
35 3.46 ‐56.24
H2O2 (3.0 mmol) at 85 °C for 4 hours. The redox reaction
40 2.84 ‐56.64 products were monitored by gas chromatography mass
spectra. Tables 6–8 reported the conversion and selectivity
percentages (TON and TOF values) of the oxidation prod-
ucts of cis‐cyclooctene, benzyl alcohol or thiophene.
To point out the optimized reactivity of the studied
22.5
complex catalysts, the catalytic processes were controlled
and controlled by time at 85 °C. From Tables 6--8, the best
22.0 time for the maximum conversion and chemoselectivity is
after 3 hours for the oxidation of cis‐cyclooctene and
21.5
bezaldehyde. Nevertheless, for the oxidation of thiophene,
ln Kf

the optimized time was 2 hours catalyzed by NiH2ID,

CuH2ID or VOH2ID. The target product of cis‐cyclooctene
21.0 is epoxy‐cyclooctane with presence of other by‐
NiH2ID
CuH2ID products.[42] Benzaldehyde is the main product of benzyl
VOH2ID alcohol oxidation with observation of benzoic acid as side
20.5
unfavored product. Oxidation of thiophene gave two
0.00320 0.00325 0.00330 0.00335 0.00340 0.00345 products, thiophene oxide as the chemoselective product,
-1
1/T ( K ) and thiophene dioxide as the other unwanted by‐product.
The oxidation reaction is considerable sensitive to the cat-
FIGURE 7 Determination of thermodynamic parameters of
alyst type hinging on the type of central metal ion.[11,43,44]
NiH2ID, CuH2ID and VOH2ID formation from ln Kf values
In aerobic catalyst‐free conditions for the oxidation of
cis‐cyclooctene, benzyl alcohol and thiophene, Table 9
The Gibb's free energy values (ΔfG) are negative which
presents the catalytic processes results in absent of the
reflect the spontaneous complex formation under given
studied complex catalysts in acetonitrile. The results
conditions. The complexation reaction could be classified
display very low percentages of uncontrol conversion
as exothermic according to the negative values of
and chemoselectivity. Hence, MH2ID are considered
ΔfH, and the formed metal‐ligand bonds took place
effective catalysts for such redox processes.
strongly.[34]
In presence of NiH2ID, CuH2ID and VOH2ID, the
catalytic processes afford high chemoselectivity in the oxi-
dation of cis‐cyclooctene, benzyl alcohol or thiophene
3.4 | Catalytic processes
(Tables 6--8). NiH2ID displays good conversion and
Epoxides, as the main products of the alkenes (ep)oxida- chemoselectivity of cis‐cyclooctene, benzyl alcohol and
tion, are the key starting reagents for a wide variety of thiophene oxidation after about 3 hours giving 69% of
products in the organic synthesis.[10,35] Aldehydes and epoxy cyclooctane, 55% of benzaldehyde and 42% of thio-
ketones are essential products and intermediates in the phene oxide, respectively (entries 3, 7 and 10, respectively,
fine chemical redox processes of alcohols. Moreover, most Table 6). CuH2ID shows better yield of conversion and
8 of 12 ADAM

TABLE 6 Oxidation process catalyzed by NiH2ID using an aqueous H2O2 in acetonitrile

Conversion (%)
Time Conversion Selectivity
a
Entry Reactant (h) Rb (residual) Pc Side products (%) (%) TONd TOFe
1 Cis‐cyclooctene 1 58 40 2 42 95 23.5 23.5
2 2 28 61 11 72 85 40.5 20.2
3 3 2 69 29 98 70 43.5 14.5
4 4 0 65 35 100 65 40 10
5 Benzyl alcohol 1 58 31 11 42 74 23.5 23.5
6 2 35 45 20 65 69 35 17.5
7 3 17 55 28 83 66 40.5 13.5
8 4 0 52 48 100 52 34 8.5
9 Thiophene 1 49 31 20 51 61 21.5 21.5
10 2 32 43 25 68 63 26 13
11 3 18 42 40 82 51 25.5 8.5
12 4 0 40 60 100 40 22 5.5
a
Ooxidation of cis‐cyclooctene, benzyl alcohol or thiophene (R) (1.0 mmol) catalyzed by NiH2ID (0.02 mmol) with an aqueous H2O2 (3.0 mmol) in 10 ml of
acetonitrile for 4 hours at 85 °C.
b
The residual amount (%) of the reactant after finishing the catalytic process (R).
c
Selectivity percentage of epoxy cyclooctane, benzaldehyde or thiophene oxide (P), and the other side products.
d
TON (turnover number) is the ratio of moles of product obtained to the moles of catalyst.
e
The corresponding TOF (turnover frequency) (TON/h) is shown as mol (mol catalyst)‐1 h‐1.

TABLE 7 Oxidation process catalyzed by CuH2ID using an aqueous H2O2 in acetonitrile

Conversion (%)
Time Conversion Selectivity
a
Entry Reactant (h) Rb (residual) Pc Side products (%) (%) TONd TOFe
1 Cis‐cyclooctene 1 49 47 4 51 92 23.5 23.5
2 2 13 81 6 87 93 40.5 20.2
3 3 1 87 12 99 87 43.5 14.5
4 4 0 80 20 100 80 40 10
5 Benzyl alcohol 1 42 47 9 56 83 23.5 23.5
6 2 17 70 13 83 84 35 17.5
7 3 0 81 19 100 81 40.5 13.5
8 4 0 68 32 100 68 34 8.5
9 Thiophene 1 34 43 23 66 65 21.5 21.5
10 2 19 52 29 81 64 26 13
11 3 7 51 42 93 54 25.5 8.5
12 4 0 44 56 100 44 22 5.5
a
Ooxidation of cis‐cyclooctene, benzyl alcohol or thiophene (R) (1.0 mmol) catalyzed by CuH2ID (0.02 mmol) with an aqueous H2O2 (3.0 mmol) in 10 ml of ace-
tonitrile for 4 hours at 85 °C.

chemoselectivity after 3 hours reporting 87, 81 and 51% (Table 8). The more Lewis acid character and the high
(entries 3, 7 and 10, respectively, Table 7). But, the most oxidation number of the central V4+ ion in VOH2ID might
effective catalyst for those reactions is VOH2ID, which be the main reasons for that higher catalytic potential of
afforded the best amount of the selective product, epoxy VOH2ID compared to those catalysts, i.e. NiH2ID and
cyclooctane (91%), benzaldehyde (85%) and thiophene CuH2ID of the low valent.[10] The high oxidation number
oxide (59%) (entries 3, 7 and 11, respectively, Table 8). of VO2+ ion progresses the interchanging of oxidation
Comparison of the catalytic efficiency between the states between V4+ and V+5 ion (see the reaction
three novel complex catalysts for all the redox processes, mechanism),[9,35] which could play the a remarkble role
VOH2ID is more effective and sufficient catalyst for the for enhancing the catalytic activity of VOH2ID. Addition-
oxidation of cis‐cyclooctene, benzyl alcohol or thiophene ally, the high reversibility of the electrochemical proper-
than those NiH2ID and CuH2ID, however, NiH2ID ties of VO2+ species compared to that of Ni2+ and Cu2+
and CuH2ID present a respectable catalytic potentials ions could be the motivated factor for its higher catalytic
ADAM 9 of 12

TABLE 8 Oxidation process catalyzed by VOH2ID using an aqueous H2O2 in acetonitrile

Conversion (%)
Time Conversion Selectivity
a
Entry Reactant (h) Rb (residual) Pc Side products (%) (%) TONd TOFe
1 Cis‐cyclooctene 1 41 56 3 59 94 28 28
2 2 11 83 6 89 93 41.5 20.75
3 3 0 91 9 100 91 45.5 15.1
4 4 0 74 26 100 74 37 9.25
5 Benzyl alcohol 1 50 47 3 50 94 23.5 23.5
6 2 28 64 8 72 88 32 16
7 3 3 85 12 97 87 42.5 14.1
8 4 0 71 29 100 71 35.5 8.87
9 Thiophene 1 27 43 22 65 66 21.5 21.5
10 2 12 57 31 88 64 28.5 14.25
11 3 4 59 37 96 61 29.5 9.83
12 4 0 47 53 100 47 23.5 5.87
a
Ooxidation of cis‐cyclooctene, benzyl alcohol or thiophene (R) (1.0 mmol) catalyzed by VOH2ID (0.02 mmol) with an aqueous H2O2 (3.0 mmol) in 10 ml of ace-
tonitrile for 4 hours at 85 °C.

TABLE 9 Catalytic oxidation process in acetonitrile and free of organic synthesis is the challenged consideration for
solvent in absence of catalysts, MH2ID, using an aqueous H2O2 the inorganic chemists.[4] Diminish of the toxic organic
Conversion, %a (Selectivity, %) solvent is the main essential development in the homoge-
neous catalytic processes.[1,5–8] This is why most of recent
acetonitrile free solvent
catalytic redox reactions take place under solvent‐free
Cis‐cyclooctene 13 (93) 17 (85)
conditions. The oxidation of cis‐cyclooctene, benzyl
Benzyl alcohol 10 (84) 13 (81) alcohol and thiophene using an aqueous H2O2 under
Thiophene 19 (62) 22 (49) solvent‐free conditions catalyzed by NiH2ID, CuH2ID
a
Cis‐cyclooctene, benzyl alcohol or thiophene oxidation (R) (1.0 mmol) with or VOH2ID for 3 hours was examined. The results
an aqueous H2O2 (3.0 mmol) for 3 hours at 85 °C under aerobic conditions. were recorded in Table 10. The results present high
conversion of cis‐cyclooctene oxidation 100% with
potential.[45,46] Furthermore, the high affinity of VO2+ NiH2ID or VOH2ID, and 98% with CuH2ID, with low
ions toward oxygenation reactions is remarked compared chemoselectivity compared to that in acetonitrile (51, 74
to that of Ni2+ and Cu2+ ions[47,48] (Scheme 2). and 83% with NiH2ID, CuH2ID and VOH2ID, respec-
Moreover, CuH2ID is little more reactive than NiH2ID tively). In acetonitrile, the chemoselectivity of cis‐
for the cis‐cyclooctene, benzyl alcohol and thiophene cyclooctene oxidation was better with NiH2ID, CuH2ID
oxidation by an aqueous H2O2 (Tables 6 and 7). This could and VOH2ID (69, 87 and 91, respectively). Similarly, oxi-
be predicted from the previous reported literatures.[43,44] dation of benzyl alcohol (49, 68 and 77%) and thiophene
Particularly, Ni(II)‐complexes are usually have good to (52, 41 and 50%) catalyzed by NiH2ID, CuH2ID and
low catalytic activity.[30,36] This probably depends upon VOH2ID, respectively, afforded good conversion under
the geometrical structure and coordination sphere of solvent free conditions with lower chemoselectvity com-
Ni(II) complexes.[11] Generally, Ni(II)‐complexes of octa- pared to those in acetonitrile (Table 10). In absence of
hedral structure have unremarkable catalytic efficiency the organic solvent, water molecules of the oxidant
towards redox processes.[49] On the other hand, the pro- (an aqueous H2O2) may reduce the catalytic reactivity of
posed tetrahedral structure of NiH2ID of para‐magnetism MH2ID which could occupy the active coordinated sites
with four coordination number explains its sufficient cat- in the catalyst complex.[41,53] Furthermore, water may
alytic potential for the oxidation processes. Accordingly, cause hydrolysis of the target products to give more yield
the catalytic activity of Ni‐octahedral complexes is lower of side unknown products. Conclusively, the redox pro-
than that of tetrahedral complexes[50] due to the steric cesses of cis‐cyclooctene, benzyl alcohol and thiophene
demand and availability of free coordination sites in tetra- pre‐catalyzed by NiH2ID, CuH2ID and VOH2ID using an
hedral geometry.[49,51,52] Therefore, NiH2ID is an effective aqueous H2O2 is more favored in acetonitrile than under
catalyst in the redox processes of cis‐cyclooctene, benzyl solvent‐free conditions.
alcohol and thiophene, as observed in Table 6. An aqueous H2O2 as terminal oxidant is an effective
The recent significant improvement of suitable, suffi- and more environmentally friendly in alkenes oxidation
cient and more environmentally friendly redox processes compared to the other organic oxides, e.g. tert‐butyl
10 of 12 ADAM

SCHEME 2 The proposed mechanism

for the oxidation of cis‐cyclootene, benzyl
alcohol and thiophene (R) by an aqueous
H2O2 catalyzed by MH2ID

hydroperoxide.[53] In particular, the catalytic redox 3.5 | A proposed mechanism for the redox
processes of various aliphatic or cyclic alkenes and reactions
alcohols catalyzed by NiH2ID, CuH2ID or VOH2ID
Mixing of an aqueous H2O2 with MH2ID (in acetonitrile)
afforded high conversion percentages with moderate to
might led to oxidation of the complex catalyst to
low chemoselectivity of the target products (Tables 11
form an active species of Ni3+, Cu3+ and V5+=O
and 12) under the optimized reaction conditions (in aceto-
ions (A) through electron transfer mechanism (see
nitrile after 3 hours at 85 °C).
Scheme 2).[8,9,35] Coordination of another oxidizing agent
molecule to the active complex A afforded another active
intermediate complex (B).[41] Oxygen transfer from the
TABLE 10 Catalytic oxidation process free solvent catalyzed by coordinated H2O2 molecule to central metal ion in B
MH2ID using an aqueous H2O2 could be carried out giving an active oxo‐ or peroxo‐
Conversion, %a (Selectivity, %)
intermediate (C) with exploring of water molecule
(Scheme 2).[54–57] The oxo‐ or peroxo‐intermediate
NiH2ID CuH2ID VOH2ID
(C) was subjected to the substrate molecule, R
Cis‐cyclooctene 100 (51) 98 (74) 100 (83) (cis‐cyclooctene, benzyl alcohol or thiophene), by
Benzyl alcohol 81 (49) 95 (68) 90 (77) coordination of R to the central metal ion in C with
Thiophene 76 (52) 85 (41) 92 (50) approach of R to the bonded oxygen in the oxo‐ or
a
Cis‐cyclooctene, benzyl alcohol or thiophene oxidation (R) (1.0 mmol)
peroxo‐intermediate liberating a new intermediate
catalyzed by MH2ID (0.02 mmol) with an aqueous H2O2 (3.0 mmol) for (D).[41,42,58] Due to the approach of R to the bonded
3 hours at 85 °C. oxygen in D, oxidation of R could be suggested giving

TABLE 11 Oxidation reaction of other aliphatic and cyclic alkenes catalyzed by MH2ID using an aqueous H2O2

Conversion, %(Selectivity, %)
a
Entry Alkene Product NiH2ID CuH2ID VOH2ID
1 86 (69) 91 (82) 94 (86)

2 90 (54) 85 (90) 88 (91)

3 52 (61) 80 (64) 83 (45)

4 54 (22) 71 (38) 89 (41)

5 45 (24) 65 (30) 81 (42)

6 66 (25) 64 (46) 69 (46)

a
Reaction condition carried out in acetonitrile (10 ml) of alkene (1.0 mmol) with aqueous H2O2 (4.0 mmol), MH2ID (0.02 mmol) at 85 °C after 3 hours.
ADAM 11 of 12

TABLE 12 Oxidation reaction of some aromatic and aliphatic alcohol catalyzed by MH2ID using an aqueous H2O2

Conversion, % (Selectivity, %)
a
Entry Alkene Product NiH2ID CuH2ID VOH2ID
1 76 (58) 85 (55) 88 (52)

2 38 (14) 81 (85) 89 (82)

3 75 (43) 88 (60) 85 (64)

4 70 (52) 90 (57) 88 (63)

5 62 (37) 65 (40) 81 (45)

6 68 (46) 72 (51) 75 (52)

a
Reaction condition carried out in acetonitrile (10 ml) of alcohol (1.0 mmol) with aqueous H2O2 (4.0 mmol), MH2ID (0.02 mmol) at 85 °C after 3 hours.

the final oxide product RO with recycling of the liberated The oxidation processes are more favored and effective in
oxidized active complex (A), as shown in Scheme 2. acetonitrile than those under solvent‐free conditions. The
oxidation processes at the optimized reaction condition in
acetonitrile of some aliphatic or cyclic alkenes and alcohols
4 | CONCLUSIONS catalyzed by NiH2ID, CuH2ID or VOH2ID afforded high
conversion potential with good to low chemoselectivity of
Dihydroindolone ligand (H4ID) was synthesized as the target products. A short proposed mechanism of the
unfavored and surprised product in presence of phenylal- catalyzed redox processes was suggested, involving electron
anine via homocoupling or dimerization of isatin. H4ID transfer and oxygen transfer steps.
was characterized by X‐ray single crystal analysis. The
ligand behaves as monobasic bidentate by complexation
ORCID
to low valent Ni2+ or Cu2+ ion and high valent VO2+
ion in 2: 1 molar ratios (ligand: metal). The synthesized Mohamed Shaker S. Adam http://orcid.org/0000-0001-
complexes (MH2ID) were characterized by various 8826-3558
physic‐chemical tools. The thermodynamic parameters
of M‐dihydroindolone complexes were determined
RE FER EN CES
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