Ferromagnetic exchange coupling in a new bis(l-chloro)-bridged copper(II)

Schiff base complex: Synthesis, structure, magnetic properties and catalytic

oxidation of cycloalkanes
Santarupa Thakurta
a
, Partha Roy
b
, Georgina Rosair
c
, Carlos J. Gmez-Garca
d
, Eugenio Garribba
e
,
Samiran Mitra
a,
*
a
Department of Chemistry, Jadavpur University, Raja S.C. Mullick Rd., Kolkata 700 032, India
b
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India
c
Department of Chemistry, School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH 14 4AS, UK
d
Instituto de Ciencia Molecular (ICMol), Parque Cientco. University of Valencia, Paterna 46980, Spain
e
Department of Chemistry, University of Sassari, Via Vienna 2, Sassari I-07100, Italy
a r t i c l e i n f o
Article history:
Received 17 November 2008
Accepted 12 December 2008
Available online 20 January 2009
Keywords:
Schiff base
Bis(l-chloro)-bridge
Ferromagnetic
Catalytic activity
a b s t r a c t
A new (l-chloro)-bridged complex [Cu(HL)Cl]
2
H
2
O (1) with the Schiff base ligand H
2
L, [2-((E)-(2-
hydroxyethylimino)methyl)-4-bromophenol], has been synthesized and characterized by elemental anal-
ysis, IR, UVVis and EPR spectroscopic studies. X-ray diffraction studies show that 1 is a binuclear Cu
II
complex with a pair of chlorine atoms bridging the copper atoms in a central Cu
2
Cl
2
core. Each copper
atom in 1 adopts a distorted square-pyramidal geometry with the imine nitrogen atom, alkoxy and phen-
oxy oxygen atoms from the Schiff base ligand and a bridging chlorine atom constructing the basal plane,
while the apical position of the pyramid is occupied by the other bridging chlorine atom. Variable tem-
perature susceptibility measurements show that complex 1 presents the highest ferromagnetic coupling
[J = +43.2(5) cm
1
] reported till date in any doubly chloro-bridged Cu
II
dimer, and a weak interdimer anti-
ferromagnetic coupling [J
0
= -0.276(8) cm
1
]. The complex also exhibits high catalytic activity towards
the oxidation of hydrocarbons using H
2
O
2
as terminal oxidant.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
The binuclear compounds of copper(II) containing chloro-
bridged Cu(l-Cl)
2
Cu motifs have received a great deal of attention
in contemporary research because of their diverse structural prop-
erties. Many of these multinuclear complexes are of special inter-
est owing to their relevance as models for active sites of
biomolecules [1] and also for their effective role in catalytic enzy-
matic reactions [24]. The other important area of research with
these complexes is molecular magnetism, leading to promising
routes to new spin clusters and single-molecule magnets [5,6]. A
substantial amount of theoretical analyses have already been car-
ried out to achieve an empirical relationship between the exchange
coupling constant and structural features for these systems [79].
Albeit, it is quite difcult to establish simple magneto-structural
correlations relating the value of the magnetic exchange constant
J to the CuClCu bonding angle, CuCl or CuCu distances. This
may be attributed to the wealth of structural features comprising
of a large variety of bond distances and angles [1012]. As a conse-
quence, for these chloro-bridged complexes, several pathways for
magnetic interactions exist and both ferro- and antiferromagnet-
ism are possible depending on the nature of the coordinated li-
gands and the distortions of the geometry of the metal center.
Therefore, each type of structural dimer has to be studied sepa-
rately in order to draw meaningful magneto-structural correlations
and moreover, detailed investigations on additional complexes are
also necessary to determine the extent of this correlation. So far,
various types of bi- or tridentate organic blockers have been suc-
cessfully employed to design the coordination sphere of the cop-
per(II) center in bis(l-chloro)-bridged complexes [1319]. In this
context, Schiff base ligands may be very effective as they can give
rise to different coordination geometries around the metal center
taking advantage of the coordination exibility of Cu
II
d
9
system.
Although the number of chloro-bridged complexes involving Schiff
base ligands is limited in literature, recently some useful examples
of such Schiff base complexes showing interesting magnetic
behavior have been reported [2024].
The dynamic properties of the earlier complexes prompted
our research group to synthesize a new dichloro-bridged copper
dimer [Cu(HL)Cl]
2
H
2
O (1), where H
2
L is derived from the 1:1
0277-5387/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2008.12.016
* Corresponding author. Tel.: +91 (033) 2414 6666x2505; fax: +91 (033) 2414
6414.
E-mail address: smitra_2002@yahoo.com (S. Mitra).
Polyhedron 28 (2009) 695702
Contents lists available at ScienceDirect
Polyhedron
j our nal homepage: www. el sevi er . com/ l ocat e/ pol y
condensation of 5-bromosalicyldehyde and ethanolamine
(Scheme 1). The salicylidene-2-ethanolamine (H
2
sae) type of
ligands can act with both bridging and chelating coordination
modes and they have a strong tendency to participate in different
kinds of phenoxide or alkoxide bridges, exploiting the property of
terminal oxygens as good bridging groups. Previously H
2
sae and its
derivatives have been incorporated into a number of alkoxo- or
phenoxo-bridged tetranuclear Cu
II
, Ni
II
and Fe
II
clusters with cub-
ane structures [2528]. However, in our case, the chelating ability
of this ONO donor ligand has been utilized selectively to achieve
the desired chloro-bridged complex. Complex 1 has been com-
pletely characterized with elemental analysis, FT-IR, UVVis, EPR
spectra, and single crystal X-ray diffraction analysis. In this paper,
we report a combined structural and magnetic study of complex 1.
Magnetic susceptibility measurements (2300 K) show a promi-
nent ferromagnetic interaction in the dimer with J =
+43.2(5) cm
1
, and a weak interdimer antiferromagnetic interac-
tion of J
0
= 0.276(8) cm
1
. To the best of our knowledge, complex
1 presents the highest ferromagnetic coupling reported till date in
any doubly chloro-bridged Cu
II
dimer. Additionally, the catalytic
activity of the complex towards the oxidation of hydrocarbons
using H
2
O
2
as terminal oxidant has also been investigated. The
results of this study reveal that complex 1 behaves as active
catalyst for oxygenation of cyclohexane and cycloheptane to their
corresponding hydroxylated and oxygenated products affording
good yield and turnover number (TON).
2. Experimental
2.1. Materials
CuCl
2
2H
2
O was purchased from Merck India Ltd. and 5-
bromosalicylaldehyde and ethanolamine from SigmaAldrich,
USA. All the chemicals and solvents employed for the syntheses
were of analytical grade and used as received without further puri-
cation. Cyclohexane, cycloheptane, cyclohexanone, cyclohexanol,
cycloheptanone, cycloheptanol, cyclopentanone were purchased
from SigmaAldrich, USA, and used as received. Solvents used for
spectroscopic studies were puried and dried by standard proce-
dures before use [29].
2.2. Syntheses
2.2.1. Synthesis of the Schiff base ligand [2-((E)-(2-
hydroxyethylimino)methyl)-4-bromophenol] (H
2
L)
Ethanolamine (0.12 ml, 2 mmol) was added to a solution of 5-
bromosalicylaldehyde (0.402 g, 2 mmol) in 20 ml methanol and
the mixture was reuxed for 1 h at 65 C. A yellow solid was
formed which was ltered, washed with methanol and vacuum
dried. Yield: 0.141 g (85%). Anal. Calc. for C
9
H
10
BrNO
2
: C, 44.29;
H, 4.13; N, 5.74. Found: C, 44.32; H, 4.10; N, 5.81%. FT-IR (KBr,
cm
1
): m(C@N) 1640. UVVis (k, nm): 261, 393.
2.2.2. Synthesis of the complex [Cu(HL)Cl]
2
H
2
O (1)
The appropriate quantity of solid Schiff base ligand H
2
L
(0.165 g, 1 mmol) was dissolved in 20 ml of methanol. This ligand
solution was added dropwise to a 10 ml methanolic solution of
CuCl
2
2H
2
O (0.160 g, 1 mmol) with constant stirring. The mixture
was reuxed for 45 min at 65 C. The resulting deep green solution
was then left undisturbed. After 7 days blue block-shaped X-ray
diffraction quality single crystals appeared. Yield: 82%. Anal. Calc.
for C
18
H
20
Br
2
Cl
2
Cu
2
N
2
O
5
: C, 30.79; H, 2.87; N, 3.99. Found: C,
30.72; H, 2.89; N, 3.94%.
2.2.3. Experimental procedure for oxidation of cyclohexane and
cycloheptane
The catalytic hydrocarbon oxidation reactions by complex 1
involving cyclohexane and cycloheptane as substrates were carried
out with the following procedure: 2.510 mmol of hydrogen per-
oxide (30% in H
2
O) was added to the metal complex (0.025 mmol)
in 3 ml of acetonitrile in a two-neck round bottom ask tted with
a condenser. To this solution, HNO
3
(0.25 mmol) was added fol-
lowed by the addition of 0.927 mmol of substrate. The reaction
was initiated by stirring the above mixture for 48 h at room tem-
perature under atmospheric pressure. Aliquots were collected after
regular time intervals and 90 ll of cyclopentanone was added as
internal standard. The substrate and products from the reaction
mixture were extracted with 10 ml of diethyl ether and they were
analyzed by gas chromatography. The identication was achieved
by comparison with known standards.
2.3. Physical measurements
The Fourier transform infrared spectra of the ligand and the
complex were recorded on a PerkinElmer Spectrum RX I FT-IR
spectrophotometer with a KBr pressed pellet in the range 4000
200 cm
1
. The electronic spectra were recorded on a PerkinElmer
Lambda 40 (UVVis) spectrometer using HPLC grade acetonitrile as
solvent in the range 800200 nm. Elemental analyses were carried
out on a PerkinElmer 2400 II Elemental Analyser. Electron para-
magnetic resonance (EPR) spectrum of 1 was recorded on a poly-
crystalline sample or in CH
3
CN and N,N-dimethylformamide
(DMF) solutions with an X-band Bruker EMX spectrometer at 298
and 120 K. The spectra were simulated with the computer program
Bruker WinEPR SimFonia. The magnetic susceptibility measure-
ments were carried out in the temperature range 2300 K with
an applied magnetic eld of 0.1 T on a polycrystalline sample of
complex 1 (mass = 45.00 mg) with a Quantum Design MPMS-XL-
5 SQUID magnetometer. The isothermal magnetization was per-
formed on the same sample at 2 K with magnetic elds up to 5 T.
The susceptibility data were corrected for the sample holders pre-
viously measured using the same conditions and for the diamag-
netic contributions of the salt as deduced by using Pascals
Br
OH
+
H
2
N OH
Br
OH
5-Bromosalicylaldehyde
(1 mmol)
Ethanolamine
(1 mmol)
N
HO
H
O
Reflux
H
2
L
Scheme 1.
696 S. Thakurta et al. / Polyhedron 28 (2009) 695702
constant tables (v
dia
= 332.3 10
6
emu mol
1
). Gas chromatog-
raphy analysis was performed with an Agilent Technologies 6890N
network GC system equipped with a fused silica capillary column
(30 m 0.32 mm) and a FID detector.
2.4. Crystallographic data collection and structure renements
A diffraction quality single crystal of 1 was mounted on a Bruker
X8 Apex 2 CCD diffractometer equipped with a graphite monochro-
mator and Mo Ka radiation (k = 0.71073 ). Data collection was
carried out using the Bruker APEX2 software [30]. Multiscan absorp-
tion correction was applied using SADABS [31]. The structure of the
complex was solved by direct methods with SHELXS, and rened
by full-matrix least squares based on F
2
with SHELXL [32]. All non-
hydrogen atoms were rened anisotropically. The C-bound H
atoms were constrained to ideal geometry and were included in
the renement in the riding model approximation while those of
the water molecules were located in difference Fourier maps. Fur-
ther crystallographic analysis and gure production were carried
out using PLATON99 [33] and ORTEP [34] programs. Details of the data
collection parameters and crystallographic information for the
complex are summarized in the Table 1.
3. Results and discussion
3.1. Infrared and electronic spectra
In the IR spectrum of complex 1, the strong absorption band at
1603 cm
1
can be assigned to the imine stretching frequency of the
coordinated ligand, whereas for the free ligand molecule the same
band is observed at 1640 cm
1
. The shift of this band towards low-
er frequency on complexation with the metal suggests coordina-
tion to the metal ion through imine nitrogen atom [35,36]. The
m(CO) mode is present as a very strong band at about
1195 cm
1
. Ligand coordination to the metal center is substanti-
ated by prominent bands appearing at 445 and 370 cm
1
which
can be attributed to m(CuN) and m(CuO), respectively. The two
bands observed at 310 and 297 cm
1
are characteristic of CuCl
vibrations [37]. The broad band at 34403255 cm
1
is attributable
to OH stretching vibrations of lattice water molecule.
The electronic spectral data for the complex in HPLC grade ace-
tonitrile solvent are in good agreement with its geometry. The two
strong absorption bands in the region 350385 nm are clearly
charge transfer in origin [38] attributed to the transition from
the coordinated unsaturated ligand to the metal ion (LMCT). Again,
the intense high energy bands at about 245 and 380 nm may be as-
signed to the intraligand p ?p
*
and n ?p
*
transitions, respec-
tively. The broad low-intensity absorption band centered at
605 nm is a typical dd band for the copper(II) ion [38,39].
3.2. Crystal structure description of complex 1
A perspective ORTEP view with the atom-labeling scheme of com-
plex 1 is presented in Fig. 1. Selected bond lengths and angles for
the complex are given in Table 2. The asymmetric unit of 1 consists
of a [Cu(HL)Cl]
2
dimeric unit with a lattice water molecule. In the
complex, the Schiff base 2-((E)-(2-hydroxyethylimino)methyl)-4-
bromophenol (H
2
L) behaves as a monoanionic, tridentate ligand
which coordinates to the metal center through its imine nitrogen,
alkoxy oxygen and deprotonated phenolic oxygen atoms. The crys-
tal structure determination reveals that complex 1 is a double
chloro-bridged dimer in which the copper ions are pentacoordinat-
ed, being bonded to three coordinating donor sites of the Schiff
base ligand and two bridging chloride anions as shown in Fig. 1.
The coordination number 5 for Cu
II
is very common and usually
presents either a square-pyramidal (SP) or a trigonalbipyramidal
(TBP) geometry (or any of the distorted intermediate geometries).
For a pentacoordinated metal center, the distortion of the coordi-
nation environment from TBP to SP can be evaluated by the Addi-
son distortion index, s dened as s = [|h U|/60], where h and U
are the two largest coordination angles and s = 0 for perfect SP
and 1 for ideal TBP [40,41]. In complex 1, the calculated s values
for Cu1 and Cu2 are 0.147 and 0.200, respectively, clearly suggest-
ing a distorted SP geometry for each copper ion. The square base of
each of the two structurally similar copper atoms is constructed by
Table 1
Summary of crystal data and renement details for 1.
Empirical formula C
18
H
20
Br
2
Cl
2
Cu
2
N
2
O
5
Formula weight 702.16
Crystal dimension (mm) 0.40 0.20 0.16
Crystal system monoclinic
Space group P2
1
/n
a () 14.1643(19)
b () 7.6871(11)
c () 21.515(3)
b () 92.241(3)
V (
3
) 2340.9(6)
Z 4
Temperature (K) 100(2)
D
calc
(g cm
3
) 1.992
l (mm
1
) 5.492
F(000) 1376
h () 1.7523.90
Total data 17644
Unique data 3412
Observed data [I > 2r(I)] 2539
R
a
0.0354
R
w
b
0.0803
Goodness-of-t on F
2
, S 1.06
R
int
0.060
Dq
max
(e
3
) 1.32
Dq
min
(e
3
) 0.78
a
R = R(|F
o
F
c
|)/R|F
o
|.
b
R
w
= {R[w(|F
o
F
c
|)
2
]/R[w|F
o
|
2
]}

.
Fig. 1. ORTEP representation of complex 1. Thermal ellipsoids have been drawn at
40% probability level. Dashed lines indicate hydrogen bonds.
S. Thakurta et al. / Polyhedron 28 (2009) 695702 697
the imine nitrogen atom, the alkoxy and phenoxy oxygen atoms
from the Schiff base ligand and a bridging chlorine atom, while
the apical position of the pyramid is occupied by the other bridging
chlorine atom. The CuN
imine
and CuO
phenolic
bond distances are in
the ranges observed for similar systems [24]. The CuO(phenolic)
distances are slightly shorter than those of the Cu-O(alkoxy). The
substantial elongation of the axial CuCl bonds [2.685(2) and
2.668(2) for Cu1 and Cu2, respectively] compared to the equato-
rial CuCl bonds [2.267(2) and 2.268(2) for Cu1 and Cu2, respec-
tively] is caused by the active JahnTeller distortion of the
copper(II) ion. Interestingly, for the Cu1 center, Cl2 occupies the
basal position of the pyramid and Cl1 is apical, whereas in case
of the other copper center (Cu2), Cl1 is in the basal plane and Cl2
is in the apical position. As a result, the geometry of the complex
consists of two square pyramids sharing one base-to-apex edge
but with nearly parallel basal planes [13,21,42]. The axialequato-
rial conguration of the two chloro bridges is depicted clearly in
Fig. 2. Both Cu1 and Cu2 are displaced from the mean equatorial
plane towards the corresponding axial chloro bridging atoms, Cl1
and Cl2, by 0.183 and 0.167 , respectively.
Within the Cu(l-Cl)
2
Cu core, the CuCu distance of
3.3371(10) is much shorter than the average value for chloro-
bridged copper(II) dimers (3.499 ) in CSD [43]. The Cu
2
Cl
2
core
is considerably distorted from an ideal square as reected from
the average ClCuCl and CuClCu bond angles of 92.97 and
84.45, respectively, both deviating from the ideal angle of 90.
Moreover, these small CuClCu angles play an important role in
determining the magnetic coupling within the dimer. The asym-
metric nature of the double bridge is also evident from the differ-
ent CuCl bond lengths. Both basal (ca. 2.27 ) and axial (ca.
2.67 ) CuCl distances are comparable with the average literature
values of 2.309 for short and 2.554 for long CuCl
bridging
dis-
tances, respectively.
On one side of the dimer, the two Schiff base ligands are intra-
molecularly connected through a hydrogen bond between atoms
H2H on alkoxy O2 and phenolic O3 (Fig. 1). As a consequence,
the two ligands are moved away from each other on the opposite
side to maintain the structural integrity of the complex. This segre-
gation generates a hole where a H
2
O solvent molecule is inserted,
optimizing the interactions at this site by creating a double hydro-
gen bond. Thus the interaction between phenolic oxygen O1 and
alkoxy oxygen O4 is mediated through the intermolecular hydro-
gen bonds O1WH12WO1 and O4H4HO1W (Table S1, Supple-
mentary data). Finally, there are two very short BrBr contacts
between adjacent dimers of only 3.6906(11) and 4.0550(2) con-
necting the dimers in the ac plane and a longer BrBr contact of
4.99 connecting the dimers in the b direction (Fig. S2, Supple-
mentary data).
3.3. EPR spectra
EPR spectra recorded at 298 and 120 K on polycrystalline com-
plex 1 are characterized by two g values (g
||
= 2.222 and
g
\
= 2.094), which follow the trend g
||
> g
\
> g
e
(Fig. 3). The forbid-
den singlet-triplet transition (DMs = 2), often detected at half-
eld for dimeric copper(II) complexes, is observable only with high
instrumental gains. The EPR spectral features can be associated to
an axial symmetry having d
x
2
y
2 as ground state [44,45], where the
geometry can correspond to an elongated octahedral, a square-
pyramidal or a square planar. The observed g values conrm that
the geometry of the binuclear species is close to the square pyra-
mid with the deprotonated phenolic and alkoxy oxygens, the imine
nitrogen and the bridging Cl

ion in the equatorial plane and a sec-

ond Cl

in the axial position.

The double chloro bridge is destroyed when complex 1 is dis-
solved in a coordinating solvent like DMF or CH
3
CN and the mono-
nuclear unit is formed. This happens because the solvent molecules
can easily replace the labile chloride ligands in the coordination
sphere of copper ion as found in many other similar complexes
[46,47]. EPR spectrum of 1 dissolved in DMF or CH
3
CN shows an
axial symmetry (Fig. 4). The spectral parameters: g
||
= 2.270 and
A
||
= 169.0 10
4
cm
1
in DMF and g
||
= 2.275 and A
||
= 176.5
10
4
cm
1
in CH
3
CN, can be explained postulating a ve-coordi-
nated structure with phenolic-O

, imine-N, alkoxo-O and a Cl

in
Table 2
Selected bond lengths and bond angles for 1.
Bond lengths ()
Cu1O1 1.913(4) Cu2O3 1.915(4)
Cu1N2 1.937(4) Cu2N1 1.939(5)
Cu1O2 2.012(4) Cu2O4 1.985(4)
Cu1Cl2 2.2672(15) Cu2Cl1 2.2680(15)
Cu1Cl1 2.6853(16) Cu2Cl2 2.6685(16)
Bond angles ()
O1Cu1N2 94.24(18) O3Cu2N1 93.26(18)
O1Cu1O2 175.70(16) O3Cu2O4 175.11(15)
N2Cu1O2 82.16(17) N1Cu2O4 82.24(18)
O1Cu1Cl2 92.93(12) O3Cu2Cl1 91.75(12)
N2Cu1Cl2 160.88(15) N1Cu2Cl1 163.11(15)
O2Cu1Cl2 89.79(11) O4Cu2Cl1 92.04(12)
O1Cu1Cl1 94.47(12) O3Cu2Cl2 93.87(12)
N2Cu1Cl1 104.31(14) N1Cu2Cl2 102.54(14)
O2Cu1Cl1 88.73(12) O4Cu2Cl2 88.99(12)
Cl2Cu1Cl1 92.76(5) Cl1Cu2Cl2 93.19(5)
Cu1Cl2Cu2 84.66(5) Cu2Cl1Cu1 84.25(5)
Fig. 2. Coordination environment of the two Cu
II
ions in complex 1 showing the
axialequatorial conguration of the two Cl bridges (inset: arrangement of the two
square pyramids).
Fig. 3. X-band EPR spectrum of polycrystalline complex 1 at 120 K.
698 S. Thakurta et al. / Polyhedron 28 (2009) 695702
the equatorial plane and one molecule of solvent weakly bound in
the axial position.
3.4. Magnetic studies
The thermal variation of the molar magnetic susceptibility
times the temperature (v
m
T) for complex 1 is shown in Fig. 5. At
roomtemperature, the value for v
m
T is ca. 0.92 emu K mol
1
which
is slightly higher than the expected one for two non interacting
copper(II) S = 1/2 ions (0.75 emu K mol
1
for g = 2.0). When cooling
down the sample, the v
m
T product remains constant down to
180 K and below this temperature it shows a continuous increase
to reach a maximum of ca. 1.14 emu K mol
1
at 12 K. Below 12 K,
v
m
T decreases to reach a value of ca. 1.07 emu K mol
1
at 2 K. This
behavior indicates that complex 1 presents predominant ferro-
magnetic interactions, as suggested by the increase in v
m
T
observed at low temperatures. The v
m
T value of the maximum
(1.14 emu K mol
1
) is close to the expected value for the S = 1 spin
ground state arising from the ferromagnetic coupling of two S = 1/2
spins. The decrease observed at low temperatures can be attrib-
uted to the presence of antiferromagnetic interactions between
the S = 1 dimers at low temperatures and/or to a zero eld splitting
(ZFS) of the S = 1 ground spin state. Since the structure of this com-
plex shows the existence of Cu
II
dimer connected by double chlo-
ride bridges, we have tted the magnetic properties of complex 1
to a simple ferromagnetic S = 1/2 dimer with an interdimer ex-
change interaction (J
0
) to account for the decrease of v
m
T at low
temperatures (the Hamiltonian is written as H = JS
i
S
i+1
) [48]:
v 2Ng
2
b
2
kT
2J
0
3 e
x

1
3 e
x

1
;
where x = J/kT.
This model reproduces very satisfactorily the magnetic data of
complex 1 in the whole temperature range with the following set
of parameters: g = 2.156(1), J = 43.2(5) K = 30.0(4) cm
1
and
J
0
= 0.276(8) K = 0.192(6) cm
1
(solid line in Fig. 5). As expected
(see below), the intradimer magnetic coupling is ferromagnetic
and the interdimer one is much weaker and antiferromagnetic.
An additional proof of the ferromagnetic nature of the coupling
in complex 1 comes from the isothermal magnetization measure-
ments at low temperature (Fig. 6). This measurement shows a sat-
uration value of ca. 2.2l
B
, very close to the expected value for an
S = 1 spin state, resulting from the ferromagnetic coupling of the
two S = 1/2 Cu
II
ions. Furthermore, the magnetization can be repro-
duced well with a Brillouin function for an S = 1 with a g value of
2.131(4) (solid line in Fig. 6).
As already mentioned in the introduction, there have been sev-
eral attempts to establish magneto-structural correlations in dinu-
clear dichloro-bridged Cu
II
complexes, from the pioneering work of
Willett and co-workers [49] and Hateld and co-workers [9,15]
that related the magnetic coupling with the CuClCu angle (a)
and with the a/R ratio, respectively (where R is the CuCl
bridge
dis-
tance), to the more recent works of Rodrguez et al. [50], Mrozinski
and co-workers [51] and Julve and co-workers [8]. All these corre-
lations indicate that the exchange coupling constant J depends on
the value of the CuClCu bridging angle, a, as well as on the bond
length of the axial (longer) CuCl bond, R in SP geometry. However,
these parameters are not the only factors playing an important role
in determining the magnetic coupling. The different types of
arrangement of the two copper(II) polyhedra have a great inuence
on the magnetic behavior of such complexes. The global arrange-
ment of the two square pyramids gives rise to three types of geom-
etries: (a) square pyramids sharing one base-to-apex edge but with
parallel basal planes (Type-I), (b) square pyramids sharing one
base-to-apex edge with the two bases nearly perpendicular to
one another (Type-II) and (c) square pyramids sharing a basal edge
with coplanar basal planes (Type-III). Complex 1 belongs to the
Type-I class of compounds, as evident from its structural features
(Fig. 2). Thus, for the parallel bases arrangement (Type-I as in the
case of the title complex), extended Hckel calculations [50] show
that the magnetic interaction occurs through a p
*
type interaction
Fig. 4. X-band EPR anisotropic spectra of complex 1 recorded at 120 K in: (a) DMF
and (b) CH
3
CN.
0.90
0.95
1.00
1.05
1.10
1.15
0 50 100 150 200 250 300

m
T

(
e
m
u
.
K
.
m
o
l
-
1
)
T (K)
1.00
1.05
1.10
1.15
0 10 20 30 40 50
Fig. 5. Thermal variation of the v
m
T product for complex 1. Solid line represents the
best t to the model (see text). Inset shows the low temperature region.
0.0
0.5
1.0
1.5
2.0
2.5
0.0 0.5 1.0 1.5 2.0 2.5
M

(

B
)
H/T (T.K
-1
)
Fig. 6. Isothermal magnetization at 2 K of complex 1. Solid line represents the best
t to the Brillouin function for an S = 1 spin state (see text).
S. Thakurta et al. / Polyhedron 28 (2009) 695702 699
between the d
x
2
y
2 Cu orbital and the p orbital of the chlorine
atoms. The extent of this magnetic coupling is decided by the small
structural deviations from the ideal square Cu
2
Cl
2
core. Recently,
Mrozinski and co-workers [51] established a theoretical correla-
tion between the magnetic coupling and both parameters (a and
R) showing that for small a values and short CuCl distances the
magnetic coupling is ferromagnetic. When the a and R values of
complex 1 [a = 84.66(5) and 84.25(5) and R = 2.6853(16) and
2.6685(16) ] are reported to this relationship, a moderately
strong ferromagnetic coupling is predicted, which is in agreement
with the experimental results. Furthermore, these a and R values
are expected to produce the strongest ferromagnetic coupling of
all the known Cu
II
dimers involving a similar dichloro bridge. Inter-
estingly, corroborating with the theoretical predictions, complex 1
is found to present the highest ferromagnetic coupling
[J = +43.2(5) cm
1
] reported so far for any bis(l-chloro) copper(II)
dimers. An analysis of the a and R values of the other known di-
chloro-bridged Cu
II
complexes [8,15,50,51] shows that the main
reason explaining this particular situation are the small a values
of complex 1, which are about 5 smaller than the average value
of 89.40(5) [14]. Previously, the smallest a value reported was
82.9 for the complex [Cu
2
(baamo)
2
Cl
2
] (baamo = 8-amino-5-aza-
4-methyl-3-octene-2-onate), where a ferromagnetic coupling of
12 cm
1
had been found even when the CuCl distance was as high
as 2.81 [52]. In the present complex the small a values are
accompanied by much shorter R values (ca. 2.67 ) compared to
the above complex, giving rise to the unusually strong ferromag-
netic coupling. A detailed look at the structure of complex 1 reveals
that the presence of the intradimer hydrogen bonds (Fig. 1) may be
responsible for the unusually small CuClCu angles since both in-
tra- and intermolecular hydrogen bonds force the copper(II) ions to
be closer, decreasing the CuClCu bond angle.
Finally, the antiferromagnetic weak interdimer exchange can be
attributed to the presence of some short interdimer BrBr contacts
(Fig. S2, Supplementary data).
3.5. Catalytic oxidation of cyclohexane and cycloheptane
The study of the oxidation of various hydrocarbons catalyzed by
a metal complex has now become an important research topic
since it involves conversion of crude oil and natural gas constitu-
ents into oxygenated derivatives of immense industrial impor-
tance, such as alcohols or carbonyl compounds.
Here, we have examined the catalytic activity of the complex
towards cyclohexane and cycloheptane oxidation using hydrogen
peroxide as oxidant under the same experimental conditions for
both the substrates. It is found that complex 1 behaves as active
catalyst for the liquid biphasic (acetonitrile/water) oxidation of
cyclohexane and cycloheptane by H
2
O
2
in a slightly acidic medium
at room temperature and atmospheric pressure. The corresponding
products are cycloalkanol and cycloalkanone. Optimization has
been achieved by varying the relative proportions of nitric acid,
hydrogen peroxide as well as time period of the reactions. In the
literature [53,54], it has been clearly pointed out that the presence
of nitric acid has a positive role. The catalyst activation is created
by the increase of unsaturation at the metal center with simulta-
neous increase in oxidation properties. As a result decomposition
of peroxide is retarded and the peroxo intermediate gets stabilized.
During the present study, we have veried that the addition of
nitric acid is mandatory in the hydrogen peroxide oxidation of
cyclohexane and cycloheptane in presence of complex 1 as the cat-
alyst. The amount of oxidized products remains almost unchanged
in the 1050 range of n(HNO
3
)/n(catalyst), whereas further in-
crease of such ratio decreases the yield. When the oxidation of
the substrate was carried out in absence of nitric acid, the reaction
did not proceed at all. The highest conversion of the substrate is
achieved when n(HNO
3
)/n(catalyst) is 10. The geometry around
the Cu center in the catalyst is pentacoordinated having labile sites
like CuCl. These would require nitric acid so as to increase unsat-
uration at the metal site as a result of ligand protonation. Such
observations evoked us to maintain a ratio of n(HNO
3
)/n(cata-
lyst) = 10 in the rest of the studies.
The results of cyclohexane oxidation are shown in Table 3a. It is
clearly seen from the table that the maximum conversions of
cyclohexane to the corresponding cyclohexanol and cyclohexa-
none are 31.4% and 20.9%, respectively, when n(H
2
O
2
)/n(catalyst)
ratio is 300 with the reaction time 48 h. Table 3b contains the de-
tails of the conversion of cycloheptane inuenced by the relative
amounts of hydrogen peroxide, amount of nitric acid and the reac-
tion period. The maximum conversions of cycloheptane to the cor-
responding cycloheptanol and cycloheptanone achieved are 24.0%
and 15.0%, respectively. The results of these oxidation reactions
are comparable with those obtained for other copper complexes
reported earlier [53,55,56]. In contrast, simple copper salt like,
Cu(NO
3
)
2
under the same reaction conditions exhibits a much low-
er activity towards oxidation of the substrates with 3.95.4% yield,
under the same peroxide-to-catalyst molar ratio. Thus it is evident
that the presence of N,O donor ligands are quite relevant.
In the case of complex 1, the coordination environment around
the copper(II) ion is easily accessible for an external ligand, as a re-
sult copper(II) can bind the peroxo-group on treatment with per-
oxides. This in situ generated intermediated peroxo-type species
seems to be capable of transferring the oxo functionality to the or-
ganic substrates to give the corresponding oxidized products. In or-
der to nd out the probable mechanisms, we have carried out the
catalytic reaction of cyclohexane with complex 1 maintaining
n(HNO
3
)/n(catalyst) ratio of 10 and n(H
2
O
2
)/n(catalyst) ratio of
300 in presence of TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl)
and diphenylamine. The yield of the reaction is greatly suppressed
in presence of these compounds. TEMPO and diphenylamine are
Table 3a
Oxidation of cyclohexane by complex 1.
Entry Catalyst n(H
2
O
2
)/n(catalyst) Time (h) Yield (%) TON
a
Cyclohexanol Cyclohexanone Total
1 Complex 1 150 6 20.1 15.4 35.5 13.2
2 48 26.3 20.1 46.4 17.2
3 300 6 24.5 14.1 38.6 14.3
4 48 31.4 20.9 52.3 19.4
5 750 6 20.5 16.9 37.4 13.9
6 48 26.0 19.1 45.1 16.7
7 Cu(NO
3
)
2
150 48 1.8 1.1 2.9
8 300 48 3.4 1.7 5.1
9 750 48 3.6 1.8 5.4
a
Turnover number.
700 S. Thakurta et al. / Polyhedron 28 (2009) 695702
well known as carbon-radical and oxygen-radical traps respec-
tively [57]. This indirectly indicates that oxidation reactions occur
mainly by mechanisms involving the formation of both carbon-
centered and oxygen-centered radicals. An electrophilic attack of
an oxidized metal-peroxo, metal-superoxo or metal-oxo center to
a CH bond of the substrate with heterolytic cleavage of this bond
to form an organocopper intermediate can be proposed which has
been noted for other metals [58].
4. Conclusion
The present complex shows the feasibility of the ONO donor
Schiff bases to form dinuclear dichloro-bridged Cu
II
complexes
with an unusually strong ferromagnetic coupling. In fact, complex
1 presents the strongest ferromagnetic coupling observed till date
in any doubly (l-chloro)-bridged Cu
II
complex. The previously
established magneto-structural correlations attribute this strong
ferromagnetic coupling to the unusually small CuClCu bond an-
gles. A detailed structural analysis reveals that the intradimer
hydrogen bonds of both intra- and intermolecular types are
responsible for bringing the two copper centers closer, thereby
decreasing the bridging angle. Besides this, the complex is also
found to possess efcient catalytic properties in the oxidation of
cyclohexane and cycloheptane by H
2
O
2
to their corresponding
alcoholic and carbonyl derivatives.
Acknowledgements
Santarupa Thakurta gratefully acknowledges the Council of Sci-
entic and Industrial Research, New Delhi, India, for the award of
Research Fellowship to her (CSIR Sanction No. 09/096(0519)/
2007-EMR-I) and thanks are extended to Prof. P. Banerjee of
Department of Inorganic Chemistry, Indian Association for the Cul-
tivation of Science, Kolkata 32, for providing valuable supports.
Carlos J. Gmez-Garca acknowledges the European Union for
nancial support (MAGMANet network of excellence) and the
Spanish Ministerio de Educacin y Ciencia (Projects MAT2007-
61584 and Consolider-Ingenio 2010 CSD 2007-00010 in Molecular
Nanoscience).
Appendix A. Supplementary data
CCDC 703082 contains the supplementary crystallographic data
for complex 1. These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.poly.2008.12.016.
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Entry Catalyst n(H
2
O
2
)/n(catalyst) Time (h) Yield (%) TON
Cycloheptanol Cycloheptanone Total
1 Complex 1 150 6 19.1 14.3 33.4 12.4
2 48 22.2 15.2 37.4 13.9
3 300 6 17.9 11.7 29.6 11.0
4 48 24.0 15.0 39.0 14.5
5 750 6 19.3 11.1 31.4 11.6
6 48 23.5 13.6 37.1 13.8
7 Cu(NO
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2
150 48 2.1 1.0 3.1
8 300 48 3.5 1.7 5.2
9 750 48 3.3 2.1 5.4
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