Conversion of 2-thiohydantoins and their derivatives to the corresponding hydantoins in the processes of complexation reactions with copper(II) chloride dihydrate

Article abstract of DOI:10.1016/j.poly.2014.03.045

The treatment of 5-pyridylmethylene-substituted 2-thiohydantoins or 2-alkylthio-3,5-dihydro-4H-imidazole-4-ones with CuCl₂ ^.2H₂O affords the mononuclear or polymeric copper(II) complexes of the corresponding hydantoins. A presumable mechanism of hydantoin moiety formation involves Lewis acid catalyzed nucleophilic substitution of a sulfur-containing leaving group in the organic ligand by a water molecule from CuCl₂^.2H₂O. The copper complexes Cu(L ¹-H)Cl(H₂O) (7; L¹ = (Z)-3-allyl-5-(pyridine-2- ylmethylene)imidazole-2,4(4H)-dione) and Cu(L²-H)₂ (9; L² = Z)-3-allyl-5-(5′-bromo-pyridine-2-ylmethylene)imidazole-2, 4(4H)-dione) were characterized by X-ray diffraction.

Full text of DOI:10.1016/j.poly.2014.03.045

Polyhedron 76 (2014) 45–50
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Conversion of 2-thiohydantoins and their derivatives
to the corresponding hydantoins in the processes
of complexation reactions with copper(II) chloride dihydrate
⇑
Elena K. Beloglazkina , Alexander G. Majouga, Andrei V. Mironov, Anna V. Yudina, Olga Yu. Kuznetsova,
Nikolai V. Zyk
M.V. Lomonosov Moscow State University, Chemistry Department, Moscow 119992, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
The treatment of 5-pyridylmethylene-substituted 2-thiohydantoins or 2-alkylthio-3,5-dihydro-4H-imid-
azole-4-ones with CuCl.22H2O affords the mononuclear or polymeric copper(II) complexes of the corre-
sponding hydantoins. A presumable mechanism of hydantoin moiety formation involves Lewis acid
catalyzed nucleophilic substitution of a sulfur-containing leaving group in the organic ligand by a water
molecule from CuCl.22H2O. The copper complexes Cu(L1-H)Cl(H2O) (7; L1 = (Z)-3-allyl-5-(pyridine-2-
ylmethylene)imidazole-2,4(4H)-dione) and Cu(L2-H)2 (9; L2 = Z)-3-allyl-5-(50-bromo-pyridine-2-ylmeth-
ylene)imidazole-2,4(4H)-dione) were characterized by X-ray diffraction.
Received 23 November 2013
Accepted 18 March 2014
Available online 2 April 2014
Keywords:
2-Thiohydantoins
2-Alkylthio-3,5-dihydro-4H-imidazole-4-
ones
Ó 2014 Elsevier Ltd. All rights reserved.
Copper(II) hydantoin complexes
X-ray diffraction
Structure
1. Introduction
AcONa or NH3 [10,21], and Hg(OAc)2 with a microwave [22]. Most
of these methods mean the use of hazardous chemicals, oxidizing
Hydantoins and their derivatives have attracted attention for
their antidiabetic [1], antiarrhythmic [2] anticonvulsant [3], antitu-
mor, antiangiogenic and antimetastatic [4], serotonin and fibrino-
gen receptor antagonistic [5] and aldose reductase inhibitory [6]
activities. Hydantoin and related moieties are also found in many
bioactive natural products [7].
Desulfurization of 2-thiohydantoin for its conversion to the cor-
responding hydantoins is a known method for the synthesis of
therapeutically relevant compounds. Existing methods for
desulfurization of 2-thiohydantoins include hydrolysis catalyzed
by protonic [8] and Lewis acids [9] or by bases [10], use of
hydrogen peroxide in combinations with different co-reagents
((DMF)/CH3COOH [11], NaHCO3/H2O [12], pyridine [13], ROH
[14]), NaOMe/MeI/DMF [15], tetrabutylammonium periodate
[16], Hg(OAc)2 with a microwave [17], HgO in AcOH [18] or nitrous
dioxide [19]. For another group of 2-thiohydantoins, the desulfur-
ization methods include the initial S-alkylation of 2-thiohydantoin
followed by treatment with HCl in EtOH or H2O [20], MeONa,
agents or strong acids.
Hydantoins, like many drugs, have metal binding sites that can
interact with metals found in serum [23]. It is known that in some
cases the biological activity and toxicity of organic compounds are
increased by the presence of metal ions, which would be expected
to be the case if the chelate is the active form of the drug [24]. The
preparation, structure and properties of some hydantoin com-
plexes with Ag(I), Au(I), Au(III), Cu(II), Co(II), Ni(II), Pd(II), Pt(II),
Pt(IV), Mn(II), Cd(II), Hg(II), Sb(V), Re(V), Sn(IV) and Ti(IV) have
been reported [23,25].
We recently synthesized a series of mono- and binuclear com-
plexes of Cu(I) and Cu(II) with 5-(pyridylmethylene)- [26] and 5-
(imidazoleylmethylene)-2-thiohydantoins [27] and demonstrated
that the primary product of the reaction of (4Z)-2-thioxo-4-
[(1-methyl-1H-imidazole-2-yl)methylene]-1-(n-propyl)-imidazole-
5(4H)-one with CuCl.22H2O is the hydantoin-containing copper(II)
complex, which apparently forms as a result of copper ion-
mediated nucleophilic substitution of a ligand sulfur atom by a
water molecule from CuCl2. 2H2O. In this work we describe the
synthesis of novel hydantoin-containing copper(II) complexes from
5-(pyridylmethylene)-2-thiohydantoin or 2-alkylthio-5-(pyridylm-
ethylene)-3,5-dihydro-4H-imidazole-4-one as the result of their
reactions with copper(II) chloride dihydrate.
⇑
Corresponding author. Tel.: +7 495 9394020.
E-mail address: bel@org.chem.msu.ru (E.K. Beloglazkina).
http://dx.doi.org/10.1016/j.poly.2014.03.045
0277-5387/Ó 2014 Elsevier Ltd. All rights reserved.

46
E.K. Beloglazkina et al. / Polyhedron 76 (2014) 45–50
(d, 2H, CH2, J = 5.97 Hz), 5.30 (t, 2H, @CH, J = 10.62 Hz), 5.85 (dt,
2. Experimental
1H, @CH, J1 = 5.97 Hz, J2 = 15.60 Hz), 7.10 (s, 1H, @CH), 7.76 (dd,
1H, Py, J1 = 2.61 Hz, J2 = 8.53 Hz), 8.57 (d, 1H, Py, J = 8.53 Hz), 8.72
All materials were obtained from commercial sources and used
as received. The melting points are uncorrected. 1H NMR spectra
were recorded on a Varian-XR-400 recorder (400 MHz for 1H).
The IR spectra in Nujol were recorded on a Perkin-Elmer 1430
spectrophotometer.
(d, 1H, Py, J = 2.60 Hz). IR, m
/cm–1: 3031, 1718, 1637, 1488. Anal.
Calc. for C26H22N6O2Br2S2 (6): C, 46.29; H, 3.26; N, 12.46; S, 9.49.
Found: C, 46.17; H, 3.24; N 12.29; S, 9.23%.
2.3. Synthesis of the coordination compounds (typical procedure)
2.1. 5-Substituted 2-thiohydantoins 3–5 (typical procedure)
A concentrated solution of ligand 3, 5 or 6 in 2 ml of CH2Cl2 and
an equimolar amount of CuCl2. 2H2O in 2 ml of EtOH were carefully
mixed and the reaction mixture, placed in an open test-tube, was
left at room temperature in a tightly capped vessel containing
10 ml of diethyl ether. After two days, crystals of the hydantoin
complexes 7–9 were formed as a result of the slow diffusion of
the ether vapor into the solution. The formed crystals were filtered
off, washed with small portions of Et2O and dried in air.
Pyridine-2-carbaldehyde or 5-bromo-pyridine-2-carbaldehyde
(1 eq) was added to a solution of thiohydantoin 1 or 2 (1 eq) in
2% KOH solution in EtOH, and this mixture was stirred at room
temperature for 3 h. The precipitate that formed was filtered off
and then suspended in water. Concentrated HCl solution was
added under stirring to bring the pH to 7. The precipitate was fil-
tered off, washed with EtOH, diethyl ether and dried in air.
2.1.1. (5Z)-2-Thioxo-3-allyl-5-[(pyridine-2-yl)methylene]-imidazole-
4(4H)-one (3)
2.3.1. (Z)-3-allyl-5-(pyridine-2-ylmethylene)imidazole-2,4(4H)-dione
copper(II) chloride hydrate (7)
0.16 g (93%) of compound 3 were obtained as a result of the
reaction between 0.1 g (0.64 mmol) thiohydantoin 1 and 0.068 g
(0.64 mmol) pyridine-2-carbaldehyde. M.p. 178 °C. 1H NMR
(DMSO-d6): 4.41 (d, 2H, CH2, J = 5.08 Hz), 5.14 (m, 2H, @CH2),
5.86 (dd, 1H, @CH, J1 = 5.36 Hz, J2 = 10.55 Hz), 6.77 (s, 1H, @CH),
7.40 (m, 1H, Py), 7.76 (d, 1H, Py, J = 7.51 Hz), 7.90 (dt, 1H, Py,
J1 = 1.46 Hz, J2 = 7.51 Hz), 8.76 (d, 1H, Py, J = 3.14 Hz), 11.76 (s,
Dark-yellow very thin plates (0.02 g, 36%) were obtained from
0.022 g (0.055 mmol) of ligand 3 and 0.007 g (0.055 mmol) of
CuCl.22H2O. M.p. 154–156 °C. IR, /cm–1: 3420, 1720, 1655, 1578,
m
1470. Anal. Calc. for C12H12N3O3ClCu (7): C, 41.75; H, 3.50; N,
12.17. Found: C, 41.64; H, 3.43; N 12.02%.
2.3.2. (Z)-3-phenyl-5-(50-bromo-pyridine-2-ylmethylene)imidazole-
2,4(4H)-dione copper(II) chloride hydrate (8)
1H, –NH). IR, m
/cm–1: 3311, 1728, 1662, 1455, 1428. Anal. Calc.
for C11H11N3OS (3): C, 58.78; H, 4.49; N, 17.14. Found: C, 58.67;
H, 4.63; N 17.09%.
Black needles (0.011 g, 37%) were obtained from 0.02 g
(0.055 mmol) of ligand 5 and 0.007 g (0.055 mmol) of CuCl.22H2O.
M.p. 215–217 °C. IR,
15H11N3O3BrClCu (7): C, 39,15; H, 2.41; N, 9.13. Found: C, 39.33;
H, 2.11; N 9.03%.
m
/cm–1: 3419, 1718, 1645. Anal. Calc. for
2.1.2. (5Z)-2-Thioxo-3-allyl-2-[(50-bromo-pyridine-2-yl)methylene]-
imidazole-4(4H)-one (4)
C
0.34 g (78%) of compound 4 were obtained as a result of the
reaction between 0.2 g (1.28 mmol) thiohydantoin 1 and 0.23 g
(1.28 mmol) 5-bromo-pyridine-2-carbaldehyde. M.p. 189–191 °C.
1H NMR (DMSO-d6): 4.41 (d, 2H, CH2, J = 5.51 Hz), 5.13 (dd, 2H,
@CH, J1 = 10.00 Hz, J2 = 15.39 Hz), 5.85 (dt, 1H, @CH, J1 = 5.51 Hz,
J2 = 11.93 Hz), 6.73 (s, 1H, @CH), 7.16 (d, 1H, Py, J = 8.08 Hz), 8.15
(d, 1H, Py, J = 8.08 Hz), 8.82 (s, 1H, Py), 11.70 (bs, 1H, –NH). IR,
2.3.3. Bis[(Z)-3-allyl-5-(50-bromo-pyridine-2-ylmethylene)imidazole-
2,4(4H)-dione] copper(II) (9)
Black spiky prisms (0.032 g, 62%), were obtained from 0.05 g
(0.074 mmol) of ligand 6 and 0.02 g (0.15 mmol) of CuCl.22H2O.
M.p. >300 °C. IR,
m
/cm–1: 3450, 3087, 1747, 1656, 1643, 1487,
/cm–1: 3240, 1730, 1680, 1460. Anal. Calc. for C11H10N3OBrS (4):
1454. Anal. Calc. for C24H14N6O4Br2Cu (9): C, 42.78; H, 2.09; N,
12.47. Found: C, 43.09; H, 2.44; N 12.66%.
m
C, 42.31; H, 3.21; N, 13.46; S, 10.26. Found: C, 42.38; H, 3.31; N
13.50; S, 10.19%.
3. Results and discussion
2.1.3. (5Z)-2-Thioxo-3-phenyl-2-[(50-bromo-pyridine-2-
yl)methylene]-imidazole-4(4H)-one (5)
3.1. Synthesis of the ligands and the complexes
0.98 g (99%) of compound 5 were obtained as a result of the
reaction between 0.5 g (2.6 mmol) of thiohydantoin 2 and 0.48 g
(2.6 mmol) 5-bromo-pyridine-2-carbaldehyde. M.p. 265–267 °C.
1H NMR (DMSO-d6): 6.81 (s, 1H, @CH), 7.37–7.69 (m, 5H, Ph),
7.77 (d, 1H, Py, J = 6.18 Hz), 8.18 (d, 1H, Py, J = 6.18 Hz), 8.88 (s,
The 3-substituted 2-thioxotetrahydro-4H-imidazole-4-ones 1
and 2 were prepared according to literature procedures [20b]. 5-
(Pyridine-2-ylmethylene)-2-thiohydantoins 3–5 were synthesized
by a base-catalyzed condensation reaction between 2-thiohydan-
toin 1 or 2 and the corresponding pyridinecarbaldehydes, as shown
in Scheme 1. 2,20-(Ethane-1,2-diylsulfanyldiyl)bis(5-(50-bromo-
pyridine-2-ylmethylene)-3,5-dihydro-4H-imidazole-4-one 6 was
obtained by alkylation of 2-thiohydantoin 4 with 1,2-dibromoeth-
ane in DMF in the presence of potassium carbonate. Compounds 3–
6 were isolated as single geometric isomers, which were identified
as the Z isomers basing on the chemical shifts of the vinylic protons
in the 1H NMR spectra [28]. The preferential generation of Z iso-
mers for these compounds may be the result of the formation of
an intramolecular hydrogen bond between the pyridine nitrogen
atom and the N–H fragment of the thiohydantoin cycle. The Z con-
figuration of ligands 3 and 6 in their coordination compounds was
also confirmed by X-ray diffraction data for complexes 7 and 9 (see
below).
1H, Py), 11.81 (bs, 1H, –NH). IR, m
/cm–1: 3262, 1729, 1654. Anal.
Calc. for C16H11N3OBrS (5): C, 51.47; H, 2.94; N, 11.26; S, 8.58.
Found: C, 51.29; H, 2.81; N 11.55; S, 8.66%.
2.2. (5Z,50Z)-2,20-(ethane-1,2-diylsulfanyldiyl)bis[5-(50-bromo-
pyridine-2-ylmethylene)-3-allyl-3,5-dihydro-4H-imidazole-4-one] (6)
1,2-Dibromoethane (0.06 g, 0.31 mmol) was added to a stirred
mixture of compound 4 (0.2 g, 0.62 mmol) and dried K2CO3
(0.9 mmol) in 50 ml DMF. The resulting mixture was stirred for
2 h at 0 °C, then for 2 h at room temperature. After this time
50 ml of water was added. The formed precipitate was collected,
washed with water, diethyl ether and dried in air. Yield 0.16 g
(62%). M.p. 230–232 °C. 1H NMR (CDCl3): 1.58 (s, 1H, CH2), 4.27

E.K. Beloglazkina et al. / Polyhedron 76 (2014) 45–50
47
lone 6 may be explained by the inclusion of a carbonyl group of
the latter compound in the cross- -conjugated bonds system,
and the absence of such a cross-coupling in the first case. The lack
of absorption of N(3)–H in the copper complexes suggests that the
copper atom is bound to the hydantoin ligand at the N(3) position.
Single crystal data for complexes 7 and 9 were collected on
R
N
R
N
p
O
S
1. KOH/EtOH
O
S
NH
N
N
CHO
2.
NH
(1), R = All
(2), R = Ph
X
SMART APEX II (Mo Ka) and CAD4 (Cu Ka) diffractometers, respec-
3. HCl/H2O
tively. Crystallographic data and refinement parameters for 7 and 9
are presented in Table 1S in the Supporting information, and
selected bond lengths are given in Table 1. The molecular struc-
tures of compounds 7 and 9 are shown in Figs. 1 and 2, respec-
tively. Both compounds 7 and 9 have similar structures. DIAMOND
drawings of each complex show that the pyridyl and imidazole
rings of the organic ligands are nearly coplanar. For both com-
plexes 7 and 9 the ligands are coordinated to the metal atom
through their nitrogen atoms with the formation of six-membered
metallacycles. The allyl fragment C3H5 is attached to the N(3) atom
of the imidazole ring in a mutually perpendicular fashion.
X
(3), R = All, X = H, 93%
(4), R = All, X = Br, 78%
(5), R = Ph, X = Br, 98%
R
N
O
S
Br(CH2)2Br
4
N
K2CO3, DMF
N
The first difference between the structures of complexes 7 and 9
is the presence of a bromine atom in the pyridine ring in the
meta-position for compound 9, but this does not have a significant
influence on the organic ligand structure: the differences in the
corresponding bond lengths of the ligand moieties for 7 and 9
mainly do not exceed 0.01 Å, with a maximal distinction of 0.03 Å.
The coordination polyhedra of the copper atoms in the struc-
tures of the coordination compounds are significantly different.
The copper atom in complex 7 is five-coordinated and the coordi-
nation polyhedra may be described as a square pyramid with an
elongated apical Cu–Cl distance (2.6572(9) Å), which is common
for such complexes [27]. In contrast, in complex 9 four nitrogen
atoms from two ligand moieties form a coordination polyhedron
around the copper atom which can be described as either a
strongly distorted tetrahedron or a deformed square. The later
description may be assumed to be preferred because of the steric
effect of the two large ligands: their planes are inclined at 58.65°
relative to each other.
Br
(6), R = All, 62%
2
Scheme 1. Synthesis of ligands 3–6.
The hydantion complexes 7–9 were obtained under the slow
diffusion of diethyl ether into a mixture of methanolic solutions
of the ligand 3, 5 or 6 and copper(II) chloride dihydrate. All the iso-
lated coordination compounds contain deprotonated hydantoin
ligands in their structures (Scheme 2).
All the complexes were characterized by IR spectroscopy and
elemental analysis; the structures of complexes 7 and 9 were also
confirmed by X-ray diffraction data.
The IR spectra of complexes 7 and 8 show shifts in the absorp-
tion bands for the C@O, C@N and C@C groups from 1730 to
1630 cmꢀ1 to lower frequencies relative to those of the initial
ligands, whereas for complex 9 there is a shift of these absorption
bands to higher frequencies as compared to the corresponding
ligand 6. The bathochromic shift of the C@O and C@N group bands
in the IR spectrum of compound 9 compared to the bis-imidazo-
An essential difference between structures 7 and 9 is also their
molecular packing. The crystal structure of 9 is stabilized by stack-
ing of pyridylmethylene-imidazolone fragments (the interplanar
distance between parallel ligands moieties from neighboring mol-
ecules is about 3.5 Å; see Fig. 1S, Supporting information). At the
R
N
R
N
Table 1
O
O
O
S
Relevant interatomic distances for compounds 7 and 9.
N
N
Cl
NH
N
Compound 7
Compound 9
CuCl2*2H2O
Cu
0
0
Atoms
Atoms
Distance (AÅ)
Distance (ÅA)
CH2Cl2/CH3OH
OH2
Cu1–N1
Cu1–N2
Cu1–Cl1
Cu1–Cl10
Cu1–O3
C6–C7
2.044(3)
1.982(3)
2.3176(9)
2.6572(9)
1.978(2)
1.346(4)
1.439(5)
Cu1–N1
Cu1–N2
2.019(2)
1.904(3)
X
X
(7), R = All, X = H, 36%
(3), R = All, X = H
(5), R = Ph, X = Br
(8), R = Ph, X = Br, 37%
C6–C7
C7–C8
1.342(4)
1.434(4)
All
Br
C6–C1
N
O
O
Imidazole ring, ranges
C–N
C–C
C–O
1.366–1.399
1.492
1.221–1.235
C–N
C–C
C–O
1.368–1.406
1.507
1.209–1.213
N
N
CuCl2*2H2O
6
Cu
N
CH2Cl2/CH3OH
N
Pyridine ring, ranges
C–N
C–C
1.361–1.363
1.374–1.399
C–N
C–C
1.342–1.361
1.353–1.417
O
O
N
Br
All
Allyl group
N3–C10
C10–C11
C11–C12
1.459(4)
1.501(5)
1.297(5)
N3–C11
C11–C12
C12–C13
1.461(5)
1.473(6)
1.299(7)
(9), 62%
Scheme 2. Syntheses of copper hydantoin complexes 7–9.

48
E.K. Beloglazkina et al. / Polyhedron 76 (2014) 45–50
The hydantoin-containing complexes 7–9 apparently form as a
result of copper ion-mediated (as a Lewis acid) nucleophilic substi-
tution of a ligand sulfur atom by a water molecule from CuCl.22H2O
(Scheme 3). In the cases of the thiohydantoins 3 and 5, the reaction
apparently involved the iminothiol containing tautomeric form of
the parent compounds. It appears that in the first stage of the com-
plexation reaction the copper(II) ion is coordinated to the pyridine
and thiohydantoin nitrogen atoms, which increases the electro-
philic reactivity of bonding with the N(3) sp2 hybridized carbon
atom. Then, after the consecutive chloride elimination, water mol-
ecule attack on the C(2) atom, proton elimination and cleavage of
the C–S bond, the hydantoin-containing copper(II) coordination
compound forms. The liberated hydrogen sulfide or 1,2-ethanedi-
thiol may bind to other copper ions, with the corresponding sulfide
or thiolate formation, which explains the fact that the yields of the
hydantoin complexes 7 and 8 do not exceed 50%.
In the course of complex 9 formation, a coordination compound,
wherein the starting bis-pyridyl-imidazolon 6 acts as a tetraden-
tate ligand, apparently forms in the first stage, as analogously
described in [26d]. Then the reaction proceeds via a mechanism
similar to the formation of complexes 7 and 8, with the sequential
replacement of two sulfur-containing fragments and the formation
of the bis-hydantoin complex (Scheme 4).
Fig. 1. Molecular structure and labelling scheme for complex 7. The copper atoms
are connected in chains via chlorine atoms.
The assumption about the initial formation of a copper complex
with pyridylmethylene-substituted 2-thio-imidazolone is con-
firmed by the number of hydantoin fragments in the complexes
formed from the bis-thio-imidazolone ligand 6 and mono-thio-
imidazolone ligands 3 and 5. In the first case, a complex having
two coordinating pyridylmethylene-2-thio-imidazolone moieties
around the metal ion should be formed in the initial stage of the
ligand interaction with CuCl.22H2O. In accordance with this pre-
organization, complex 9 also contains two hydantoin moieties in
the copper coordination sphere. In contrast, the interaction of the
mono-pyridylmethylene-2-thio-imidazolone ligands 4 and 5 with
Cu(II) leads to the formation of complexes containing a single thi-
ohydantoin ligand and this results in the mono-hydantoin com-
plexes 7 and 8.
Fig. 2. Molecular structure and labelling scheme for complex 9.
An alternative mechanism involving a ring opening-ring closure
sequence, which have been proposed for thiohydantoin hydrolysis
in alkaline medium [15], is unlikely in the absence of a sufficiently
strong nucleophile. Note, that anhydrous copper(II) chloride does
not form crystalline products under reaction with ligands 3–6
under the same conditions.
same time, compound 7 may be considered as 1D structure with
(–Cl–Cu–Cl–) zigzag chains propagating along the a direction of
the unit cell. The imidazole ligands are perpendicular to the chains
and are parallel to each other, being about 3.7 Å apart.
R
N
R
N
R
O
O
S
SH
N
O
SH
OH2
OH2
tautomerization
CuCl2*2H2O
N
N
N
H
Cu
N
N
N
Cl
Cl
3, 5
- Cl -
R
N
R
N
R
O
SH
OH
O
O
N
O
SH
N
N
N
- H+
OH2
OH2
Cl
-H2S
OH2
Cu
Cu
Cu
Cl
N
N
OH2
N
Cl
7, 8
Scheme 3. A possible mechanism of hydantoin moiety formation during the preparation of complexes 7 and 8.

E.K. Beloglazkina et al. / Polyhedron 76 (2014) 45–50
49
2+
R1
N
R1
N
R1
N
R1
N
O
S
S
O
O
S
S
O
OH2
N
N
N
2Cl-
N
N
N
CuCl2*2H2O
Cu
N
N
OH2
Br
Br
Br
- Cl -
Br
6
HS
R1
N
R1
N
+
+
R1
N
R1
O
O
S
O
N
O
S
S
OH2
O
- H+
N
N
N
Cl-
Cl-
N
N
Cu
OH2
Cu
N
N
N
OH2
Br
- Cl -
Br
Br
Br
HS
R1
N
R1
N
O
O
S
O
- H+
- HS(CH2)2SH
N
N
9
Cu
H2O
N
N
Br
Br
Scheme 4. A possible mechanism for complex 9 formation.
4. Conclusion
References
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