Five complexes containing N, N -bis(2-hydroxyethyl)-ethylenediamine with tetracyanidopalladate(II): Synthesis, crystal structures, thermal, magnetic, and catalytic properties

Article abstract of DOI:10.1080/00958972.2013.820827

Five cyanide complexes, [Ni(N-bishydeten)Pd(CN)₄] (1), [Cu(N-bishydeten)Pd(-CN)₂(CN)₂]_n (2), [Cu(N-bishydeten)₂][Pd(CN)₄] (3), [Zn(N-bishydeten)Pd(CN) ₄] (4), and [Cd(N-bishydeten)₂][Pd(CN)₄] (5) (N-bishydeten = N,N-bis(2-hydroxyethyl)-ethylenediamine), have been synthesized and characterized using various techniques. Different structures were formed when the M: L ratio was varied in copper complexes. The single-crystal X-ray diffraction analysis reveals that 2, a 1-D cyanide-bridged complex with 2,2-CT-type zigzag chain, was obtained by using 1: 1 M: L ratio whereas 3 was formed as a complex salt in a molar ratio of 1: 2. The thermal stabilities determined from DTGmax values of the first decomposition stages change in the order 1 > 5 > 4 > 3 > 2. Although an EPR signal was not observed for 1, the g parameters obtained from the EPR spectra of 2 and 3 indicate that Cu^II ions are located in tetragonally distorted octahedral sites (D4_h), and the ground state of the unpaired electron is ( ²B1_g). The magnetic behavior indicates a very small antiferromagnetic interaction below 10 K for 1-3. In 3, there is a temperature-independent paramagnetism (α) due to the orbital moments of the d electrons. 1-3 were tested as catalysts in Suzuki and Heck coupling reactions. 102013

Full text of DOI:10.1080/00958972.2013.820827

Journal of Coordination Chemistry, 2013
Vol. 66, No. 17, 3072–3091, http://dx.doi.org/10.1080/00958972.2013.820827
Five complexes containing N,N-bis(2-hydroxyethyl)-
ethylenediamine with tetracyanidopalladate(II): synthesis,
crystal structures, thermal, magnetic, and catalytic properties
Ş. ASLAN KORKMAZ†, A. KARADAĞ*‡, N. KORKMAZ‡, Ö. ANDAÇx
N. GÜRBÜZ{, İ. ÖZDEMIR{ and R. TOPKAYAk
†Aquaculture Department, Vocational College, Tunceli University, Tunceli, Turkey
zChemistry Department, Gaziosmanpaşa University, Tokat, Turkey
xChemistry Department, Ondokuz Mayıs University, Samsun, Turkey
{Chemistry Department, İnönü University, Malatya, Turkey
kPhysics Department, Gebze Institute of Technology, Kocaeli, Turkey
(Received 4 March 2013; in final form 6 June 2013)
Five cyanide complexes, [Ni(N-bishydeten)Pd(CN)4] (1), [Cu(N-bishydeten)Pd(μ-CN)2(CN)2]n (2),
[Cu(N-bishydeten)2][Pd(CN)4] (3), [Zn(N-bishydeten)Pd(CN)4] (4), and [Cd(N-bishydeten)2][Pd
(CN)4] (5) (N-bishydeten = N,N-bis(2-hydroxyethyl)-ethylenediamine), have been synthesized and
characterized using various techniques. Different structures were formed when the M : L ratio was
varied in copper complexes. The single-crystal X-ray diffraction analysis reveals that 2, a 1-D
cyanide-bridged complex with 2,2-CT-type zigzag chain, was obtained by using 1 : 1 M : L ratio
whereas 3 was formed as a complex salt in a molar ratio of 1 : 2. The thermal stabilities determined
from DTGmax values of the first decomposition stages change in the order 1 > 5 > 4 > 3 > 2.
Although an EPR signal was not observed for 1, the g parameters obtained from the EPR spectra
of 2 and 3 indicate that CuII ions are located in tetragonally distorted octahedral sites (D4h), and
the ground state of the unpaired electron is dx2ꢀy2 (2B1g). The magnetic behavior indicates a very
small antiferromagnetic interaction below 10 K for 1–3. In 3, there is a temperature-independent
paramagnetism (α) due to the orbital moments of the d electrons. 1–3 were tested as catalysts in
Suzuki and Heck coupling reactions.
Keywords: Tetracyanidopalladate; N,N-bis(2-hydroxyethyl)-ethylenediamine; Thermal analysis;
Magnetic susceptibility; Suzuki–Heck coupling reaction
1. Introduction
The wide availability of transition metal cyanide complexes in terms of both diverse
bonding and structural chemistry has led to widespread application of these complexes in
materials chemistry. Cyanide is an efficient ligand for stabilization and the formation of
one- (1-D), two- (2-D), or three-dimensional (3-D) structures. The versatility of cyanide
results from its ability to act as both a σ-donor and a π-acceptor, its negative charge, and
its ambidentate nature [1]. A terminal cyanide can participate in simple hydrogen bonds of
*Corresponding author. Email: ahmet.karadag@gop.edu.tr
Ó 2013 Taylor & Francis

Tetracyanidopalladate(II)
3073
the CNꢁ ꢁ ꢁHꢀX type (X is an electronegative atom). These hydrogen bonds play an
important role in forming high-dimensional structures, packing and stabilizing the
structures formed, and serving as a possible exchange path for magnetic interactions [2].
Cyanide has been widely used in luminescence [3, 4], catalysis [5, 6], molecular sieves
[7–10], ion exchange [11], selective binding of guest molecules [12–14], and magnetism
[15–20].
The controlled assembly of inorganic building blocks is very important in design of
high-dimensional systems. These systems are formed using [M(CN)n]yꢀ (M = Ni, Pd, Pt,
Cu and Au; n = 2 or 4; y = ꢀ1 or ꢀ2) in conjunction with a transition metal complex
because of the ability of cyanide to connect various central atoms to build molecular
assemblies [21]. Among these cyanidometallates, the tetracyanidopalladate, [Pd(CN)4]2ꢀ, is
an ideal building block that has rarely been studied. Square planar PdII units have attracted
attention as catalysts in C–C coupling reactions. Palladium-catalyzed C–C cross-coupling
reactions, such as the Suzuki–Miyaura [22–29] and the Heck–Mizoroki [30–34], are
among the most essential transformations in organic and organometallic chemistry.
Functional cyanide complexes can be synthesized with di- or poly-dentate ligands [35].
The tripodal N-bishydeten used in this study is a neutral ligand that has two N- and two
O-donors, and behaves as a multidentate ligand, generally coordinated with NN′O or NN′
O2 donors [36, 37]. It has rarely been used in cyanide complexes.
We reported a number of cyanidometallate complexes in which [Pd(CN)4]2ꢀ has been
utilized. Previous studies on structures of 1-D bimetallic polymeric cyanide complexes
[M(hydeten)2Pd(CN)4]n {MII = Ni, Cu, Zn and Cd; hydeten = N-(2-hydroxyethyl-ethylenedi-
amine)} [38–40] revealed that Cu/Pd and Zn/Pd binuclear complexes, having 2,2-TT-type
chains, were isostructural whereas Cd/Pd complexes formed in 2,2-CT-type chains. The
cyanide-bridged complexes [M(bishydeten)Pd(CN)4] {MII = Ni, Cu, Zn and Cd;
bishydeten = N,N′-bis(2-hydroxyethyl)-ethylenediamine} were synthesized and character-
ized, and the catalytic properties of Ni/Pd and Cu/Pd complexes were studied [41]. As an
extension of our work on these systems, here we report the synthesis and characterization
(FT-IR spectra, elemental analysis, EPR spectra, and thermal properties) of 1–5. The crys-
tal structures of 2 and 3, and the magnetic behavior and catalytic properties of 1–3 were
also determined.
2. Experimental
2.1. Materials and instrumentation
High purity PdCl2 (Alfa Aesar), NiCl2·6H2O (Surchem), CuCl2·2H2O (Merck), ZnCl2 (Panreac),
CdSO4·8/3H2O (Sigma), KCN (Merck), and N,N-bis(2-hydroxyethyl)-ethylenediamine
(C6H16N2O2) (Aldrich) were used as received.
Elemental analyses for C, H, and N were carried out by standard methods using a
CHNS-932 (LECO) Elemental Analyzer at the Middle East Technical University and
İnönü University. IR spectra were recorded on a Jasco 430 FT-IR spectrophotometer with
KBr pellets from 4000 to 400 cmꢀ1 (Gaziosmanpaşa University, TURKEY). Perkin–Elmer
PYRIS Diamond TG/DTA thermal analyzer was used to record simultaneous TG, DTG,
and DTA curves under nitrogen at a heating rate of 10 °C minꢀ1 from 35 to 1350 °C using
platinum crucibles (Gaziosmanpaşa University, TURKEY). The EPR powder spectrum was

3074
S.A. Korkmaz et al.
recorded with a Bruker EMX X-band spectrometer (9.8 GHz) with about 20 mW
microwave power and 5 kHz magnetic field modulation. The 10–300 K magnetization
v
measurements were carried out on a Quantum Design PPMS system. The –T graphs were
recorded under constant magnetic fields of 0.5 kOe and 5 kOe (Gebze Institute of Technol-
ogy, TURKEY). Concurrently, all reactions were monitored on an Agilent 6890 N GC
system by GC-FID with a HP-5 column of 30 m length, 0.32 mm diameter, and 0.25 μm
film thicknesses for catalysis. Column chromatography was performed by using silica gel
60 (70–230 mesh) (solvent ratios are given as v/v) (İnönü University, TURKEY).
2.2. Synthesis
2.2.1. [Ni(N-bishydeten)Pd(CN)4] (1). Solid KCN (4 mM) and NiCl2·6H2O (1 mM)
were added to a water-ethanol solution (1 : 1; 20 mL) of PdCl2 (1 mM). To the resulting light
blue mixture, an ethanolic solution (15 mL) of N,N-bis(2-hydroxyethyl)-ethylenediamine
(N-bishydeten) (1 mM) was added dropwise and the reaction mixture was stirred for 45 min.
The lilac precipitate formed was filtered, washed with water and ethanol, and dried in air.
Yield: 60%. Elemental analyses (C, H, and N) were carried out. Anal. Calcd for 1
{C10H16N6O2NiPd (417.39)} (%): C, 28.78; H, 3.86; N, 20.13. Found: C, 28.63; H, 3.93;
N, 19.63. Infrared spectra exhibited the following absorptions: 3602, 3310 (νOH); 3195
(νNH); 2979, 2910, 2862 (νCH); 2178, 2145 (νC≡N); 1621 (δNH); 1462 (δCH2); 1113 (νCN);
1023 (νCO).
2.2.2. [Cu(N-bishydeten)Pd(μ-CN)2(CN)2]n (2). KCN (4 mM) was added to
a
water–ethanol solution (1 : 1; 20 mL) of PdCl2 (1 mM) and CuCl2·2H2O (1 mM) was added
to the resulting colorless clear solution. An ethanolic solution (15 mL) of N-bishydeten
(1 mM) was then slowly added to the green cloudy mixture. A brilliant blue solution
formed, was stirred for an hour and then filtered. After a few weeks, shiny deep blue
single crystals were obtained for X-ray analysis by slow evaporation at room temperature.
Yield: 37%. Elemental analyses (C, H, and N) were carried out. Anal. Calcd for 2
{C10H16N6O2CuPd (422.24)} (%): C, 28.45; H, 3.82; N, 19.90. Found: C, 28.45; H, 3.78;
N, 19.30. Infrared spectra exhibited the following absorptions: 3490 (νOH); 3264, 3232,
3147 (νNH); 2985, 2952, 2885, 2835 (νCH); 2187, 2143 (νC≡N); 1598 (δNH); 1455 (δCH2);
1130 (νCN); 1060 (νCO).
2.2.3. [Cu(N-bishydeten)2][Pd(CN)4] (3). The synthesis of 3 was carried out using the
same procedure as described for 2, but this time 2 mM N-bishydeten was added, yielding
prism-shaped dark violet single crystals by slow evaporation. Yield: 37%. Elemental analy-
ses (C, H, and N) were carried out. Anal. Calcd for 3 {C16H32N8O4CuPd (570.44)} (%):
C, 33.69; H, 5.65; N, 19.64. Found: C, 33.94; H, 5.61; N, 19.71. Infrared spectra exhibited
the following absorptions: 3385, 3289 (νOH); 3229, 3151 (νNH); 2979, 2949, 2889 (νCH);
2127 (νC≡N); 1595 (δNH); 1471 (δCH2); 1152 (νCN); 1083, 1059 (νCO).
2.2.4. [Zn(N-bishydeten)Pd(CN)4] (4). 4 was synthesized by the procedure adopted for
1 using ZnCl2 instead of NiCl2·6H2O. Yield: 31%. Elemental analyses (C, H, and N) were

Tetracyanidopalladate(II)
3075
carried out. Anal. Calcd for 4 {C10H16N6O2ZnPd (424.08)} (%): C, 28.32; H, 3.80; N,
19.82. Found: C, 28.83; H, 4.00; N, 19.37. Infrared spectra exhibited the following absorp-
tions: 3316 (νOH); 3271, 3142 (νNH); 2967, 2922, 2871, 2838 (νCH); 2164, 2137 (νC≡N);
1585 (δNH); 1474 (δCH2); 1161 (νCN); 1070, 1016 (νCO).
2.2.5. [Cd(N-bishydeten)2][Pd(CN)4] (5). 5 was synthesized by the procedure adopted
for 3 using CdSO4·8/3H2O instead of CuCl2·2H2O. Yield: 44%. Elemental analyses (C, H,
and N) were carried out. Anal. Calcd for 5 {C10H16N6O2CdPd (619.31)} (%): C, 31.03;
H, 5.21; N, 18.09. Found: C, 31.31; H, 5.21; N, 18.28. Infrared spectra exhibited the
following absorptions: 3353 (νOH); 3353, 3292 (νNH); 2970, 2883, 2829 (νCH); 2141, 2129
(νC≡N); 1595 (δNH); 1450 (δCH2); 1146 (νCN); 1079 (νCO).
2.3. Catalysis studies
2.3.1. General procedure for the Heck coupling reaction. 1 (1.0%, molar ratio), aryl
bromide (1.0 mM), styrene (1.5 mM), Cs2CO3 (2 mM), and DMF (3 mL) were added to a
small Schlenk tube in air and the mixture was heated at 80 °C for 6 h. When the reaction
was completed, the mixture was cooled, extracted with ethyl acetate/hexane (1 : 5), and
filtered through a pad of silica gel with copious washing, and then concentrated and puri-
fied using flash chromatography on silica gel. The same procedure was performed for 2
and 3 using K2CO3 instead of Cs2CO3, and the reaction mixtures were heated for 15 h.
The purity of the compounds was checked by NMR and GC, and the yields were based
on aryl bromide. All reactions were monitored by GC-FID with an HP-5 column of 30 m
length, 0.32 mm diameter, and 0.25 μm film thicknesses.
2.3.2. General procedure for the Suzuki coupling reaction. 1 (1.0 mM%), aryl
bromide (1.0 mM), phenylboronic acid (1.5 mM), Cs2CO3 (2 mM), and dioxane (3 mL)
were added to a small Schlenk tube in air and the mixture was heated at 80 °C for 6 h. At
completion of the reaction, the mixture was cooled, extracted with ethyl acetate/hexane
(1 : 5), filtered through a pad of silica gel with copious washings, concentrated, and puri-
fied using flash chromatography on silica gel. The same procedure was performed for 2
and 3 using K2CO3 instead of Cs2CO3, and the reaction mixtures were heated for 15 h.
The purity of the compounds was checked by NMR and GC, and yields are based on aryl
bromide.
2.4. Crystallographic data collection and structure refinement
Of the synthesized complexes, 2 and 3 were obtained as single crystals for X-ray analysis.
Single crystal X-ray diffraction intensities of 2 were collected at room temperature using
a four-circle Rigaku R-AXIS RAPID-S diffractometer with a 2-D IP area detector at room
temperature. Graphite-monochromated MoKα radiation (λ = 0.71073 Å) and oscillation scan
techniques (Δω = 5° for one image) were used for data collection. The lattice parameters
were determined by least-squares on the basis of all reflections with F2 > 2σ(F2). The inten-
sity integrations, correction for Lorentz and polarization effects, and cell refinement were
performed using Crystal-Clear software [42].

3076
S.A. Korkmaz et al.
Intensity measurements of 3 were made at room temperature on a STOE IPDS 2 image
plate detector system using graphite monochromated MoKα radiation (λ = 0.71073 Å).
STOE X-AREA [44] was used for data collection and cell refinement, and STOE X-RED
[45] was used for data reduction.
The structures were solved by direct methods using SHELXS-97 [43] and nonH atoms
were refined using full-matrix least-squares with anisotropic temperature factors (SHEL-
XL-97) [43]. Calculated positive residual density and deepest hole around Pd are observed
in both structures.
C7 of N-bishydeten in 2 are disordered about a mirror plane which bisects C6, N4, N5,
Cu1, N2, C2, Pd1, C3 and N3. Due to the disorder of C7, the positions of hydrogens
attached to N5 and C6 were also disordered.
Uncoordinated hydroxyl oxygen (O2a, O2b) of N-bishydeten in 3 is positionally disor-
dered over two position with a ratio of 0.75(1)/0.25(1). Similarity restraints SAME, SIMU,
and DELU were applied to disordered oxygen.
Molecular graphics were obtained using ORTEP-3 [45] for Windows; DIAMOND [46]
and material for publication was prepared using WinGX [47] programs. Crystallographic
data for 2 and 3 are reported in table 1.
CCDC ID 881936 and CCDC ID 840626 contain the crystallographic data for 2 and 3,
respectively. These data can be obtained free charge of via https://www.ccdc.cam.ac.uk/
Table 1. Crystal data and structure refinement parameters for 2 and 3.
2
3
Empirical formula
Formula weight
F(000)
C10H16N6O2CuPd
422.23
836
C16H32N8O4CuPd
570.44
582
Temperature [K]
Crystal size [mm]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
293(2)
293(2)
0.23 ꢂ 0.14 ꢂ 0.10
0.41 ꢂ 0.35 ꢂ 0.27
Monoclinic
P21/c
10.2975(19)
7.4922(11)
16.813(3)
90
Orthorhombic
Pnma
14.9784(2)
11.8554(2)
8.5875(2)
90
β [°]
90
90
121.211(12)
90
1109.4(3)/2
1.708
γ [°]
V [Å3]/Z
1524.92(5)/4
1.839
2.583
DCalcd [g/cm3]
μ [mmꢀ1
]
1.808
h range [°]
Index ranges
2.72–26.41
2.31 – 27.55
ꢀ13 6 h 6 13,
ꢀ9 6 k 6 9,
ꢀ21 6 l 6 21
7844
ꢀ18 6 h 6 18,
ꢀ14 6 k 6 13,
ꢀ10 6 l 6 10
31,528
1503
1639/0/109
Reflections collected
Reflections observed
Data/restraints/parameters
R1/wR2
1928
2559/6/149
0.0462/0.1135
1.074
0.0324/0.0775
1.12
GooF
Absorption correction
w
Multi-scan
Integration
1/[σ2ðF02Þ+(0.0278P)2 + 0.0843P]
1/[σ2ðF02Þ+(0.0604P)2 + 0.7275P]
P ¼ ðF02 þ 2Fc2Þ=3
1.12/0.001
0.359/ꢀ0.839
P ¼ ðF02 þ 2Fc2Þ=3
1.073/0.000
0.951/ꢀ1.815
S, (Δ/σ)max
Δρmax, Δρmin (eÅꢀ3
)
n
h
i
h
io
1=2
P
P
P
P
2
2
R1 ¼ jjF0j ꢀ jFcjj= jF0j; wR2 ¼
wðF02 ꢀ Fc2Þ
=
wðF02Þ
.

Tetracyanidopalladate(II)
3077
services/structure_deposit/ or from the Cambridge Crystallographic Data Center, 12 Union
Road, Cambridge CB2 1EZ, UK; Fax: (+44) 1223-336-033 or E-mail: deposit@ccdc.cam.
ac.uk.
3. Results and discussion
3.1. FT-IR spectra
In the FT-IR spectrum of N-bishydeten, absorption bands arising from υOH and υNH2,
υCH2, δNH2, δCH2, υC–N, and υCO are observed at 3400–3250, 2948–2832, 1570, 1471,
1148, and 1036 cmꢀ1, respectively [36]. The FT-IR spectra of 1–5 exhibit absorptions that
confirm the presence of all functional groups of N-bishydeten, which coordinates via its
NH2 and OH.
The characteristic feature in spectra of metal complexes that contain cyanide are sharp
and strong bands between 2000 and 2200 cmꢀ1 resulting from υ(C≡N). The number and
positions of υ(C≡N) absorptions reveal bridging or terminal cyanide in the complexes.
Cyanide stretches of ionic cyanides such as NaCN and KCN are observed at 2080 cmꢀ1
,
and this peak shifts to 2143 cmꢀ1 in [Pd(CN)4]2ꢀ because of coordination of cyanide to
palladium as a terminal ligand. As a result of bridging cyanide (Pd–CN–M′), the cyanide
stretch is above 2143 cmꢀ1. Splitting of cyanide stretch is evidence of the existence of
bridging and terminal cyanide [48]. IR spectra of 1 and 4 exhibit two sharp bands (2178
and 2145 cmꢀ1 for 1 and 2164 and 2137 cmꢀ1 for 4) that are attributed to the presence of
both bridged and terminal CN-; the lower wavenumber corresponds to a nonbridging
cyanide and the higher wavenumber corresponds to a bridging cyanide. The intensity of
the lower wavenumber is stronger than that of the higher wavenumber. Such shifts have
been observed in cyanide-bridged complexes such as [Zn(hydeten)2Pd(CN)4] and [Cd
(hydeten)2Pd(CN)4] [39], [M(bishydeten)Pd(CN)4] (MII = Ni,Cu and Zn) [41], [Cu(dpt)Pd
(CN)4] (dpt = 3,3'-iminobispropylamine) [49], [Ni(edbea)Pd(CN)4], and [Zn2(edbea)2Pd
(CN)4] (edbea = 2,2'-(ethylenedioxy)bis(ethylamine)) [50].
Descriptions of the spectra of 2 and 3 are more useful when the crystal structures of the
complexes are known. The spectrum of 2 exhibits a split band at 2187 and 2143 cmꢀ1
,
indicating bridging and terminal cyanide. These data were confirmed by the X-ray analysis
that 2 is a polymeric substance of the form [Cu(N-bishydeten)Pd(CN)4]n. 3 has only one
absorption at 2127 cmꢀ1 from terminal cyanide in the anion. This result was confirmed by
the X-ray analysis. This has also been observed in [Cu(edbea)2Pd(CN)4] and [Cd(edbea)2]
[Pd(CN)4] [50]. In 5, the CNꢀ stretches at 2127 and 2141 cmꢀ1 correspond to nonequiva-
lent terminal CNꢀ. The lower wavenumber is attributed to the isolated [Pd(CN)4]2ꢀ; the
band at 2141 cmꢀ1 is attributed to a pair of terminal cyanides involved in different
hydrogen bonding.
3.2. X-ray single crystal analysis
Notably, varying the M (metal) : L (ligand) ratio results in formation of different structures.
2 has a composition of [Cu(N-bishydeten)Pd(CN)4] (2) with a molar ratio 1 : 1 and 3 has a
composition of [Cu(N-bishydeten)2][Pd(CN)4] (3) with a molar ratio 1 : 2.

3078
S.A. Korkmaz et al.
3.2.1. Crystal structure of {catena-poly[[dicyanido-1κ2C-μ-cyanido-1 : 2κ2C:N-[N,N-
bis(2-hydroxyethyl)-ethylenediamine-2κ4N,N',O,O']copper(II)palladium(II)]-μ-cyanido-
1 : 2'κ2 C:N]},[Cu(N-bishydeten)(μ-CN)2(CN)2]n (2). The crystal structure of 2 depicts
a 1-D cyanide-bridged polymeric zigzag chain which is isostructural with [Zn(hydeten)2Pt
(CN)4] [35] and [Cd(hydeten)2Pd(CN)4] [39] (figure 1(a)). Bridging cyanide groups are cis
in the cationic segment whereas these groups occupy trans positions in the anionic part.
Therefore, the chain of 2 can be classified as a 2,2-CT-type chain. There are only a few
examples of Pd-containing cyanide-bridged complexes exhibiting zigzag chain structures
with a 2,2-CT-type chain [39] (figure 1(b)).
Heterometallic assembly is formed by achiral [Cu(N-bishydeten)]2+ and square-planar
[Pd(CN)4]2ꢀ building blocks connected by μ–CNꢀ. N-bishydeten is bulky and tetradentate
in this compound. Thus, it surrounds Cu. The cis positions in the equatorial plane of CuII
are occupied by nitrogens of the bridging cyanide. Cu1 coordination sphere exhibits
distorted octahedral geometry with four donors from one N-bishydeten (N4, N5, O1 and
O1i) and two from different tetracyanidopalladates (N2 and N3ii) (symmetry codes: (i)
xꢀ2, ꢀyꢀ3/2, zꢀ2; (ii) xꢀ1/2, y, ꢀzꢀ3/2). Extremely long axial semi-coordination
Cu1-O1 bonds of 2 are observed. In accord with the pseudo Jahn–Teller effect, axial
Figure 1. (a) The molecular structure of polymeric 2, with the atom-numbering scheme, and (b) the zigzag chain
of polymeric structure of 2 (symmetry codes: (i) xꢀ2, ꢀyꢀ3/2, zꢀ2; (ii) xꢀ1/2, y, ꢀzꢀ3/2).

Tetracyanidopalladate(II)
3079
Cu1–O1 bond distances are longer than equatorial bond distances (Cu1–N2, Cu1–N3ii,
Cu1–N4, and Cu1–N5), as shown in table 2. The bond observed between tertiary amine
nitrogen and CuII (Cu1–N4: 2.066(3) Å) is longer than that of the primary amine nitrogen
(Cu1–N5: 1.997(4) Å), from different steric environments of the amines. Bond lengths in
the coordination environment of the CuII ion follow the order O1 > N4 > N5 > N2 > N3ii.
The Cu1–N bond distances in 2 are similar to those of other CuII complexes of this type
[36, 38, 39, 41, 49–56]. The N–Cu1–N bond angles deviate from ideal values (84.6(15)°
and 178.4(16)°), attributed to steric effects arising from the shape of the ligand. The crystal
packing of 2 is shown in figure 2.
Each PdII is coordinated by four cyanides in a square planar geometry, and the Pd1–C
and C≡N bond lengths are 1.984(4)–2.001(4) Å and 1.130(6)–1.142(5) Å, respectively.
These data are within the range of typical values for cyanide-bridged complexes containing
tetracyanidopalladate [38, 39, 49–54, 57–59]. However, a slight bending occurs at N-C-Pd
angles. There are two terminal and two bridged cyanides in [Pd(CN)4]2ꢀ, and the bridging
Pd1–C2 and Pd1–C3 bond distances (1.990(4) and 2.001(4) Å) are longer than the Pd1–C1
(1.984(4) Å) bond distance. All nitrogens of terminal [Pd(CN)4]2ꢀ moieties in 2 are
involved in intermolecular N-Hꢁ ꢁ ꢁN and O–Hꢁ ꢁ ꢁN hydrogen bonds (figure 3).
In N-H···N weak hydrogen bonds, the upper limit for the Nꢁ ꢁ ꢁN distance is 3.38 Å
[51]. In 2, N5ꢁ ꢁ ꢁN1 interactions involving H5C and H5D, respectively, are shorter than
3.38 Å (table 3).
3.2.2. Crystal structure of [Cu(N-bishydeten)2][Pd(CN)4] (3). Single crystal X-ray
analysis reveals that 3 is an ionic complex salt, isostructural with [Cu(N-bishydeten)2][Ni
(CN)4] [36] and [Ni(N-bishydeten)2][Pt(CN)4] [60]. This type of structure can be typically
seen in the literature [61–65]. In 3, N-bishydeten serves as a tridentate ligand with N,N′,O
Table 2. Selected bond distances and angles of 2.
Bond lengths (Å)
Cu1–N2
Cu1–N3
Cu1–N4
Cu1–N5
Cu1–O1
1.977(4)
1.973(3)
2.066(3)
1.997(4)
2.449(3)
Pd1–C1
Pd1–C2
Pd1–C3
C1–N1
C2–N2
C3–N3
1.984(4)
1.990(4)
2.001(4)
1.142(5)
1.130(6)
1.131(5)
Bond angles (°)
N2–Cu1–N5
N3ii–Cu1–N4
O1–Cu1–O1i
N3ii–Cu1–N2
N2–Cu1–O1
N5–Cu1–N4
N3ii–Cu1–N5
N2–Cu1–N4
N4–Cu1–O1
N5–Cu1–O1
N3–Cu1–O1
178.4(16)
174.5(15)
154.0(9)
91.7(17)
87.0(15)
84.6(15)
89.9(16)
93.8(15)
77.6(15)
92.7(15)
102.7(15)
C1i–Pd1–C1
C1–Pd1–C2
C1–Pd1–C3
C2–Pd1–C3
N1–C1–Pd1
N2–C2–Pd1
N3–C3–Pd1
C2–N2–Cu1
C3–N3ii–Cu1
C6–N4–Cu1
C4–N4–Cu1
C7–N5–Cu1
177.3(18)
88.7(9)
91.2(9)
179.7(16)
177.5(3)
178.9(4)
179.1(4)
179.8(4)
176.5(4)
108.7(3)
108.1(2)
109.7(3)
Symmetry codes: (i) xꢀ2, ꢀyꢀ3/2, zꢀ2; (ii) xꢀ1/2, y, ꢀzꢀ3/2.

3080
S.A. Korkmaz et al.
Figure 2. The crystal packing of 2.
donors. The complex salt consists of [Cu(N-bishydeten)2]2+ and [Pd(CN)4]2ꢀ, and the atom
labeling scheme is shown in figure 4.
In the structure of 3, CuII and PdII both occupy sites of inversion centers. The CuII is
six-coordinate with four nitrogens (N1, N2, N1ii and N2ii) in the equatorial plane and two
oxygens (O1 and O1ii) in the axial positions provided by the two tridentate N-bishydeten
ligands (symmetry code: (ii) 1ꢀx, 1ꢀy, 1ꢀz). The Cu1–N1 (2.004(3) Å) bond with the
nitrogen of primary amine is shorter than Cu1–N2 (2.103(3) Å) with the nitrogen
belonging to the tertiary one. This difference may be a result of steric hindrance from the
noncoordinating ethanol edge of the N-bishydeten ligand (table 4). A d9 system forms
slightly distorted and tetragonally elongated octahedral coordination. Therefore, these
Cu–N distances are significantly shorter than observed for Cu–O1 (2.401(2) Å). The Cu–N
bond distances in 3 are similar to those of other CuII complexes of this type [36, 38, 40,
41, 49–56].
The diamagnetic [Pd(CN)4]2ꢀ (figure 5) has Pd1-C bond distances identical (within 3σ),
with an average value of 1.998 Å. Like CuII, PdII in the inversion center forms linear bond
angles with cyanido carbons. The C≡N bonds (1.145(4) and 1.152(5) Å), and the
Pd1–C≡N angles (177.6(3) and 177.3(3)°) are in accord with other tetracyanidopalladates
[40, 41, 52–54, 57–59] (table 4).
The presence of nonbridging cyanide does not mean that cyanides are unimportant for
stabilization of the crystal structure. In fact, these cyanides participate in a series of bifur-
cated hydrogen bonds with NH2, CH2, and OH of N-bishydeten. All hydrogen bonds have
Dꢁ ꢁ ꢁA distances ranging from 2.84(9) to 3.13(7) Å, and are effective in forming a layered
structure (table 5, figure 6a and b).
3.3. Thermal studies
Thermal decomposition of cyanide complexes containing N-donor ligands is characterized
by liberation of the N-donor ligands followed by decomposition of the cyanide groups, as

Tetracyanidopalladate(II)
3081
Figure 3. Hydrogen bonds of 2 formed by terminal cyanide along (a) the a axis and (b) the c axis.
observed in previous studies [66–70]. The thermal decomposition of 1–5 is consistent with
this and has multi-step processes (Supplementary material). The DTA signal was automati-
cally converted to a DSC signal and the enthalpy values (ΔH, J/g) of the decomposition
steps were determined. The thermal analysis results are given in table 6.

3082
S.A. Korkmaz et al.
d(H...A)
Table 3. Hydrogen bonds of 2 (Å and °).
D–Hꢁ ꢁ ꢁA
d(D–H)
d(D...A)
\ (DHA)
N5–H5Cꢁ ꢁ ꢁN1i
N5–H5Dꢁ ꢁ ꢁN1ii
O1–H1ꢁ ꢁ ꢁN1ii
0.90
0.90
0.82
2.30
2.15
2.30
3.01(4)
3.01(4)
2.99(4)
135.73
158.96
143.32
Symmetry codes: (i) ꢀx + 1/2, ꢀy, z + 1/2; (ii) ꢀx + 1/2, y + 1/2, z + 1/2.
Figure 4. The molecular structure of 3 showing the atom numbering scheme (symmetry codes: (i) ꢀx, 1ꢀy, ꢀz;
(ii) 1ꢀx, 1ꢀy, 1ꢀz).
Table 4. Selected bond distances and angles of 3.
Bond lengths (Å)
Cu1–N1
Cu1–N2
Cu1–O1
2.004(3)
2.103(3)
2.401(2)
Pd1–C8
Pd1–C7
C7–N3
C8–N4
1.997(3)
1.996(4)
1.145(4)
1.152(5)
Bond angles (°)
N1–Cu1–N1ii
N2–Cu1–N2ii
O1–Cu1–O1ii
N1–Cu1–N2ii
N1–Cu1–N2
N1–Cu1–O1ii
N1–Cu1–O1
N2–Cu1–O1ii
N2–Cu1–O1
C1–N1–Cu1
180.0
C2–N2–Cu1
N3–C7–Pd1
N4–C8–Pd1
C8–Pd1–C8i
C7–Pd1–C7i
C8–Pd1–C7
C8–Pd1–C7i
C3–N2–Cu1
C5–N2–Cu1
107.0(2)
180.0(18)
180.0(16)
84.3(11)
95.7(11)
97.2(10)
82.8(10)
77.6(10)
102.4(10)
106.5(2)
177.6(3)
177.3(3)
180.0(2)
180.0(2)
92.5(12)
87.5(12)
109.8(18)
106.3(2)
Symmetry codes: (i) ꢀx, 1ꢀy, ꢀz; (ii) 1ꢀx, 1ꢀy, 1ꢀz.
The thermal degradation of 1 is realized in two stages which can be distinguished clearly.
The TG curve for 1 indicates that it is stable to 238 °C, at which decomposition begins.
From 238 to 428 °C, weight loss of 48.40% corresponds to release of one N-bishydeten and
two cyanides (Calcd 47.98%) by an endothermic process. In the second step, decomposition
of the remaining two cyanides occurs from 438 to 733 °C with weight loss of 11.53%
(Calcd 12.47%). The final product is a mixture of metallic Ni+Pd (solid residue 40.07%;
Calcd 39.55%) for 1.

Tetracyanidopalladate(II)
3083
Figure 5. 3-D view of 3. Hydrogens are omitted for clarity.
Table 5. Hydrogen bonds of 3 (Å and °).
D–Hꢁ ꢁ ꢁA
d(D–H)
d(H...A)
d(D...A)
\ (DHA)
N1–H1Cꢁ ꢁ ꢁN4i
N1–H1Dꢁ ꢁ ꢁN4ii
O1–H1ꢁ ꢁ ꢁN3iii
0.90
0.90
0.82
0.82
0.82
2.29
2.17
2.33
2.10
2.11
3.13(7)
3.05(7)
3.11(4)
2.86(5)
2.84(9)
155.7
166.5
158.0
154.6
148.9
O2A–H2Cꢁ ꢁ ꢁN3iv
O2B–H2Dꢁ ꢁ ꢁN3iv
Symmetry codes: (i) x, 5/2ꢀy, 1/2 + z; (ii) ꢀx, y + 1/2, ꢀz + 1/2; (iii) xꢀ1, 5/2ꢀy, 1/2 + z; (iv) x, ꢀ1 + y, z.
The thermal decomposition of 2 is similar to 1, consisting of three stages. Two
degradation steps at 145–206 °C and 206–438 °C with weight loss of 47.22% (Calcd
47.43%) correspond to release of one N-bishydeten and two cyanides (these steps are
consecutive). The last stage from 438 to 735 °C, with observed weight loss of 12.32%,
involves decomposition of two cyanides. The weight increase indicates formation of metal
oxide in the last stage, arising from formation of CuO; the final product is a mixture of
metallic CuO+Pd (solid residue 41.04%; Calcd 40.25%) for 2 [54,71].
The thermal decomposition of 3 occurs in three steps at 167–259 °C, 259–553 °C, and
553–1214 °C corresponding to release of two N-bishydeten and four cyanides. 4
decomposes in three steps with liberation of N-bishydeten and four cyanides at 209–294,
294–484, and 484–804 °C.
The DTA profile of 5 shows that the endothermic transition at 125 °C corresponds to a
solid–solid transition because no melting was detected. The same behavior was also
observed for [Cd(hydeten)2Pt(CN)4] [35] and [Cu(hydeten)2Pd(CN)4] [38]. The first step
which proceeds from 179 to 417 °C with an observed weight loss of 47.78% corresponds
to decomposition of two N-bishydeten ligands (DTAmax 259 °C; Calcd 47.86%). The four
cyanides leave upon further heating, and Cd is liberated with a DTGmax at 927 °C. The
final thermal decomposition product is metallic Pd (solid residue 17.73%; Calcd 17.19%).
The thermal stabilities determined from DTGmax values of the first decomposition stages
change in the order of 1 > 5 > 4 > 3 > 2 and deviate from the Irving-Williams series. The
most probable thermal decomposition mechanisms of 1–5 are illustrated in scheme 1.

3084
S.A. Korkmaz et al.
Figure 6. Hydrogen bonds of 3 along (a) the a axis and (b) the b axis.
3.4. Catalytic studies
3.4.1. Heck coupling reaction. The palladium-catalyzed Heck arylation has proven to
be one of the most powerful means of forming carbon–carbon bonds in organic synthesis
[72] (scheme 2). This efficient metal-catalyzed cross-coupling reaction is regulated by a
number of factors such as base, solvent, temperature, and reaction time [73].
The effects of Cs2CO3, K2CO3, K3PO4, and t-BuOK on the reaction system were stud-
ied; Cs2CO3 was effective, whereas the other bases resulted in lower conversions. Solvents
such as DMF, DMSO, toluene, dioxane, THF, and CH3CN had remarkable effects on the

Tetracyanidopalladate(II)
3085
Table 6. Thermoanalytical data for 1–5.
Mass loss,
Δm (%)
Complex Stage Temperature range (°C) DTGmax. (°C)
ΔH (J/g)
Obs.
Calcd Liberated group
1
2
1
2
1
2
3
1
2
3
1
2
3
1
2
3
238–428
428–733
145–206
206–438
438–735
167–259
259–553
553–1214
209–294
294–484
484–804
179–417
417–905
905–1350
354
586
181
317
544
236
288
1068
256
311
497
259
804
927
17000.26 48.40 47.98 C6H16N2O2 + 2CN
2085.71 11.53 12.47 2CN
ꢀ141.65
2.15 47.43 C6H16N2O2 + 2CN
1426.68 45.07
ꢀ408.90 11.74 12.32 2CN
3413.26 26.39 25.98 C6H16N2O2
ꢀ15684.23 32.69 32.69 C6H16N2O2+2CN
3
4
5
63136.08
8.82
9.12 2CN
197.71 19.72 34.94 C6H16N2O2
246.02 14.11
ꢀ259.55 25.02 24.54 4CN
4346.09 47.78 47.86 2C6H16N2O2
827.42 16.48 16.80 4CN
ꢀ42921.42 18.01 18.15 Cd
238-428oC
428-733oC
-2CN
PdNi
[Ni(C6H16N O )Pd(CN) ]
[NiPd(CN)2]
[CuPd(CN)2]
(1)
2
2
4
-C6H16N2O2
-2CN
145-438oC
438-735oC
-2CN
[Cu(C6H16N2O2)Pd(CN)4] (2)
CuO+Pd
-C6H16N2O2
-2CN
167-259oC
259-553oC
553-1214oC
-2CN
[Cu(C6H16N2O2)2][Pd(CN)4] (3)
[Cu(C6H16N2O2)][Pd(CN)4]
[CuPd(CN)2]
CuPd
-C6H16N2O2
-C6H16N2O2
-2CN
209-484oC
484-804oC
-4CN
[Zn(C6H16N2O2)Pd(CN)4] (4)
[ZnPd(CN)4]
ZnPd
-C6H16N2O2
179-417oC
417-905oC
-4 CN
905-1350oC
-Cd
[Cd(C6H16N O ) Pd(CN) ]
(5)
4
[CdPd(CN)4]
Pd
CdPd
2
2 2
-2C6H16N2O2
Scheme 1. Estimated thermal decomposition schemes for 1–5.
1 (1 mmol %)
Br
R
+
DMF, 80 0C, 6 h
Cs2CO3 (2 equiv.)
R
Scheme 2. The Heck reaction of aryl halides with styrene.
coupling reaction. To verify the R group effect in Heck coupling, we investigated a
series of reactions involving different R groups (table 7). The optimized conditions of the
Pd-catalyzed cross-coupling of 4-bromobenzene with styrene involved performing the
reaction in DMF at 80 °C using 1 mol% of 1, 2, or 3. Two equivalents of Cs2CO3
were added for 1 and two equivalents of K2CO3 were added for 2 and 3; the best
conversions occurred within 6 h for 1 to obtain acceptable yields. The results are
summarized in table 7 for these reactions.

3086
S.A. Korkmaz et al.
Table 7. The Heck coupling reaction of aryl bromides with styrene.
R
Catalyst
Yielda (%)
COCH3
CHO
CH3
H
1
1
1
1
48
43
31
35
aReaction conditions: 1.0 mM of R–C6H4Br-p, 1.5 mM of styrene, 2 mM Cs2CO3, 1 mM% Pd complex, DMF
(3 mL). Purity of compounds was checked by NMR and yields are based on aryl bromide. All reactions were
monitored by GC, 80 °C, 6 h. b2 mM K2CO3 as a base, 15 h.
Under these reaction conditions, a wide range of aryl bromides bearing electron-donating
or electron-withdrawing groups react with styrene, affording the coupled products in yields
of 31–48% (table 7, entries 1–4). The activity follows the order R=COCH3
> CHO > H > CH3. Enhancements in activity, although less significant, were also observed
when 4-bromomethylbenzene (entry 3) was used instead of 4-bromoacetophenone (entry 1).
Under the optimized conditions, 2 and 3 do not catalyze the Heck reaction; therefore, these
complexes are much more stable. Additionally, under these conditions, 1 proved to be a
more effective catalyst than 2 and 3.
3.4.2. Suzuki coupling reaction. The Suzuki reaction is an extremely powerful method
for C–C bond formation [27, 74, 75]. To survey the parameters for the Suzuki reaction, we
selected Cs2CO3, K2CO3, and K3PO4 as bases and DMF, DMSO, toluene, dioxane, THF,
and CH3CN as solvents. We found that reactions performed with Cs2CO3 and 1 in dioxane
at 80 °C for 6 h are best. The use of 1% mM 2 and 2 mM K2CO3 in dioxane at 80 °C led to
the best conversion within 15 h. Table 8 summarizes the results obtained in the presence of
1 and 2 (entries 1–5). The activity follows the order CHO > CH3 > COCH3 > H. The highest
catalytic activity observed was 61% for 1 and 75% for 2 (table 8). The scope of the
cross-coupling reaction with respect to aryl bromide was also investigated; 2 is an effective
complex for coupling unactivated, activated, and deactivated bromides (scheme 3).
3.5. EPR studies
We were unable to obtain EPR spectra of 1 because of the short relaxation times of NiII in
an octahedral environment at room temperature.
Table 8. The Suzuki coupling of aryl bromides with phenylboronic acid.
R
Catalyst
Yielda (%)
COCH3
CHO
CH3
1
1
1
1
2
49
61
56
H
39
COCH3
75b
aReaction conditions: 1.0 mM of R–C6H4Br-p, 1.5 mM of phenylboronic acid, 2 mM Cs2CO3, 1 mM% Pd com-
plex, dioxane (3 mL). Purity of compounds was checked by NMR and yields are based on aryl bromide. All reac-
tions were monitored by GC, 80 °C, 6 h. b2 mM K2CO3 as a base, 15 h.

Tetracyanidopalladate(II)
3087
1 (1 mmol %)
R
B(OH)2
R
Br
+
Dioxan, 80 oC, 6 h
Cs2CO3 (2 equiv.)
Scheme 3. The Suzuki coupling of aryl bromides with phenylboronic acid.
The room temperature powder EPR spectra of 2 and 3 are shown in Supplementary
material. Hyperfine splitting could not be resolved because of line broadening originating
from spin-exchange and spin-orbit interactions that result from excess spin concentration.
The g‖ and g\ values extracted from the powder spectra are: g‖ = 2.224, g\ = 2.060 for 2
and g‖ = 2.252, g\ = 2.063 for 3. These g parameters indicate that the paramagnetic center
for each powder sample is axially symmetric, attributed to a CuII (S = 1/2, I = 3/2). Because
g‖ > g\ > ge (free electron g value, ge = 2.0023), it can be concluded that CuII is in tetrago-
nally distorted octahedral sites (D4h) elongated along the z-axis, and the ground state of
the paramagnetic electron is dx2ꢀy2 (2B1g state) [76–79].
The PdII ions in these complexes have square-planar coordination geometries and are
low spin (S=0) and thus, diamagnetic. For this reason, no EPR signal for Pd ions is
observed.
3.6. Magnetic properties
The magnetic susceptibility of 1–3 was obtained from 10 to 300 K. The temperature
dependence of the molar magnetic susceptibilities (χm) and χmT are shown in figures 7–9
for these complexes. The variable temperature dependence of χm for 1 and 2 was fitted
using the relation C/(T–h), where C is the Curie constant and h is the Weiss constant [80].
From this fitting process, the relationships C = 1.2006 0.0002 emuK/mol.Oe and
h = ꢀ0.968 0.002 K were determined for 1 and C = 0.459 0.00004 emuK/mol.Oe and
Figure 7. The temperature dependence of the molar magnetic susceptibility χm for 1. Solid line represents a fit
by the Curie–Weiss law. Inset: the temperature dependence of χmT.

3088
S.A. Korkmaz et al.
Figure 8. The temperature dependence of the molar magnetic susceptibility χm for 2. Solid line represents a fit
by the Curie–Weiss law. Inset: the temperature dependence of χmT.
Figure 9. The temperature dependence of the molar magnetic susceptibility χm for 3. Solid line represents a fit
by the Curie–Weiss law. Inset: the temperature dependence of χmT.
h = ꢀ1.022 0.001 K for 2. The effective magnetic moment, μeff, was calculated to be 3.10
for 1 and 1.917 for 2 using the relation μeff = 2.83(C)1/2 and is expressed in Bohr magn-
etons (μB). The values of μeff for 1 and 2 are greater than the spin-only value due to mix-
ing of some spin-orbital angular momentum from excited states via spin-orbit coupling
[81].

Tetracyanidopalladate(II)
3089
For 3, the temperature dependence of χm was fitted using the relation α + C/(T–h),
where α is the temperature-independent susceptibility [80]. Based on this fitting, the
relationships C = 0.39778 0.00005 emuK/mol.Oe, α = 0.00029 0.0000005 emu/mol.Oe,
and h = ꢀ0.672 0.001 K were determined. Thus, there is temperature-independent para-
magnetism (α), originating from coupling between the ground state and the excited states
due to orbital moments of the d electrons or from the presence of conducting electrons.
The effective magnetic moment for 3, μeff, was calculated to be 1.783 in Bohr magnetons
(μB).
Below 10 K, there may be a slight antiferromagnetic interaction in 1–3, as observed
from the insets of figures 7–9. The insets also measure effective magnetic moment
pffiffiffiffiffiffiffiffi
(μeff = 2.83 vmT). This magnetic interaction might be between and within the chains
involving CNꢀ bridges and hydrogen bonds.
4. Conclusion
Five heterometallic cyanide complexes containing tetracyanidopalladate and N-bishydeten
have been prepared and two of these complexes were characterized using X-ray crystallog-
raphy. Different assembly chemistry of [Cu(N-bishydeten)n]+2 (n = 1 or 2) with the
[Pd(CN)4]2ꢀ complex anion is observed. N-bishydeten is a tetradentate ligand in 2 and
tridentate in 3 with NN′O donors.
The N–Hꢁ ꢁ ꢁ(N≡C) interactions are shorter than the upper limit for an Nꢁ ꢁ ꢁN distance.
IR spectra of 1–5 were recorded and confirmed the presence of all functional groups in the
complexes. According to DTGmax values, the first decomposition stage changes
1 > 5 > 4 > 3 > 2 and deviates from the Irving-Williams series.
1–3 were tested as catalysts, and 1 proved to be more effective in Heck coupling and 2
is an effective complex for coupling unactivated, activated, and deactivated bromides in a
Suzuki reaction.
Below 10 K, there may be a slight antiferromagnetic interaction in the structures of 1–3.
This magnetic interaction might be between and within chains involving CNꢀ bridges and
hydrogen bonds.
Acknowledgments
The authors thank the Scientific and Technical Research Council of Turkey (TUBİTAK,
Grant TBAG-104T205) and the Gaziosmanpaşa University Research Foundation (Grant
2010/110) for financial support.
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