Indian Journal of Chemistry

Vol. 57A, November 2018, pp. 1351-1357

C-S bond cleavage influenced by metal coordination in Zn(II) bound Schiff base
complex: synthesis, structural characterization, catecholase and phenoxazinone
synthase activities
Ayon Kanti Ghosha, Arnab Chatterjeea, Sarat Chandra Kumara, Chandra Shekhar Purohitb & Rajarshi Ghosh a,*
a
Department of Chemistry, The University of Burdwan, Burdwan 713 104, India
b
Department of Chemical Sciences, National Institute of Science Education and Research, Bhubaneswar 751 005, India
Email: [email protected]
Received 1 March 2018; revised and accepted 23 October 2018

A new zinc(II) Schiff base complex (1) has been synthesized and X-ray crystallographically characterized. It crystalizes
in P2/c space group with monoclinic crystal system. One C-S bond in a (N,S,O) donor organic ligand has been found to be
cleaved on reaction with the zinc(II) perchlorate hexahydrate to yield 1 with new ligand formulation. Complex 1 is found to
be both catecholase and phenoxazinone synthase active in MeOH at room temperature. Michaelis-Menten kinetics for each
of the activities has been investigated. The turn over numbers for catecholase and phenoxazinone synthase activities are
4.31×102 and 5.27×105 h-1, respectively.

Keywords: Zinc(II), Schiff base, X-ray structure, Catecholase activity, Phenoxazinone synthase activity

Molecular models of the active sites of different includes activation (cleavage) of different bonds
metalloenzymes and their use to activate like C-H15, C-C 16, C-S17, etc., upon transition
molecular/aerial oxygen for different organic metal coordination. Among these the C-S bond
transformations are very much important as the method cleavage is important not only in organic synthesis17 but
is easy, green as well as economic1,2. Mimicking also in petroleum industry where removal of organo-
catechol oxidase is a trend in synthetic coordination sulphur compounds present in petroleum-based
chemistry since its discovery in 19983-6. Catechol feedstock18 is important.
oxidase is a copper containing protein7 which catalyses
the catechol-quinone conversion (Scheme 1) in the
plant tissues. Copper compounds of different nuclearity
which catalyse to convert catechol to quinone in
laboratory are reported in literature4-6. Phenoxazinone
synthase is another multicopper oxidase which is found
in the bacterium Streptomyces antibioticus. This is
responsible for six electron oxidative coupling of two
molecules of an o-aminophenol derivative, 4-methyl-3-
hydroxyanthraniloyl pentapeptide to phenoxazinone
chromophore (Scheme 2). Few copper complexes
which mimic the phenoxazinone synthase are reported
in literature8. Now a days a number of non-copper
complexes of different nuclearity are found in literature
which are catalysing catecholase and/or phenoxazinone
synthase activities9-14. Few redon inactive Zn(II)
complexes which are redox inactive are known to
catalyse those activities11,12.
Different synthetic strategies towards synthesis of
coordination molecules of different functionalities
1352 INDIAN J CHEM, SEC A, NOVEMBER 2018

In our present report, synthesis of a separated by filtration. Salicyaldehyde (8 mmol, 0.97 g)

mononuclear Zn(II) complex [Zn(L)2] [HL = 2-((E)- was added to this solution of 2-(3-aminopropylthio)ethanol
(3-mercaptopropylimino)methyl)phenol] (1) is found to and this mixture was refluxed for 4 h. The ligand H2L
pass through a C-S bond cleavage in the original organic was thus obtained. The synthesized H2L was extracted
ligand framework. The synthesized compound is from the mixture by solvent extraction.
crystallographically characterized and shows catecholase Yield, 1.434 g (75% based on aldehyde).
and phenoxazinone synthase activities in MeOH at Anal (%):Calc.: C12H17NO2S (HL): C, 60.22; H, 7.16;
room temperature. N, 5.85. Found: C, 60.12; H, 7.23; N, 5.89. IR cm-1
(KBr): 3361s, 2866-2922w. 1629(s), 754(m); UV-vis
Materials and Methods (MeOH, nm): λmax nm: 214, 254, 315, 401. 1H NMR
High purity 2-mercaptoethanol, 3-chloropropylamine, δ (ppm): 2.17 (q, J = 6.4 Hz, 2H), 2.63 (t, J = 7.2 Hz,
salicylaldehyde and zinc(II) perchlorate hexahydrate 2H), 2.88 (t, J = 6.0 Hz, 2H), 3.62 (t, J = 6.0 Hz, 2H),
were purchased from Sigma Adrich, India and used as 3.90 (t, J = 6.0 Hz, 2H), 6.87–6.89 (m, 1H), 6.90–6.96
received. (m, 1H), 7.23–7.27 (m, 1H), 7.28–7.33 (m, 1H),
Elemental analyses (carbon, hydrogen and 8.37 (d, J = 10.8 Hz, 1H), 13.28 (bs, 1H).
nitrogen) were performed on a Perkin-Elmer 2400
CHNS/O elemental analyser. IR spectrum was Synthesis of Complex 1
recorded (KBr discs, 4000–300 cm-1) using a Solid zinc(II) perchlorate hexahydrate (0.1 mmol,
Perkin-Elmer RX1 FTIR spectrometer. Ground 0.037 g) was slowly added to the hot ethanolic solution
state absorption was measured with a JASCO of H2L (0.2 mmol, 0.048 g) with continuous stirring
V-530 UV-vis spectrophotometer. for 3 h. The brown colour of the ligand solution
Synthesis of H2L changed to pale yellow on dissolution of the metal salt.
2-Mercaptoethanol (8 mmol, 0.625 g) was added This reaction mixture was kept open in air for slow
gradually into the cooled sodium ethoxide solution evaporation. Light orange coloured X-ray quality
which was prepared by the addition of metallic sodium crystals of 1, where one C-S bond of the ligand
to dry ethanol with continuous stirring. Then framework was found to be cleaved were obtained after
3-chloropropylamine (8 mmol, 1.04 g) was added keeping the solution in open air after a week or so. This
slowly to this reaction mixture and the mixture was resulted in a new Zn(II) bound ligand HL (molecular
stirred for about 1 h. During this stirring, sodium structure of the complex was confirmed X-ray
chloride was precipitated , which confirms the crystallographically later) (Scheme 3).
formation of the 2-(3-aminopropylthio)ethanol Yield, 0.03174g (70% based on metal salt).
(Scheme 3).The precipitated sodium chloride was Anal (%):Calc.: C20H24N2O2S2Zn (1): C, 52.87; H, 5.32;
 GHOSH et al.: C-S BOND CLEAVAGE INFLUENCED BY Zn(II) 1353

N, 6.17. Found: C, 52.51; H, 5.35; N, 6.14. IR cm-1 (KBr): microscope. Diffraction data at 293(2) K were
2915s, 1622s, 752s, 654s. UV-vis (MeOH, nm): λmax () collected on a Smart Apex CCD diffractometer
at 239, 258, 321 and 363. using Mo-K radiation (λ = 0.71073 Å). Systematic
absence led to the identification
X-ray diffraction study of space group P2/c. The structure was solved by
A summary of the crystallographic data and direct methods, and the structure solution
structure refinement parameters are given in and refinement were based on |F|2. All
Table 1. Single crystals [size: 0.23×0.30×0.38 mm3] non-hydrogen atoms were refined with anisotropic
of 1 were obtained by slow evaporation of MeOH- displacement parameters whereas hydrogen
H2O solution of the reaction mixture. Light orange atoms were placed in calculated positions where
crystals suitable for X-ray crystallographic analysis possible and given isotropic U values 1.2 times that
were selected following examination under a of the atom to which they are bonded. At
convergence the final residuals were R1 = 0.0559;
Table 1 –– Crystal data and structure refinement parameter of wR2 = 0.1526 with I2(I), goodness-of-fit = 1.041.
compound 1 The final differences Fourier map showed the
CCDC No. 1563187 maximum and minimum peak heights at 0.573 and
Emperical formula C20H24 N2O2 S2Zn -0.493 e Å-3. All calculations were carried out
Formula weight 453.96 using SHELXTL 5.1019.
Temperature (K) 293(2)
Wavelenght (Å) 0.71073 Results and Discussion
Crystal system Monoclinic Synthesis and formulation
Space group P2/c The organic ligand H2L was prepared by
Unit cell dimensions abstracting the proton of 2-mercaptoethanol by
a (Å) 18.4340(7) sodium ethoxide which was prepared in situ.
b (Å) 5.7108(2) 3-Chloropropylamine was mixed with this reaction
c (Å) 20.3467(7)
mixture to get 2-(3-aminopropylthio)ethanol which on
α (˚) 90
further condensation with salicyaldehyde resulted in
β (˚) 97.354(2)
the ligand H2L. This was characterized through
γ (˚) 90
proton NMR (Supplementary Data, Fig. S1a and
Volume (Å3) 2124.34(13)
S1b). Zinc(II) perchlorate was added to the solution of
Z 4
Calculated densisty Dcalc (mg m-3) 1.820
the H2L with stirring. This produced the metal
Absorption coefficient(mm-1) 1.600 complex 1 which on single crystal X-ray diffraction
F(000) 1176 revealed that one of the C-S bonds in the ligand
Crystal size (mm3) 0.38×0.3×0.23 framework was cleaved and the zinc(II) complex of
Theta range for data collection (˚) 1.114 - 25.378 HL (which appeared as a new metal bound ligand)
Index ranges –22 ≤ h ≤ 22, –5 ≤ k ≤6, was generated. C-S bond cleavage in presence of
–24 ≤ l ≤24 metal salts reported in literature17. As we used Zn(II)
Reflections collected 19576 perchlorate for the synthesis of the metal complex, a
Independent reflections 3886 [Rint = 0.0475] question may arise whether the resulting perchloric
Completeness of theta 99.8 % [θ = 25.378] acid resulted in the reaction is cleaving the C-S bond
Absorption correction Multi-scan of the ligand framework or not. To evaluate this
Tmax and Tmin 0.5969 and 0.7452 aspect we repeated the reaction with Zn(II) acetate
Refinement method Full matrix and got the same complex with the same molecular
Data/restrains/parameters 3886/0/ 236 structure as from the single crystal X-ray diffraction
Goodness-of fit (GOF) F2 1.041 (Supplementary Data, Table S1). Here the resulting
Final R index [l >2σ(l)] R1 = 0.0559 and acetic acid being weak might not be able to cleave the
wR2 = 0.1526 C-S bond. So it is clearly seen that
R index (all data) R1 = 0.0946 and
metal coordination is playing the sole role for
wR2 = 0.1790
0.607, –0.439
this very cleavage and not the acid which was formed
Largest difference between peak and
hole (e Å-3) as a by-product.
1354 INDIAN J CHEM, SEC A, NOVEMBER 2018

X-ray structure This makes it easily oxidizable to the corresponding

The thermal plot (ORTEP) of 1 and X-ray ortho-quinone derivative 3,5-di-tert-butyl quinone
crystallographic data are provided in Fig. 1 and Table 1, (3,5-DTBQ) which is highly stable and shows a
respectively. Complex 1 crystalizes in P2/c space maximum absorption at 401 nm in methanol20.
group. Considering bond angle and bond distance data Spectral bands at 239, 258, 321 and 363 nm appear in
(Table 2) coordination geometry around zinc(II) centre the electronic spectrum of complex 1, whereas
is best described as distorted tetrahedron. Only the 3,5-DTBC shows a single band at 282 nm. Upon
imine nitrogens [N(2) and N(2i)] and phenoxy oxygens treatment of methanolic solution of 1 equivalent of 1
[O(1) and O(1i)] are coordinated to meta centres. The into 100 equivalents of 3,5-DTBC under aerobic
thiol groups remain uncoordinated. The maximum and conditions, the repetitive UV-vis spectral scan was
minimum bond distances of the metal centre with the recorded (Fig. 2). The colourless solution gradually
coordinated atoms are 2.005 and 1.917 Å ( = 0.088 Å) turned deep brown which indicated conversion of 3,5-
respectively. DTBC to 3,5-DTBQ. In UV-vis spectrophotometer,
after this addition, the spectral scan shows very
Catecholase activity smooth increase of a quinone band at around ~390 nm
Spectrophotometric study which shifts ultimately to 401 nm, as reported by
The catecholase activity study was carried out Krebs et al20. The same reaction was carried out by
using the substrate 3,5-di-tert-butyl catechol scaling up the reagents and 3,5-DTBQ was purified
(3,5-DTBC) having two bulky t-butyl substituents on by column chromatography. Chromatographically
the ring and low quinone-catechol reduction potential. pure 3,5-DTBQ was characterized by determining its
melting point (~110 °C) which agreed well with that
reported in literature21.
The time dependent change in absorbance at a
wavelength of 401 nm, which was characteristic of
3,5-DTBQ in methanol, was observed for 60 min to
comprehend the reaction kinetics and find out the
reaction rate between 3,5-DTBC and 1. The
difference in absorbance ΔA at 401 nm, was plotted
against time to obtain the rate/velocity for that
particular catalyst to substrate concentration ratio
(Supplementary Data, Fig. S2). A first-order catalytic
reaction is observed, with rate 3.36×10-4 min-1.
Control experiments were done with only
3,5-DTBC, and 3,5-DTBC and Zn(II) perchlorate in
Fig. 1 –– ORTEP of Complex 1 with 20% ellipsoid probability methanol. No peak growth at ~400 nm was observed
(hydrogen atoms have been excluded for clarity).

Table 2 — Bond lengths (Å) and bond angles (˚) of compound 1

Bond lengths (Å)
Zn(1)-O(1) 1.917(3)
Zn(1)-O(1) 1.917(3)
Zn(1)-N(2) 2.005(4)
Zn(1)-N(2) 2.005(4)
Bond angles (○)
O(1)-Zn(1)-N(2) 95.85(14)
O(1)-Zn(1)-N(2) 122.77(15)
O(1)-Zn(1)- O(1) 108.7(2)
O(1)-Zn(1)-N(2) 95.85(14)
O(1)-Zn(1)-N(2) 122.77(15)
Fig. 2 –– Change in spectral pattern of complex 1 after reaction
N(2)-Zn(1)-N(2) 113.0(2) with 3,5-DTBC (the reaction was observed for 6 h in methanol).
 GHOSH et al.: C-S BOND CLEAVAGE INFLUENCED BY Zn(II) 1355

in UV-vis repetitive scan which continued for 2 h quinone [3,5-DTBQ]-Na+ (Supplementary Data, Fig.
(Supplementary Data, Figs. S3 and S4). S6). To obtain a mechanistic inference of the
catecholase activity and to get an idea about the
Enzyme kinetics study complex-substrate intermediate, the formation of a
Kinetic experiments were performed complex-substrate adduct is identified by the peak at
spectrophotometrically with complex 1 and the m/z = 675.59 (Supplementary Data, Fig. S7). The
substrate 3,5-DTBC in methanol, thermostated at proposed structure of this adduct is given in Scheme 4.
20 °C. The complex solution (0.04 mL), with a The catechol derivative, 3,5-DTBC gets oxidised to
constant concentration of 1×10-4 M, was added to 2 mL quinone in presence of oxygen. The aerial oxygen that
of 3,5-DTBC of a particular concentration (varying its oxidises 3,5-DTBC to 3,5-DTBQ in this process is
concentration from 1×10-3 M to 1×10-2 M) to achieve converted to H2O2. H2O2 thus liberated was identified
the final concentration of the complex as 1×10-4 M. and characterized spectrophotometrically. Details of
The conversion of 3,5-DTBC to 3,5-DTBQ was spectrophotometric detection of H2O2 in the oxidation
monitored with time at a wavelength of 401 nm for reaction22 are given as supplementary data.
solutions in MeOH. The rate for each concentration of
the substrate was determined by the initial rate method. Phenoxazinone synthase activity
The rate versus concentration of substrate data Spectrophotometric study
were analyzed on the basis of Michaelis-Menten The phenoxazinone synthase activity study was
approach of enzymatic kinetics to obtain the carried out using the substrate o-aminophenol
Lineweaver-Burk (double reciprocal) plot as well as (OAPH). OAPH shows bands at 286 and 232 nm in
the values of the various kinetic parameters viz.,Vmax,
KM and Kcat. The observed rate versus [substrate] plot
as well as Lineweaver-Burk plot in methanol
solutions are given in Fig. 3. The kinetic parameters
are listed in Supplementary Data, Table S2. The
turnover number (Kcat) is 4.31×102 h-1.

Reaction mechanism
The catalytic process follows a two-step
mechanistic pathway. The first step is the rate
determining step. Probably, in this step, the 1:1 adduct
of catechol and the zinc complex is formed and a
1:100 mixture of complex 1 and 3,5-DTBC is
obtained. The complex 1 exhibits a peak at m/z =
453.64 (Supplementary Data, Fig. S5). The peak at
m/z = 243.56 can be assigned to sodium aggregate of

Fig. 3 –– Plot of rate versus [substrate] (3,5-DTBC) in presence of Fig. 4 –– Change in spectral pattern of complex 1 after reaction
1 in MeOH. [Inset: Lineweaver-Burk plot]. with OAPH (the reaction was observed for 6 h in methanol).
1356 INDIAN J CHEM, SEC A, NOVEMBER 2018

with a constant concentration of 1×10-4 M, was added

to 2 mL of OAPH of a particular concentration
(varying its concentration from 1×10-3 M to 1×10-2 M)
to achieve the final concentration of the complex as
1×10-4 M. The conversion of OAPH to APX was
monitored with time at a wavelength of 417 nm for
solutions in MeOH. The rate for each concentration of
the substrate was determined by the initial rate
method. The rate versus concentration of substrate
data, were analyzed on the basis of Michaelis-Menten
approach of enzymatic kinetics to get the Lineweaver-
Burk (double reciprocal) plot as well as the values of
the various kinetic parameters viz., Vmax, KM and
Kcat. The observed rate versus [substrate] plot in
Fig. 5 –– Plot of rate versus [substrate] (OAPH) in presence of
1 in MeOH. [Inset: Lineweaver-Burk plot].
methanol solution as well as Lineweaver-Burk plot is
given in Fig. 5. The kinetic parameters are listed in
pure methanol. Upon treatment of methanolic solution Supplementary Data, Table S3. The turnover number
of 1 into 100 equivalents of OAPH under aerobic (Kcat) is 5.27×105 h-1 in methanol.
conditions, the repetitive UV-vis spectral scan was
Reaction mechanism
recorded (Fig. 4). The colourless solution gradually To elucidate mechanistic pathway of the reaction, it
turned deep brown which indicates conversion of is found that initially OAPH forms an adduct with 1
OAPH to 2-aminophenoxazine-3-one (APX). The which is trapped by mass spectrometry at
spectral scan shows very smooth growth of APX band m/z = 564.46 (OAPH-1) (Supplementary Data,
at 427 nm8c. APX was identified by HRMS with Fig. S12). This adduct generates 2-amoinophenoxazine-
m/z = 235.54 (sodium aggregate of APX) 3-one through some intermediate reaction with
(Supplementary Data, Fig. S8). The time dependent molecular oxygen. Reduced molecular oxygen in the
change in absorbance at a wavelength of 427 nm, form of H2O2 was detected spectrophotometrically
characteristic of APX in methanol, was observed for (details are provided as supplementary data)22.
50 min to comprehend the reaction kinetics and find
out the reaction rate between OAPH and 1. The Conclusions
difference in absorbance ΔA at 427 nm, was plotted Synthesis and X-ray crystallographic structure of
against time to obtain the initial rate for that particular Complex 1 along with C-S bond cleavage of its
catalyst to substrate concentration ratio organic ligand backbone during its synthesis has been
(Supplementary Data, Fig.S9). A first-order catalytic reported. The compound is found to catalyse both
reaction is observed, with initial rate 1.64×10-2 min-1. catechol to quinine, and 2-aminophenol to
Control experiments were carried out with only corresponding phenoxazinone chromophore reactions.
OAPH, and, OAPH and Zn(II) perchlorate Some other Zn(II) complexes of different nuclearities
in methanol. In reaction with only OAPH, a UV-vis have been reported in literature, which catalyze
peak growth suggesting the formation of 3,5-DTBC11,12. To the best of our knowledge no
phenoxazinone was found (Supplementary Data, Zn(II) complexes were found to show phenoxazinone
Fig. S10), but the peaks were not very regular as with synthase activity so far. The turn over number for the
1 (Fig. 4). No band for phenoxazinone (in the UV-vis catecholase activity is found to be better than a
repetitive scan) was found in the reaction mixture of reported work13b. Similarly, the turn over number for
OAPH and Zn(II) perchlorate (Supplementary compound (1) of phenoxazinone synthase activity is
Data, Fig. S11). also better than one the reported in literature14.
Enzyme kinetics study Supplementary Data
Enzymatic kinetic experiments were performed Crystallographic data for the structural analysis of
using UV-vis spectrophotometry under thermostated complex 1 have been deposited with Cambridge
condition at 25 °C with complex 1 and the substrate Crystallographic Data Centre, under CCDC No.
OAPH in MeOH. The complex solution (0.04 mL), 1563187. Copy of this information may be obtained
 GHOSH et al.: C-S BOND CLEAVAGE INFLUENCED BY Zn(II) 1357

free of charge from: The Director, CCDC, 12 Union Gasque L, Dalton Trans, 2008, 1857; (c) M Mitra M, Kundu T,
Road, Cambridge CB2 1EZ, UK (fax: 44-1223-336- Kaur G, Sharma G, Choudhury A R, Singh Y & Ghosh R,
RSC Adv, 6 (2016) 58831.
033: Email: [email protected]). Other 7 (a) Koval I A, Gamez P, Belle C, Selmeczi K & Reedijk J,
supplementary data associated with this article are Chem Soc Rev, 35 (2006) 814; (b) Dey S K & Mukherjee A,
available in the electronic form at Coord Chem Rev, 310 (2016) 80.
http://www.niscair.res.in/jinfo/ijca/IJCA_57A(11) 8 (a) Maurya M R, Sikarwar S, Joseph T & Halligudi S B,
J Mol Cat A: Chemical, 236 (2005) 132; (b) Mukherjee C,
1351-1357_SupplData.pdf.
Weyhermüller T, Bothe E, Rentschler E & Chaudhuri P,
Inorg Chem, 46 (2007) 9895.
Acknowledgement 9 (a) Kar P, Ida Y, Kanetomo T, Drew M G B, Ishida T &
The authors sincerely thank PURSE programme, DST, Ghosh A, Dalton Trans, 44 (2015) 9795; (b) Chakraborty P,
Govt of India, for different infrastructural facilities. RG is Majumder S, Jana A & Mohanta S, Inorg Chim Acta, 410
thankful to Department of Higher Education, Science & (2014) 65; (c) Das M, Nasani R, Saha M, Mobin S M &
Mukhopadhyay S, Dalton Trans, 44 (2015) 2299.
Technology and Biotechnology, Government of West 10 (a) Singh R, Banerjee A & Rajak K K, Inorg Chim Acta, 363
Bengal [No. 781(Sanc.)/ST/P/S&T/4G-4/2013 dated (2010) 3131; (b) Mitra M, Maji A K, Ghosh B K,
04-12-2014], India, for financial assistance. AKG thanks Raghavaiah P, Ribas J & Ghosh R, Polyhedron, 67 (2014)
CSIR, New Delhi, India for his CSIR-SRF fellowship. 19; (c) Mahapatra T S, Basak D, Chand S, Lengyel J,
SC-XRD facility provided by USIC (BU) is also Shatruk M, Bertolasi V & Ray D, Dalton Trans, 45 (2016)
13576; (d) Mitra M, Raghavaiah P & Ghosh R, New J Chem,
gratefully acknowledged. 39 (2015) 200.
11 (a) Guha A, Chattopadhyay T, Paul N D, Mukherjee M,
References Goswami S, Mondal T K, Zangrando E & Das D, Inorg Chem,
1 (a) Costas M, Mehn M P, Jensen M P & Que Jr L, Chem Rev, 51 (2012) 8750; (b) Mal S K, Mitra M, Purohit C S & Ghosh R,
104 (2004) 939; (b) Company A, Prat I, Frisch J R, Polyhedron, 101 (2015) 191; (c) Sanyal R, Dash S K, Das S,
Mas-Ballest R, Güell M, Juhász G, Ribas X, Münck E, Luis Chottopadhyay S, Roy S & Das D, J Biol Inorg Chem, 19
J M, Que Jr L & Costas M, Chem Eur J, 17 (2011) 1622; (2014) 1099; (d) Kaizer J, Pap J, Speier G, Parkanyi L,
(c) Prat I, Company A, Postils V, Ribas X, Que Jr L, Luis Jr Korecz L & Rockenbauer A, J Inorg Biochem, 91 (2002)
J M & Costas M, Chem Eur J, 19 (2013) 6724; (d) McDonald 190; (e) Nanjundan N, Narayanasamy R, Geib S,
A R, Heuvelen K M V, Guo Y, Li F, Bominaar E L, Münck E Velmurugan K, Nandhakumar R, Balakumaran M D &
& Que Jr L, Angew Chem Int Ed, 51 (2012) 9132. Kalaichelvan P T, Polyhedron, 110 (2016) 203.
2 (a) Paria S, Que Jr L and Paine T K, Angew Chem Int Ed, 50 12 Dhara A K, Singh U P & Ghosh K, Inorg Chem Front, 3
(2011) 11129; (b) Chakraborty B, Halder P, Banerjee P R & (2016) 1543.
Paine T K, Eur J Inorg Chem, (2012) 5843; 13 (a) Baruah B & Chakravorty A, Indian J Chem, 42A (2003)
(c) Mukherjee A, Cranswick M A, Chakrabarti M, Paine T 2677; (b) Mal S K, Mitra M, Yadav H R, Purohit C S,
K, Fujisawa K, Münck E & Que Jr L, Inorg Chem, 49 (2010) Choudhury A R & Ghosh R, Polyhedron, 111 (2016) 118.
3618; (d) Dutta S, Peng S M & Bhattacharya S, Inorg Chem, 14 (a) Mitra M & Ghosh R, Indian J Chem, 55A (2016) 681;
39 (2000) 2231. (b) Panja A, RSC Adv, 4 (2014) 37085; (c) Panja A, Dalton Trans,
3 Klabunde T, Eicken C, Sacchettini J C & Krebs B, Nat Struct 43 (2014) 7760; (d) Panja A, Shyamal M, Saha A & Mandal T K,
Biol, 5 (1998) 1084. Dalton Trans, 43 (2014) 5443; (e) Kumar S C, Ghosh A K, Chen J
4 (a) Abuhijleh A L, Pollitte J & Woods C, Inorg Chim Acta, D & Ghosh R, Inorg Chim Acta, 464 (2017) 49.
215 (1994) 131; (b) Malachowski M R, Davidson M G & 15 (a) Lyons T W & Sanford M S, Chem Rev, 110 (2010) 1147;
Hoffman J N, Inorg Chim Acta, 157 (1989) 91; (b) Acharyya R, Basuli F, Wang R -Z, Mak T C W &
(c) Malachowski M R & Davidson M G, Inorg Chim Acta, Bhattacharyya S, Inorg Chem, 43 (2004) 704.
162 (1989) 199; (d) Mitra M, Maji A K, Ghosh B K, Kaur G, 16 (a) Chakraborty B, Halder P, Banerjee P R & Paine T K, Eur
Choudhury A R, Lin C H, Ribas J & Ghosh R, Polyhedron, J Inorg Chem, (2012) 5843; (b) Paria S, Halder P & Paine T
61 (2013) 15. K, Angew Chem Int Ed, 51 (2012) 6195
5 (a) Koval I A, Selmeczi K, Belle C, Philouze C, Saint-Aman E, 17 (a) Jana M & Majumdar A, Inorg Chem, 57 (2018) 617;
Gautier-Luneau I, Schuitema A M, van Vliet M, Gamez P, (b) Das B, Sarkar S, Zangrando E & Chattopadhyay P, Inorg
Roubeau O, Lüken M, Krebs B, Lutz M, Spek A L, Pierre J L & Chem Comm, 12 (2009) 1112
Reedijk J, Chem Eur J, 12 (2006) 6138; (b) Merkel M, 18 (a) Bianchini C, Meli A, Acc Chem Res 31 (1998) 109;
Mçller N, Piacenza M, Grimme S, Rompel A & Krebs B, (b) Choudhary T V, Malandra J, Green J, Parrott S, Johnson B,
Chem Eur J, 11 (2005) 1201; (c) Thio Y, Yang X & Vittal J J, Angew Chem Int Ed, 45 (2006) 3299.
Dalton Trans, 43 (2014) 3545; (d) Banu K S, Chattopadhyay T, 19 Sheldrick G M, Acta Crystallogr, Sect A: Found Crystallogr,
Banerjee A, Bhattacharya S, Suresh E, Nethaji M, Zangrando E 64 (2008) 112.
& Das D, Inorg Chem, 47 (2008) 7083; (e) Dasgupta S, 20 Zippel F, Ahlers F, Werner R, Haase W, Nolting H F &
Majumder I, Chakroborty P, Zangrando E, Bauza A, Frontera A Krebs B, Inorg Chem, 35 (1996) 3409.
& Das D, Eur J Inorg Chem, (2017) 133. 21 Tsuruya S, Yanai S I & Masai M, Inorg Chem, 25 (1986) 141.
6 (a) Majumder S, Sarkar S, Sasmal S, Sanudo E C & Mohanta S, 22 Vogel A I, Textbook of Quantitative Inorganic Analysis, 3rd edn,
Inorg Chem, 50 (2011) 7540; (b) Mijangos E, Reedijk J & (Longmans,Green and Co. Ltd, London), 1961 p. 366.