Received: 17 May 2016 Revised: 29 June 2016 Accepted: 2 July 2016

DOI 10.1002/aoc.3574

F U L L PA P E R

Schiff base complexes and their versatile applications as catalysts

in oxidation of organic compounds: part I
Wail Al Zoubi | Young Gun Ko*

School of Materials Science & Engineering,

Yeungnam University, Gyeongsan 38541, Republic Schiff bases and their complexes are good candidates as versatile compounds which
of Korea are synthesized by the condensation of a primary amino compound with either
Correspondence aldehydes or ketones for a variety of industrial applications. They can act as cata-
Young Gun Ko, School of Materials Science &
lysts in the catalytic oxidation of organic compounds. Recent researches in oxidation
Engineering, Yeungnam University, Gyeongsan
38541, Republic of Korea. catalysis have focused on how to employ the metal‐catalyzed oxidation of organic
Email: [email protected] substrates. This review summarizes the current developments of the last few decades
for the oxidations of organic compounds that proceed through Schiff base com-
plexes. The chemical syntheses of Schiff bases and their complexes are outlined.

KE YWO RD S

catalyst, oxidation, Schiff bases, sulfide, Synthesis

1 | IN T RO D U C T IO N the range of applications of artificial oxygen carrier com-

plexes, such as their use as catalysts for the oxidation of
Schiff bases are prepared when any primary amine (NH2) unsaturated organic compounds. For example, cobalt Schiff
reacts with an aldehyde (COH) or a ketone (CO) under spe- base complexes are interesting because, in aprotic solvents,
cific conditions of pH and temperature. Structurally, Schiff they exhibit dioxygenase‐like activities as well as reversible
bases (also known as imine or azomethine) are the nitrogen formation. The solvent (B) was a monodentate ligand in the
analogue of an aldehyde or ketone in which the carbonyl axial position of Co(II) Schiff base complex. The oxygen
group has been replaced by an imine or azomethine group affinity of the chelate increased with increasing base strength
(Figure 1). They are widely used as organic compounds due of B, making it possible to understand the thermodynamic
to their excellent coordinative capability and have a wide behavior of O2. The oxygen absorption properties of Co
variety of industrial applications in many fields including (II) complexes of N,N′‐bis(salicylidene)‐2,2′‐dimethyl‐1,
analytical, biological, coordination and inorganic chemistry, 3‐propanediimine ligand derivatives, so‐called CoSaldmpr,
in organic synthesis, such as pigments, dyes and catalyst have been reported. The complexes generated significant
intermediates, and as polymer stabilizers. The chemistry of results in N‐methyl‐2‐pyrrolidinone (an organic compound
Schiff bases is an important area of research with increasing consisting of a five‐membered lactam) solution. For com-
interest due to the simple synthesis, versatility and diverse plexes with 2‐pyridinecarbonitrile as axial base, loading
ranges of applications of their metal complexes, e.g. in biol- of Co(3‐methoxysaldmpr), measured in (g O2/g solution)
ogy and as catalysts in various reactions. Thus, a review remained ca 35% higher than that of Co(3‐methoxy‐Salen)
highlighting the oxygen affinity of Schiff base complexes for at least four absorption–desorption cycles.[5]
would be needed.[1–4] The oxygen absorption–desorption processes for square
planar Mn(II), Co(II) and Mn(II) complexes of tetradentate
Schiff base ligands (Figure 2) in N,N‐dimethylformamide
2 | OXYG E N A F F IN I T Y O F S C HI F F BA S E (DMF) and chloroform solvents have been investigated.
COMPLEXES The sorption processes were undertaken in the presence
and absence of (pyridine) axial base in 1:1 molar ratio of
Schiff bases and their complexes have potential applications pyridine:metal(II) complexes. Complexes in DMF indicated
by virtue of their abilities to bind oxygen; this field spans better oxygen affinity than those in chloroform. Also, Co(II)

Appl. Organometal. Chem. 2016; 1–12 wileyonlinelibrary.com/journal/aoc Copyright © 2016 John Wiley & Sons, Ltd. 1
2 AL ZOUBI AND KO

catalysts, Schiff base complexes have been supported on

heterogeneous materials.[11,12] Among them, salicylidene
Schiff base(salen)(chelating ligand) can be easily synthesized
using condensation of salicylaldehyde and an amino com-
pound. On the other hand, salen complexes of transition
metals are stable compounds used as catalysts for various
organic reactions. Among transition metals, Ni, Co, Cr, Cd
and Zn Schiff base complexes are the most versatile catalysts
desirable for organic transformations.[13–15]

FIGURE 1 General scheme for formation of Schiff bases 3.1 | Oxidation of organic compounds
Life would not exist without oxidation, which is very
important from scientific and practical points of view. In
organic chemistry, oxidation reactions are some of the most
important ones. Thus, selective catalytic oxidations represent
a severe challenge for modern organic chemistry, and their
importance has been highlighted in terms of Nobel Prizes.
The reaction between ONS donor ligands H2L (derived
FIGURE 2 Representative structures of Schiff ligands (A) H2Salen, (B)
from salicylaldehyde or its derivatives or 2‐hydroxy‐1‐
H2Hacen and (C) H2Acacen
naphthaldehyde and o‐aminothiophenol) and [RuHCl(CO)
complexes showed significant sorption to greater extent as (PPh3)] afforded new Ru(II) complexes of [Ru(L)(CO)
compared to Mn(II) and Ni(II) complexes. The presence (PPh3)] (L = dianionic ONS donor Schiff base ligand).
of pyridine axial base resulted in an increase in oxygen Theses complexes were found to be effective for the
affinity. Thus, this kind of material could be used as a oxidations of alcohols and sulfides at room temperature using
catalyst in oxidative reactions in organic chemistry and N‐methylmorpholine‐N‐oxide as oxidant. This provided a
petrochemicals, which was reproducible and was considered general method for the oxidations of different kinds of alco-
also environmentally friendly.[6] hols under mild conditions. Benzylic primary and secondary
The reversible binding reactions of oxygen to alcohols were oxidized to products in excellent yield, and
N,N′‐ethylenebis(salicylideniminato)cobalt (CoS), to which aliphatic and cyclic alcohols gave carbonyl compounds in
a photoisomerizable stilbazole residue of copolymer was moderate yield.[16]
coordinated, were investigated. The E form of the stilbazole Four dioxidomolybdenum(VI) complexes, [Mo(VI)O2
residue coordinating to CoS, (E)‐1‐CoS, showed (dha‐bhz)MeOH)](H2dha‐bhz), [MoO2(dha‐inh)(MeOH)],
photoisomerization into the Z form, (Z)‐1‐CoS, on direct [MoO2(dha‐nah)MeOH)] and [MoO2(dha‐fah)MeOH)], and
ultraviolet irradiation and negligible reverse isomerization. their corresponding oxidoperoxidomolybdenum(VI) com-
The oxygen binding equilibrium constant (K) values for plexes, [MoO(O2)(dha‐bhz)(MeOH)], [MoO(O2)(dha‐inh)
(E)‐1‐CoS and (Z)‐1‐CoS in toluene were 3.3 × 10−2 and (MeOH)], [MoO(O2)(dha‐nah)(MeOH)] and [MoO(O2)
4.8 × 10−3 mmHg−1, respectively, at 283 K. Although the (dha‐fah)(MeOH)], with ONO tridentate Schiff base ligands
pKa values of the E and Z forms of the stilbazole residue were derived from 3‐acetyl‐6‐methyl‐(2H)‐pyran‐2,4‐(3H)‐dione
quite similar to each other, the oxygen‐binding affinity of (dehydrocetic acid, Hdha) and aromatic hydrazides (benzoyl
(Z)‐1‐CoS was small in terms of the liner correlation of ln hydrazide (bhz), isonicotinoyl hydrazide (inh), nicotinoyl
K versus pKa.[7] hydrazide (nah) and furoyl hydrazide (fah)) have been pre-
pared, and then analyzed by elemental analysis, infrared,
UV–visible, [1]H NMR and 13C NMR spectroscopies and
3 | S C H I F F BAS E C O M P L E X E S A S thermogravimetric analyses. The dioxidomolybdenum(VI)
CATALYSTS complexes have been studied as catalysts for the homoge-
neous oxidation of secondary alcohols (1‐phenylethanol,
A number of Schiff base complexes of metal ions with high 2‐propanol and 2‐butanol; Scheme 1), using 30% H2O2 as
catalytic activity play a significant role in enhancing yield an oxidant. Both microwave and liquid‐phase oxidation
and product selectivity. In organic synthesis, the convenient methods have been tested for catalytic reactions. Also, the
route of synthesis and thermal stability of Schiff base ligands various parameters of the reaction, such as amount of
have contributed significantly to their possible applications in catalyst, oxidant, solvent and temperature, have been taken
catalysis as metal complexes.[8] At present, Schiff base into consideration for the maximum conversion of substrates.
complexes have emerged for the development of a variety Under the optimized reaction conditions, secondary alcohols
of efficient catalysts.[9,10] To enable the separation of the gave high yields of the respective ketones. Addition of
AL ZOUBI AND KO 3

A new bidentate ON Schiff base ligand (HL) was pre-

pared by simple condensation reaction of isopropylamine
and salicylaldehyde in methanol or chloroform as solvent at
ambient temperature. Then, by reaction of HL and VO
(acac)2 in a ratio of 2:1 in the presence of triethylamine at
room temperature, a new oxovanadium(IV) Schiff base
complex, VOL2, was prepared. The catalytic performance of
the VOL2 complex was tested in the selective oxidation of
SCHEME 1 Oxidation of alcohols and sulfides into corresponding alde-
hydes and sulfoxides thioanisole with the green oxidant H2O2 (35% aqueous)
under solvent‐free conditions and with organic solvent
N‐based additive reduced the reaction time and increased the (EtOH, CHCl3, CH2Cl2, DMF, CH3CN, EtOAc) as model
conversion of alcohol.[17] reaction. Owing to the excellent catalytic performance of
Amiri et al.[18] have reported the preparation of four the VOL2 complex (Figure 3) under solvent‐free conditions,
Schiff base complexes, CoL(NO3)2, NiLCl2, ZnL(NO3)2 this complex was used for the oxidation of various sulfides
and Pd2LCl4, by direct reaction of the ligand (L) to the corresponding sulfones under solvent‐free conditions.
which were prepared by the condensation reaction of The use of H2O2 as oxidant and the absence of solvent made
1,2‐bis(2′‐aminophenoxy) with 2‐pyridinecarbaldehyde these reactions interesting from environmental and economic
(1:2) and appropriate metal salts. The prepared complexes points of view. The amounts of H2O2 played an important
had very poor solubility in all polar and non‐polar role in leading to the selective oxidation of thioanisole into
solvents, such as H2O, MeOH, EtOH, CH3CN, the corresponding sulfone. Also, different sulfides, such as
dimethylsulfoxide, DMF, CHCl3, CH2Cl3, CH2Cl2 and tetra- phenylalkyl sulfides, dialkyl sulfides and unsaturated
hydrofuran. They have been used as heterogeneous catalysts. sulfides, were converted into the corresponding sulfones in
Hence, catalytic performances of the complexes were tested the presence of VOL2 as catalyst. Sulfide with C═C double
in the oxidation of thioanisole using H2O2 as oxidant. The bond was selectively oxidized into its corresponding sulfone
palladium Schiff base complex, Pd2LCl4, showed better without affecting reactive functional groups.[20]
catalytic activity than the other complexes. Therefore, the Pd Khorshidifard et al.[21] have reported the preparation an
(II) Schiff base complex has been used as a catalyst for the asymmetric bidentate Schiff base ligand (HL; 2‐tert‐
oxidation of various sulfides to their corresponding sulfones butyliminomethylphenol) from the reaction of salicylaldehyde
in acetonitrile with H2O2 as oxidant. and tert‐butylamine in absolute methanol as solvent at ambient
An efficient asymmetric oxidation of prochiral sulfides temperature. Co(II), Cu(II), Zn(II) and Pd(II) complexes,
catalyzed by a series of in situ complexes based on chiral CoL2, CuL2, ZnL2 and PdL2, were synthesized from the
Schiff base ligands (Scheme 2) with Ti(OiPr)4 (0.013 mmol) reaction of CoCl2⋅6H2O, CuCl2⋅2H2O, Zn(NO3)2⋅6H2O and
was carried out with H2O2 (30% aqueous) as oxidant in PdCl2 with ligand HL in methanol. The catalytic activity of
dichloromethane at 273 K. Prochiral sulfides were converted these complexes has been evaluated for the selective oxidation
to respective chiral sulfoxides efficiently with good conver- of sulfides with the green oxidant H2O2 (35% aqueous) under
sion of 93% in 10 h. It was found that the solvent played a solvent‐free conditions. For all the catalysts, using optimized
crucial role, and a slight change in the steric or electronic reaction conditions, various sulfides (Figure 4) were converted
environment of the catalyst greatly influenced the outcome to the corresponding sulfones. ZnL2 showed a higher catalytic
of the reaction, behaving like a completely different catalyst. performance for the green oxidation of the sulfides to the
Also demonstrated was a significant steric influence of the
substituent attached on both aryl and alkyl moieties on the
enantioselectivity. Kinetic studies of the catalytic reaction
showed first‐order dependence on substrate and catalyst
whereas it was zero‐order for the oxidant. Kinetic studies in
combination with UV–visible spectral studies were used to
propose a catalytic cycle for the sulfoxidation reaction.[19]
FIGURE 3 Oxidation of sulfides to corresponding sulfones under solvent‐
free conditions

SCHEME 2 Catalytic asymmetric oxidation of methyl phenyl sulfide using FIGURE 4 Oxidation of sulfides to corresponding sulfones under solvent‐
chiral Schiff base ligands with Ti(Oi‐Pr)4 free conditions
4 AL ZOUBI AND KO

corresponding sulfones. Also, the amount of catalyst had a consecutive runs without significant loss of its catalytic
considerable effect on the conversion of thioanisole to the efficiency.[23]
corresponding sulfone. Hence, the role of the catalyst was very Complexes of transition metals (M = Fe(II), VO(IV))
important in the reaction because this reaction has low conver- with Schiff base ligands that were synthesized by simple
sion without any catalyst. condensation of 2‐hydroxyacetophenone and/or 2‐hydroxy‐
Novel heterogeneous catalysts of Schiff base complexes 5‐chloroacetophenone with ethylenediamine have been
of transition metal ions supported on silica‐coated magnetic entrapped within nanopores of zeolite‐Y using a flexible
cobalt nanoparticles were successfully synthesized. The cata- ligand method. These synthesized catalysts have been utilized
lytic activity of the catalysts was studied in the oxidation of as heterogeneous catalysts for liquid‐phase oxidation of
various aromatic alcohols (Scheme 3) with environmentally cyclohexene. Therefore, the reaction parameters have been
friendly oxidant using different solvents and under solvent‐ tuned to optimize higher cyclohexene conversion along with
free conditions. Also, the effects of parameters such as sol- higher selectivity towards the formation of corresponding
vent, amount of oxidant and catalyst, reaction temperature allylic products (Figure 5). These catalysts were recovered
and utilization efficiency of hydrogen peroxide were investi- and reused three times without marked loss of activity. More-
gated. The synthesized catalysts acted selectively and over, the intermediate species involved during the catalytic
converted the alcohols to corresponding aldehydes with high oxidation reaction was synthesized and identified by Fourier
yield. The results showed outstanding catalytic performance transform infrared (FT‐IR) and UV–visible spectroscopy.[24]
with selective conversion of alcohols at 50°C with and A new Schiff base Mn(II) complex was successfully
without solvent. This high activity and selectivity was most synthesized and covalently immobilized on silica‐coated
probably related to the Lewis acidity of the catalysts.[22] magnetic cobalt nanoparticles as a support. The prepared
In recent works, oxidation of sulfides to sulfoxides and heterogeneous catalyst showed a high catalytic activity in
oxidative coupling of thiols into their corresponding the oxidation of alcohols (benzyl alcohol was used as a
disulfides (Scheme 4) were carried out using hydrogen sample) with high yield and under mild conditions. The
peroxide as oxidizing agent in the presence of Ni, Co, Cr, reaction progress was monitored by TLC. The synthesized
Zn or Cd complexes immobilized on Fe3O4 magnetic hybrid nanomaterials were fully characterized by FT‐IR
nanoparticles (M‐Salen‐MNPs) as stable, heterogeneous, spectroscopy, X‐ray diffraction and energy‐dispersive X‐ray
efficient and magnetically recoverable nanocatalysts under analysis. The morphology of the nanonmaterial was deter-
mild reaction conditions. Also, a variety of aromatic and mined by scanning and transmission electron microscopies.
aliphatic sulfides and thiols with various functional groups Moreover, the synthesized catalyst showed a high catalytic
were successfully oxidized with short reaction times in good activity in the oxidation of alcohols and sulfides to the
to excellent yields. Recovery of the catalyst is easily achieved corresponding aldehydes and sulfoxides (Scheme 5). The
by magnetic decantation and it can be reused for several oxidation reaction was carried in the absence of the catalyst
and it was found that the reaction yield was only 4%, which
confirms the importance of the catalyst for reaction
completion (Table 1).[25]
In previous work, 12 bi−/tridentate Schiff base ligands
were designed, prepared and coordinated with ion‐exchanged
Co–MOR (mordenite) forming a series of Co–MOR(L)
composite catalysts, for which various analyses and

SCHEME 3 The catalytic activity in oxidation of various aromatic alcohols

with environmentally friendly oxidant under different solvents and solvent
free conditions

SCHEME 4 Oxidation of sulfides to sulfoxides and oxidative coupling

thiols into their corresponding disulfides by using hydrogen peroxide and
Ni, Co, Cr, Zn or Cd complexes on Fe3O4 magnetic nanoparticles
(M‐Salen‐MNPs) as stable FIGURE 5 Oxidation of cyclohexene to corresponding allylic products
AL ZOUBI AND KO 5

FIGURE 6 Epoxidation of alkene to corresponding allylic products

SCHEME 5 Oxidation of sulfides and alcohols into the corresponding (SAP) backbone with OH substituents on the salicyl arene
aldehydes and sulfoxides
ring. All dimeric complexes [MoO2L]2 were studied for the
epoxidation of cyclooctene and cyclohexene under organic
characterizations were conducted. Selective catalytic epoxi- solvent‐free conditions using aqueous TBHP as oxidant
dation (Figure 6) of α‐pinene in DMF at 90°C with dry air (Figure 7(b)). The effect of OH substituents at different
over Co–MOR(L) catalysts has been carried out, where tert‐ positions of the salicyl ring of the Schiff bases has been
butyl hydroperoxide (TBHP) was used in small amounts as evaluated and studied for the epoxidation of cyclooctene
the initiator (one‐tenth of the added olefin). Among these and cyclohexene using aqueous TBHP catalyzed by dimeric
Co–MOR(L) catalysts, Co–MOR(L8) (R1 = OH, R2 = H) Mo(II) complexes [MoO2L]2. The position of the OH
exhibits the best activity leading to 85.8% conversion substituent at the ortho and para positions of the salicyl
and 90.8% selectivity of epoxide. Some factors such as ring and the nature of the substrate had a slight influence
the structure of ligands, oxidants, solvents, amount of on the catalytic activity. Moreover, density functional
catalyst and reaction temperature and time play important theory calculations for the catalytic cycle yield energy spans
roles in controlling the epoxidation. Studies of the elec- in agreement with the experimentally observed activity
trochemical behaviors of Co species in Co–MOR(L) trend.
revealed the importance of reversible change between Romanowskiron and Kira[28] have reported the prepara-
Co oxidation states for the epoxidation of α‐pinene with tion a series of vanadium(V) complexes with chiral tridentate
air.[26] Schiff base ligands, obtained by the single condensation of
Wang et al.[27] have reported the synthesis and character- R‐(−)‐phenylglycinol with salicylaldehyde and its deriva-
ization of Mo(II) complexes with ONO tridentate Schiff base tives. The vanadium(V) complexes have the ability to cata-
ligands (Figure 7(a)) based on salicylideneaminophenolato lyze the oxidation of sulfides (PhSR; R = Me, Bz) in

TABLE 1 The optimized amounts of the catalyst and oxidant in oxidation reactiona
Entry Co@SiO2@[Mn(III)SB] (g) H2O2 (30%): μl, mmol Product Selectivity Isolated Yield (%)
Initial test
1 0.02 30, 0.293 Benzaldehyde 100 32
Experiments to obtain optimized conditions
2 0.02 40, 0.391 Benzaldehyde 100 44
3 0.02 50, 0.489 Benzaldehyde 100 51
4 0.02 60, 0.587 Benzaldehyde 100 63
5 0.03 60, 0.587 Benzaldehyde 100 72
6 0.03 70, 0.685 Benzaldehyde 100 81
7 0.03 80, 0.783 Benzaldehyde 100 89
8 0.03 90, 0.881 Benzaldehyde 100 92
9 0.03 100, 0.979 Benzaldehyde 100 94
10 Not used 90, 0.881 Benzaldehyde 100 4
Amount of metal loaded on magnetic support and calculation of TON and TOF numbers
Entry Catalyst Amount of metal loaded (wt%) TONb TOF (h−1)
11 Co@SiO2@Mn(III)SBC 7.19 95 87
a
Reaction conditions: benzyl alcohol (0.6 mmol), 45°C, solvent: ethyl acetate (3 ml).
b
Moles of substrate converted per moles of metal in the catalyst ([substrate]/[metal] × 100).
6 AL ZOUBI AND KO

FIGURE 9 Various oxidation products of styrene catalyzed by

oxidovandium(V) complexes

FIGURE 10 Oxidation of sulfides catalyzed by [MoO(O2)L(CH3OH)]

oxidation reactions giving high yield, turnover number

(TON; mmol of product/mmol of catalyst) and selectivity.[29]
Aiping et al.[30] have reported the preparation of a catalyst
system of VO(acac)2 and Schiff base ligands derived from
3,5‐dibromosalicylaldehyde or 3,5‐diiodosalicylaldehyde
FIGURE 7 (a) Access routes to H2L pro‐ligands and molybdenum com- and inexpensive chiral amino alcohols (Figure 11). This
plexes. (b) Epoxidation of cyclohexene
catalyst leads to good yield and moderate to high
enantioselectivity for the asymmetric oxidation of arylmethyl
excellent yields and enantiomeric excesses (over 90%) sig-
sulfides at room temperature when 1% catalyst (VO(acac)2‐to‐
nificantly depending on the nature of the catalyst, utilizing
ligand molar ratio of 1:2) and H2O2 oxidant were used. Also,
aqueous 30% H2O2 or α,α‐dimethylbenzyl hydroperoxide
the catalytic oxidation reaction of methyl‐p‐bromophenyl
as the oxidant (Figure 8). These complexes were also catalyt-
sulfide using VO(acac)2 and L3 (R = i‐Pr, X = Br) or L4
ically active in the oxidation of styrene (Figure 9), using
(R = i‐Pr, X = I) provides high yields (80–82%) and marked
aqueous 30% H2O2 or TBHP as the oxidant, to styrene
enantioselectivity (89–92%), whereas the electron‐deficient
oxide, benzaldehyde, benzoic acid, phenylacetaldehyde and
sulfide bearing a nitro group on the para position of the aryl
1‐phenylethane‐1,2‐diol.
A new oxido–peroxido molybdenum(VI) complex
[MoO(O2)L(CH3OH)] (Figure 10) was synthesized, using
salicylidene benzoyl hydrazine as tridentate ONO donor
Schiff base ligand (H2L). This complex functions as a facile
olefin epoxidation catalyst with H2O2 as terminal oxidant
and sodium hydrogen carbonate (NaHCO3) as co‐catalyst at
room temperature. When H2O2 was used as a sole oxidant
the catalytic efficiency was not high (Figure 10), but when
NaHCO3 was added the efficiency of the system increased
many fold. The catalyst showed very high efficiency in the

FIGURE 8 Sulfoxidation of thioethers catalyzed by oxidovanadium(V)

complexes FIGURE 11 Asymmetric oxidation of aromatic sulfides
AL ZOUBI AND KO 7

group results in moderate yields (51–60%) and relatively low

enantioselectivity (24–32%). As the nitro group is replaced by
a methoxy group in the ring, the values increase to 69–70%.
The ligands derived from (S)‐valinol exhibit considerably
higher enantioselectivity than those derived from
(S)‐phenylalaninol and (R)‐leucinol. The enantiomeric excess
values were improved up to 88% for methylphenyl sulfoxide
and 92% for methyl‐p‐bromophenyl sulfoxide by slow
dropwise addition of H2O2 with the ligand prepared from
3,5‐diiodosalicylaldehyde and (S)‐valinol. The catalytic
efficiency of VO(acac)2/Schiff base systems cannot be
improved by the addition of carboxylic acids or carboxylate
salts (5%).
The catalytic activity of new binuclear cobalt com-
plexes with Schiff base ligand and amino acid (Figure 12)
was investigated in the reaction of partial cyclohexane
oxidation with air and high activity and selectivity for
FIGURE 13 Aerobic oxidation of amines
cyclohexanol and cyclohexanone formation were demon-
strated. The possibility of complex reuse in cyclohexane
oxidation was studied, and it was shown that the activity complex catalyst, CPS‐[MoO2(ALCL)2], has very high cata-
slightly decreases in a second oxidation cycle along with lytic activity. Under mild conditions such as at ordinary pres-
changes in main product distribution due to partial transfer sure of dioxygen at a lower temperature of 90°C, benzyl
of Co(III) to Co(II).[31] alcohol could be transformed to benzaldehyde with a conver-
Amino acid D,L‐threonine‐derived ionic liquid was sation of 63% in 10 h. It was found that CPS‐[MoO2(ALGL)2]
treated with salicylaldehyde to give corresponding Schiff has excellent catalytic selectivity, and it specially catalyzes
base which subsequently was complexed with Fe(III) and the oxidation reaction of benzyl alcohol to benzaldehyde.
used as a green catalyst for aerobic oxidation of amines Also, it was found that the solvent polarity greatly affects
under solvent‐less conditions. An efficient, green and the catalyst activity. The catalytic activity of the Schiff com-
reusable amino acid‐derived ionic liquid‐supported Schiff plex may be attributed to easier formation of Mo alkoxide
base was developed for aerobic oxidation of various species between substrate benzyl alcohol and Mo atom of
benzylamines, aliphatic amines and secondary amines to the complex that acts as a Lewis acid site, and a plausible
the corresponding nitriles and imines (Figure 13), with reaction mechanism is proposed as follows: (1) in the
1 atm of dioxygen.[32]
Gao et al. investigated the oxidation reaction of benzyl
alcohol using molecular oxygen. In the oxidation reaction
of benzyl alcohol, a heterogeneous dioxomolybdenum(VI)

FIGURE 12 Synthesis of complex from 5‐chloro‐2‐hydroxy‐3‐ FIGURE 14 Catalytic mechanism of CPS‐[MoO2(ALGL)2] catalyst in oxi-
nitrobenzaldehyde, L‐valine and cobalt(II) acetate tetrahydrate dation of benzyl alcohol to benzaldehyde using molecular oxygen
8 AL ZOUBI AND KO

presence of dioxomolybdenum(VI) complex (Figure 14), had a marked effect on the oxidation reaction, while acetoni-
molecular oxygen decomposes, and one oxygen atom com- trile was the best among the solvents.
bines with one oxygen atom around the Mo atom to form a Judy‐Azar and Mohebbi[35] have reported the synthesis of
peroxy radical; (2) the hydrogen atom of the hydroxyl group novel heterogeneous catalysts of Schiff base complexes of
of benzyl alcohol transfers onto the peroxy radical, and at the transition metal ions supported on silica‐coated magnetic
same time, alkoxide anion forms and it coordinates to Mo metallic cobalt nanoparticles. The catalytic activity of the cat-
atom; (3) the activated oxygen atom attacks alkoxides coordi- alysts was studied in the oxidation of various aromatic alco-
nated to the Mo atom to form carbonyl compound benzalde- hols (Figure 16) with an environmentally friendly oxidant
hyde and water by dehydrogenation; (4) dioxomolybdenum and with various solvents and under solvent‐free conditions.
(VI) complex returns to its original structure and a new cata- Also, the effects of parameters such as solvent, amount of
lytic cycle resumes.[33] oxidant and catalyst, reaction temperature and utilization
Gogoi et al.[34] have described a straightforward, efficient efficiency of hydrogen peroxide were investigated. The syn-
and selective oxidation of sulfide to sulfoxide with 30% H2O2 thesized catalysts acted selectively and converted the alcohols
catalyzed by copper (II)–Schiff base complex (Figure 15). to corresponding aldehydes with high yield.
The reaction was carried out under mild conditions in aceto- Sulfoxidation catalysts generated in situ from titanium
nitrile at room temperature to provide a variety of aryl and (IV) isopropoxide and enantiopure Schiff bases promote the
alkyl sulfoxides in excellent yield. The authors indicated that enantioselective oxidation of alkylaryl sulfides to the corre-
complex 1 is an efficient catalyst for the oxidation of both sponding sulfoxides (Figure 17) at low catalyst loadings (less
aryl and alkyl sulfides to the corresponding sulfoxides with than 1 mol%), with over 90% chemoselectivity and 60%
hydrogen peroxide. However, use of more than 0.5 mol% cat- yield. The optimized catalytic conditions were formulated
alyst 1 did not enhance the yield (Table 2). Using 0.5 mol% based on the examination of ligand interaction with tita-
copper(II)catalyst 1, a chemoselectivity of 95:5 could be nium(IV) isopropoxide and following the oxidation kinetics
achieved in 6 h. A catalyst loading of 0.5 mol% gave a higher using NMR spectroscopy. In that work, a chiral Schiff base
catalytic efficiency due to the short reaction time. Also,
catalyst 1 was found to be the most effective and the product
3b (Figure 15) was obtained in 95% yield. Dichloromethane

FIGURE 16 Process of alcohol oxidation catalyzed by magnetic Schiff base

complexes

FIGURE 15 Copper(II) Schiff base complex‐catalyzed oxidation of 2‐ FIGURE 17 Titanium‐catalyzed asymmetric oxidation of sulfides to
nitrophenylbenzyl sulfide with hydrogen peroxide sulfoxides

TABLE 2 Oxidation of 2‐nitrophenylbenzyl sulfide using 30% aqueous H2O2 catalyzed by 1a

Entry Catalyst (mol%) Solvent Time (h) Sulfoxide yield (%)b Sulfone yield (%)b
1 1(0.5) CH3CN 6 95 5
2 1(0.05) CH3CN 10 68 10
3 1(1.0) CH3CN 6 90 8
4 1(0.5) CH3COCH3 6 70 10
5 1(0.5) CH2Cl2 8 90 8
6 1(0.5) CH3OH 8 84 7
7 CuCl2(0.5) CH3CN 8 70 12
8 Cu(C5H7O2)2(1.0) CH3CN 7 75 10
9 [CoL]H2O (0.5) CH3CN 8 78 18
10 [NiL]H2O (0.5) CH3CN 8 57 15
a
Reaction condition: substrate (2 mmol), complex 1 (0.5 mol%), 30% H2O2 (5 mmol) stirred at room temperature in solvent (2 ml).
b
Isolated yield.
AL ZOUBI AND KO 9

ligand derived from 1‐amino‐2‐indanol was tested and (hap‐SBDTC)(solv)] (1b) and cis‐[MoO2(hap‐SMDTC)
displayed moderate activity.[36] (solv)] (2b), where hap‐SBDTC and hap‐SMDTC are Schiff
Menati et al.[37] have reported the synthesis of a new bases derived from o‐hydroxyacetophenone (hap) and
Schiff base ligand from the condensation reaction of 1,2‐bis S‐benzyldithiocarbazate (SBDTC) or S‐methyldithiocarbazate
(2′‐aminophenoxy)benzene with 2‐pyridinecarbaldehyde in (SMDTC), respectively. The catalytic tests were carried out in
a mole ratio of 1:2. Schiff base complexes were prepared by DMF solvent at 60°C under 1 atm O2. The final oxidation
reaction of the ligand and metal ions. The synthesized com- products were found to be 1‐hexanal for 1‐hexene, styrene
plexes were used as heterogeneous catalysts. Performance of epoxide and phenylacetaldehyde (81:19) for styrene and
the complexes was studied in the oxidation of thioanisole cyclohexene epoxide and 2‐cyclohexen‐1‐ol (85:15) for
(Figure 18) using H2O2 as the oxidant. The Schiff base com- cyclohexene (Figure 20).[39]
plexes allow the selective oxidation of sulfides to sulfones. Kumar and Mathur[40] have reported using a Cu(II) com-
The selective oxidation of sulfides to sulfones with Schiff base plex with a new N‐substituted benzimidazolyl Schiff base
complexes as catalysts is very rare. Also, the amount of com- ligand as catalyst for oxidation of 1‐phenylpropyne. The oxi-
plex had a considerable effect on the conversion of sulfides to dation was carried out under mild conditions using stoichio-
the corresponding sulfones. The maximum conversion for the metric amounts of oxidant and catalytic amounts of Cu(II)
reaction was observed with 5 mg of catalyst for all four com- complex as catalyst. Also, the effect of acid/base and oxidant
plexes, but there was no major difference in the conversion was studied. The three complexes were efficient catalysts for
when 10 and 20 mg of catalyst were used. Therefore, 5 mg the oxidation of 1‐phenylpropyne. In the case of
of catalyst was taken as the optimum amount. 1‐phenylpropyne (Figure 21) three diverse products are
Schiff base complexes of oxovanadium(IV), whose formed: diketone, aldehyde and acid. Diketone is the major
ligands have amino acid side chains with coordinating func- product under acidic conditions while aldehyde formation is
tional groups (Figure 19), retained their coordination geome- highest under basic conditions. Formation of diketone sug-
tries in which the amino acid side chains were probably gests complete oxidation of the triple bond, while formation
coordinated in the axial position with a phenolate oxygen, a of benzoic acid suggests the cleavage of the alkynes. How-
carboxylate oxygen, an imine nitrogen and a solvent mole- ever, the maximum conversion is found with the NO3− bound
cule being bound in the equatorial plane. Peroxo complexes complex.
prepared from the Schiff base complexes of oxovanadium Zhu at al.[41] have reported the synthesis and characteri-
(V) converted methylphenyl sulfide to the corresponding zation of several chiral copper(II) complexes of optically
sulfoxide in 80–90% yield in CDCl3 and in 30–70% yield active Schiff bases (R,R)‐4a‐c, which have central seven‐
in CD3OD in 30 min. They converted the sulfide in a membered chelate rings. The complexes have been tested as
stereoselective manner yielding the sulfoxide in small enan- catalysts for asymmetric oxidation of methylphenyl sulfide
tiomeric excess (5–20%). The penta‐coordinate square‐pyra- (Figure 22). The mechanism of the catalytic reaction in the
midal complexes of oxovanadium(V) afforded slightly presence of these complexes has been tentatively elucidated.
higher rates of oxidation of the sulfide than the hexa‐coordi-
nate octahedral complexes in CD3OD.[38]
The homogeneous catalytic air oxidation of 1‐hexene,
cyclohexene and styrene has been reported using cis‐[MoO2

FIGURE 18 Oxidation of thioanisole with hydrogen peroxide in the

presence of CoL(NO3)2, NiLCl2, ZnL(NO3)2 and Pd2LCL4 Schiff base
complexes as catalysts

FIGURE 20 Epoxidation of hexane, cyclohexene and styrene using com-

plexes cis‐[MoO2(hap‐SBDTC)] (1b) and cis‐[MoO2(hap‐SMDTC)] (2b)

FIGURE 19 Schiff base ligands prepared with amino acids and amino acid FIGURE 21 Process of 1‐phenylpropyne oxidation catalyzed by magnetic
esters Schiff base complexes
10 AL ZOUBI AND KO

epoxidation of alkenes was achieved using compound 1 as a

catalyst.[44]
A series of V(V) complexes were prepared with chiral
tridentate Schiff base ligands, obtained by a single condensa-
tion of R‐(−)‐1‐amino‐2‐propanol with salicylaldehyde and
its derivatives. These complexes have the ability to catalyze
the oxidation of sulfides (PhSR; R = Me, Bz) in good yields
and enantiomeric excesses, utilizing aqueous 30% H2O2 or
cumene hydroperoxide (CHP) as oxidant (Figure 24(b)).
Catalytic activity of these complexes and also those derived
from R‐(−)‐1,2‐diaminopropane, resulting in ONO‐ and
ONN‐type tridentate ligands, respectively, was tested in the
oxidation of styrene, using aqueous 30% H2O2 or TBHP as
oxidant. In addition (Figure 24(a)), to test the catalytic
potential of the prepared V(V) complexes in the oxidation
of olefins, the oxidation of styrene was chosen as a model
reaction. These complexes were able to catalyze the oxidative
conversion of styrene, with 30% H2O2 or TBHP as oxidant,
to styrene oxide and successive products derived from
styrene oxide, but according to our studies, no clear trend
FIGURE 22 Asymmetric oxidation of methylphenyl sulfide of different catalytic reactivity was found upon the change
of substituent in the salicylidene part of the Schiff base
The mechanism of the asymmetric oxidation of sulfide cata- ligand. The oxidation of styrene after 6 h of reaction time
lyzed by a Cu(II) complex with Schiff base ligands is still gives at least five different products. Using 30% H2O2 as
unclear at present. Recently Decinti and co‐workers have pro- oxidant, conversion of styrene was distinctly low, but due to
posed that the mechanism of styrene epoxidation with the strong oxidizing nature of H2O2 the formation of benzal-
iodosylbenzene in the presence of copper(II) Schiff base dehyde was preferred, whereas expected product styrene
complexes involves the formation of Cu(II)–iodosylbenzene oxide was found only in small yield. The presence of a large
adducts as intermediates.[42] amount of water in the reaction mixture may be responsible
Nayak et al.[43] have reported the synthesis of four coordi- for the lowering of the conversion. On the other hand, TBHP
nation compounds in high yields from various transition
metal ions (Fe(III), Co(II) and Cu(II)) and in situ generated
Schiff base ligand, i.e. 2‐methoxy‐6‐((quinolin‐8‐ylimino)
methyl)phenol (MQMPH) (Figure 23). Besides the synthesis,
the Fe(III) complex (1) was an efficient catalyst for the oxida-
tion of alkanes and alkenes, under aerobic conditions with the
temperature being maintained at 50°C (temperature at which
the catalyst efficiency is optimal, compared to 40 and 60°C)
and H2O2 as terminal oxidant. The complex was found to
be an efficient oxidation catalyst for the activation of C─H
bond. The catalytic efficiency of 1 was examined using
cyclohexane, n‐heptane, cyclohexene and cis‐cyclooctene as
substrates. The corresponding alcohols and ketones were
the major oxidation products. However, in the case of
cis‐cyclooctene oxidation, a high selectivity was found for
the epoxide formation. Also, a good selectivity towards the

FIGURE 23 Schiff base ligand (MQMPH), with a NNO donor set, used for FIGURE 24 Sulfoxidation of thiothers catalyzed by vanadium (V)
preparation of coordination compounds Complexes
AL ZOUBI AND KO 11

supports was one of the desirable strategies for facilitating

catalyst separation and recycling.
The topics reviewed in this study are industrially promis-
ing in the fields of catalysis with multi‐ and interdisciplinary
approaches. Although the developments of interest have been
made in oxidation catalysis using Schiff base complexes as
discussed herein, it is necessary to address further the devel-
FIGURE 25 Complexes of chiral and achiral tetradentate Schiff bases with
Cu(II), Ni(II) and VO2(II)
opment of green processes. Consequently, the use of H2O2 as
a mild oxidant in the presence of the synthesized catalysts
would provide an efficient, easy and safe approach, leading
to oxidations of alcohols to corresponding compounds. The
heterogeneous catalysts would cause organic reactions with
a Lewis acid. Thus, green (using H2O2), simple, clean and
economical procedures for oxidation of various organic
compounds is recommended.

REFERENCES
[1] W. Al Zoubi, N. Al Mohanna, Spectrochim. Acta 2014, 132, 854.
[2] W. Al Zoubi, F. Kandil, M. Khaled Chebani, Arab. J. Chem. 2016, 9, 526.
FIGURE 26 Asymmetric bifunctional (salen) CoX complexes [3] W. Al Zoubi, F. Kandil, K. Chebani, Phys. Sci. Int. 2014, 2, 12.
[4] W. Al Zoubi, F. Kandil, M. Khaled Chebani, Sep. Sci. Technol. 2012,
proved to be an excellent oxidant giving even 99.2% conver- 47, 1754.
sion of styrene with benzaldehyde as the main product.[45] [5] S. Park, V. K. Mathur, R. P. Planalp, Polyhedron 1998, 17, 325.
Bunce et al.[46] have reported the synthesis and character- [6] A. A. Emara, A. M. Ali, A. F. El‐Asmy, E. S. M. Ragab, J. Chem. Soc. 2014,
ization of several new complexes of chiral and achiral 18, 762.
tetradentate Schiff bases (Figure 25) with Cu(II), Ni(II) and [7] T. Suzuki, Y. Suzuki, N. Oda, J. Ohkubo, H. Shinozaki, J. Phys. Chem. B
VO2(II) ions. The copper, nickel and vanadyl complexes were 2007, 111, 8823.
screened as homogeneous catalysts for the oxidation, using [8] K. C. Gupta, A. K. Sutar, Coord. Chem. Rev. 2008, 252, 1420.
TBHP or H2O2, of PhMeS to PhMeSO. [9] S. M. Sadeghzadeh, F. Daneshfar, M. Malekzadeh, Chin. J. Chem. 2014,
32, 349.
Tian et al.[47] have reported the synthesis of aluminium
[10] A. Ghorbani‐Choghamarani, G. Azadi, RSC Adv. 2015, 5, 9752.
salen complexes (Figure 26) bearing appended quaternary
ammonium salt substituents and showed them to be effective [11] B. Atashkar, A. Rostami, B. Tahmasbi, Catal. Sci. Lett. 2013, 3, 2140.

catalysts for the coupling of epoxides and carbon dioxide to [12] Z. Abbasi, M. Behzad, A. Ghaffari, H. Amiri, Inorg. Chim. Acta 2014,
414, 78.
generate cyclic carbonates. The onium salt group tethered
[13] F. Dehghani, A. R. Sardarian, M. Esmaeilpour, J. Organometal. Chem. 2013,
on the salen ligand was found to play an important role in 743, 87.
enhancing the catalytic activity. The effects of reaction [14] V. Ayala, A. Corma, M. Iglesias, F. Sanchez, J. Mol. Catal. A 2004, 221, 201.
variables such as temperature, time, pressure and molar ratio [15] V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J. M. Basset,
of epoxide to catalyst on the catalytic performance were Chem. Rev. 2011, 111, 3036.
systematically investigated. These bifunctional catalysts were [16] A. Ghorbani‐Choghamarani, Z. Darvishnejad, M. Norouzi, Appl.
found to be highly stable to moisture and oxygen, resistant to Organometal. Chem. 2015, 29, 170.
impurities, and recyclable with only minor losses in catalytic [17] M. R. Maurya, N. Saini, F. Avecilla, Polyhedron 2015, 90, 221.
activity.[48,49] [18] H. Amiri Rudbari, M. Riahi Farsani, S. Lanza, G. Bruno, B. Yadollahi, C. R.
Chim. 2015, 18, 391.
[19] P. K. Bera, D. Ghosh, S. H. R. Abodi, N. H. Khan, R. I. Kureshy, H. C. Bajaj,
4 | C O NC LUS I O N S J. Mol. Catal. A 2012, 361–362, 36.
[20] S. Menati, H. A. Rudbari, M. Korshidifard, F. Jalilian, J. Mol. Struct. 2016,
Schiff bases are known as an important class of organic 1103, 94.

compounds because of their capacities to bind metal ions [21] M. Khorshidifard, H. A. Rudbari, B. Askari, M. Sahihi, M. Riahi Farsani,
F. Jalilian, G. Bruno, Polyhedron 2015, 95, 1.
from environmental media as well as being efficient catalysts
[22] A. R. Judy Azar, S. Mohebbi, J. Mol. Catal. A 2015, 397, 158.
for oxidation of alkanes and alcohols, epoxidation of alkenes
[23] D. R. Godhani, H. D. Nakum, D. K. Parmar, J. P. Mehta, N. C. Desai, J. Mol.
and sulfoxidation of organic compounds in the presence of
Catal. A 2016, 415, 37.
suitable oxidants, e.g. alkyl hydroperoxides, H2O2 or O2,
[24] D. R. Godhani, H. D. Nakum, D. K. Parmar, J. P. Mehta, N. C. Desai, J. Mol.
under mild conditions. The results reviewed here showed that Catal. A 2016, 1, 37.
Schiff bases and their complexes exhibit efficient catalytic [25] A. R. Judy Azar, E. Safaei, S. Mohebbi, Mater. Res. Bull. 2015, 70, 753.
activity towards the selective epoxidation of simple alkenes, [26] X. H. Lu, J. Lei, X. L. Wei, X. T. Ma, T. J. Zhang, W. Hu, D. Zhou, Q. H. Xia,
and primary and secondary alcohols. Immobilization on solid J. Mol. Catal. A 2015, 400, 71.
12 AL ZOUBI AND KO

[27] W. Wang, J. C. Daran, R. Rinaldo, D. A. Poli, J. Mol. Catal. A 2016, 416, 117. [41] H. B. Zhu, Z. Y. Dai, W. Huang, K. Cui, S. H. Gou, G. J. Zhu, Polyhedron
[28] C. Romanowskiron, J. Kira, Polyhedron 2013, 53, 172. 2004, 23, 1131.

[29] M. Bagherzdeh, M. Amini, H. Parastar, M. Jalali‐Herzvi, A. Ellern, L. K. Woo, [42] S. Zolezzi, E. Spodine, A. Decinti, Polyhedron 2003, 22, 1653.
Inorg. Chem. Commun. 2012, 20, 86. [43] S. Nayak, P. Gamez, B. Kozlevčar, A. Pevec, O. Roubeau, S. Dehnen,
[30] G. Aiping, W. Mei, W. Dongping, Z. Lu, L. Haibin, T. Wei, S. Licheng, J. Reedijk, Polyhedron 2010, 29, 2291.
Chinese J. Catal. 2006, 2, 743. [44] G. Romanowski, J. Kira, M. Wera, Polyhedron 2014, 67, 529.
[31] L. I. Rodionova, A. V. Smirnov, N. E. Borisova, V. N. Khrustalev, [45] G. Romanowski, J. Mol. Catal. A 2013, 368–369, 137.
A. A. Moiseeva, W. Grunert, Inorg. Chim. Acta 2012, 392, 221. [46] S. Bunce, R. J. Cross, L. J. Farrugia, S. Kunchandy, L. L. Meason, K. W. Muir,
[32] M. Varyani, P. K. Khatri, S. L. Jain, Tetrahedron Lett. 2016, 57, 723. M. O. Donnell, R. D. Peacock, D. Stirling, S. J. Teat, Polyhedron 1998, 17,
[33] B. Gao, M. An, J. Men, Y. Zhang, Appl. Catal. A 2012, 439–440, 156. 4179.

[34] P. Gogoi, M. Kalita, T. Bhattacharjee, P. Barman, Tetrahedron Lett. 2014, [47] D. Tian, B. Liu, Q. Gan, H. Li, D. J. Darensbourg, ACS Catal. 2012, 2, 2029.
55, 1028. [48] B. Chen, L. Wang, S. Gao, ACS Catal. 2015, 5, 5851.
[35] A. R. Judy‐Azar, S. Mohebbi, J. Mol. Catal. A 2015, 397, 158. [49] Y. N. Belokon, V. I. Maleev, M. North, V. A. Larionov, T. F. Savel'yeva,
[36] K. P. Bryliakov, E. P. Talasi, J. Mol. Catal. A 2007, 264, 280. A. Nijland, Y. V. Nelyubina, ACS Catal. 2013, 3, 1951.

[37] S. Menati, H. A. Rudbari, B. Askari, M. R. Farsani, F. Jalilian, G. Dini, C. R.

Chim. 2016, 19, 347.
How to cite this article: Al Zoubi, W., and Ko, Y. G.
[38] R. Ando, H. Inden, M. Sugino, H. Ono, D. Sakaeda, T. Yagyu, M. Maeda,
Inorg. Chim. Acta 2004, 357, 1337.
(2016), Schiff base complexes and their versatile appli-
[39] S. N. Rao, N. Kathale, N. N. Rao, K. N. Munshi, Inorg. Chim. Acta 2007,
cations as catalysts in oxidation of organic compounds:
360, 4010. part I, Appl. Organometal. Chem., doi: 10.1002/
[40] R. Kumar, P. Mathur, Spectrochim. Acta 2015, 136, 818. aoc.3574