Novel ditopic organic ligands containing the terpyridine and 2-thiohydantoin fragments

Full text of DOI:10.1007/s11172-013-0386-5

Russian Chemical Bulletin, International Edition, Vol. 62, No. 12, pp. 2631—2633, December, 2013
2631
Novel ditopic organic ligands containing
the terpyridine and 2ꢀthiohydantoin fragments
E. A. Manzhelii, E. K. Beloglazkina, A. G. Majouga, and N. V. Zyk
Department of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119991 Moscow, Russian Federation.
Eꢀmail: bel@org.chem.msu.ru
Organic ligands containing two dissimilar chelating
fragments are of interest for the preparation of homoꢀ and
heteropolynuclear metal complexes. Such metal complexꢀ
es with ligands having electronꢀdonating conjugated sysꢀ
tems are attractive because of their special photochemical
(absorption and emission) properties.1 Continuing our inꢀ
vestigations into the synthesis of terpyridines,2,3 thioꢀ
hydantoins,4,5 and their coordination compounds, we obꢀ
tained novel organic ligands 1 and 2 combining both the
aforementioned structural units and studied their methylaꢀ
tion with MeI and complexation reactions of compound 2
with CoII and RhIII chlorides (Scheme 1).
For the synthesis of terpyridineꢀcontaining (tpy) 2ꢀthioꢀ
hydantoins, we employed two alternative approaches: conꢀ
densation of 4´ꢀ(4ꢀformylphenyl)ꢀ[2,2´:6´,2]terpyridine
with N(3)ꢀsubstituted 2ꢀthiohydantoins (A) and threeꢀ
component condensation of 4´ꢀ(4ꢀformylphenyl)ꢀ
[2,2´:6´,2]terpyridine with isothiocyanate and glycine (B)
(the latter approach was used only to obtain N(3)ꢀphenyl
derivative 2).
Thiohydantoins 1 and 2 were alkylated with iodoꢀ
methane to give 2ꢀmethylthioꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ
4ꢀones 3 and 4, which are also of interest as potential
ligands in complexation reactions. The Zꢀconfiguration of
the exocyclic C=C bond in compounds 1—4 was deterꢀ
mined from the chemical shifts of the signals for the vinylꢀ
ic protons in the 1H NMR spectra.6
Reactions of ligand 2 with cobalt and rhodium chloꢀ
rides gave polynuclear complexes 5 and 6, which were
identified by IR spectroscopy, elemental analysis, and mass
spectrometry. The shift of the absorption band of the C=O
group in the IR spectra of compounds 3—6 by 15—35 cm–1
to the lower wavenumbers (compared to its position in the
spectra of thiohydantoins 1 and 2) suggests that the carboꢀ
nyl group is involved the system of conjugated ꢀbonds.
Plausible structures of complexes 5 and 6 are shown in
Scheme 1. However, Xꢀray diffraction is required to deꢀ
termine their true structures.
a harder and stronger base7,8) has not been documentꢀ
ed earlier. The ligands obtained seem to be promising
for subsequent preparation of complexes of dissimilar
metal ions.
1
H NMR spectra were recorded on a Bruker Avance instruꢀ
ment (400 MHz). IR spectra were recorded on a TermoNicolet
IR200 FTIR spectrometer. Mass spectra (MALDIꢀTOF) were
measured on a Bruker Autoflex II instrument (FWHM resoluꢀ
tion 18 000, nitrogen laser,  = 337 nm, TOF mass analyzer,
accelerating voltage 20 kV). Samples were applied to a polished
steel substrate; the anthracene matrix was used.
Synthesis of (5Z)ꢀ5ꢀ[4ꢀ(2,2´:6´,2ꢀterpyridinꢀ4´ꢀyl)benzylꢀ
idene]ꢀ2ꢀthioxoimidazolidinꢀ4ꢀones (general procedure). A.
4ꢀ(2,2´:6´,2ꢀTerpyridinꢀ4´ꢀyl)benzaldehyde (1 equiv.) was addꢀ
ed to a solution of thiohydantoin and KOH in EtOH (40 mL).
The resulting mixture was stirred at 60 C for seven days, conꢀ
centrated in vacuo to half its volume, and acidified with HCl to
pH  5. The precipitate that formed was filtered off on a porous
filter, washed with ethanol and diethyl ether, and dried in air.
B. 4ꢀ(2,2´:6´,2ꢀTerpyridinꢀ4´ꢀyl)benzaldehyde (1 equiv.)
and phenyl isothiocyanate (1 equiv.) were added to a solution of
glycine in glacial acetic acid (3 mL). The reaction mixture was
refluxed for 3 h. On cooling, the precipitate that formed was
filtered off on a porous filter, washed with ethanol and diethyl
ether, and dried in air.
(5Z)ꢀ3ꢀMethylꢀ5ꢀ[4ꢀ(2,2´:6´,2ꢀterpyridinꢀ4´ꢀyl)benzylꢀ
idene]ꢀ2ꢀthioxoimidazolidinꢀ4ꢀone (1). A. The synthesis from
4ꢀ(2,2´:6´,2ꢀterpyridinꢀ4´ꢀyl)benzaldehyde (0.337 g, 1 mmol),
3ꢀmethylꢀ2ꢀthioxoimidazolidinꢀ4ꢀone (0.13 g, 1 mmol), and
KOH (0.066 g, 1.1 mmol) yielded 0.26 g (58%) of compound 1
1
as a yellow powder. H NMR (DMSOꢀd6), : 12.45 (s, 1 H,
NH); 8.65—8.80 (m, 6 H, H(3), H(3´), H(3), H(5´), H(6),
H(6 tpy); 7.90—8.10 (m, 6 H, H(4), H(4 H(5), H(5 tpy;
HAr(2), HAr(6)); 7.55 (d, 2 H, HAr(3), HAr(5), J = 9 Hz); 6.62
(s, 1 H, =CH); 3.21 (s, 3 H, NMe). IR (KBr), /cm–1: 1714 (C=O).
MS (MALDIꢀTOF), m/z (Irel (%)): 450 [M + H]+ (100).
(5Z)ꢀ3ꢀPhenylꢀ5ꢀ[4ꢀ(2,2´:6´,2ꢀterpyridinꢀ4´ꢀyl)benzylidꢀ
ene]ꢀ2ꢀthioxoimidazolidinꢀ4ꢀone (2). A. The synthesis from
4ꢀ(2,2´:6´,2ꢀterpyridinꢀ4´ꢀyl)benzaldehyde (0.253 g, 0.75 mmol),
3ꢀphenylꢀ2ꢀthioxoimidazolidinꢀ4ꢀone (0.144 g, 0.75 mmol), and
KOH (0.05 g, 0.83 mmol) yielded 0.215 g (56%) of compound 2
as a yellow powder.
To sum up, we synthesized a novel type of ditopic
organic ligands in which chelating fragments differ in baꢀ
sicity. Such a combination of electronꢀdonating centers
(sulfur is a soft base of medium strength, while nitrogen is
B. The synthesis from 4ꢀ(2,2´:6´,2ꢀterpyridinꢀ4´ꢀyl)benzꢀ
aldehyde (0.1 g, 0.3 mmol), glycine (0.022 g, 0.3 mmol), and
phenyl isothiocyanate (0.035 mL, 0.3 mmol) yielded 0.064 g
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2631—2633, December, 2013.
1066ꢀ5285/13/6212ꢀ2631 © 2013 Springer Science+Business Media, Inc.

2632
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 12, December, 2013
Manzhelii et al.
Scheme 1
R = Me (1, 3), Ph (2, 4, 5, 6)
Reagents and conditions: i. A:
, KOH, EtOH, 50 C or B: PhNCS, glycine, AcOH, ; ii. MeI, EtONa, EtOH;
iii. CoCl2, MeOH, ; iv. RhCl3•H2O, EtOH—H2O.
1
(42%) of compound 2; yellow powder, m.p.. 290 C. H NMR
(DMSOꢀd6), : 12.77 (br.s, 1 H, NH); 8.80—8.95 (m, 6 H, H(3),
H(3´), H(3), H(5´), H(6), H(6 tpy); 8.30 (d, 2 H, H(4), H(4),
tpy, J = 6 Hz); 8.00—8.15 (m, 4 H, HAr); 7.75 (d, 2 H, H(5),
H(5 tpy, J = 6 Hz); 7.45—7.60 (m, 3 H, HPh); 7.43 (d, 2 H,
HPh, J = 8 Hz); 6.77 (s, 1 H, =CH). IR (KBr), /cm–1: 1740
(C=O). MS (MALDIꢀTOF), m/z (Irel (%)): 510 [M – H]+ (80).
Synthesis of (5Z)ꢀ2ꢀmethylthioꢀ5ꢀ[4ꢀ(2,2´:6´,2ꢀterpyridinꢀ
4´ꢀyl)benzylidene]ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀones (general proꢀ
cedure). (5Z)ꢀ5ꢀ[4ꢀ(2,2´:6´,2ꢀTerpyridinꢀ4´ꢀyl)benzylidene]ꢀ2ꢀ
thioxoimidazolidinꢀ4ꢀone and metallic sodium were successiveꢀ
ly dissolved in ethanol (20 mL). The iodomethane was added,
and the reaction mixture was stirred at 40 C for 24 h. On coolꢀ
ing, the precipitate that formed was filtered off, washed with
water, cold ethanol, and cold diethyl ether, and dried in air.
(5Z)ꢀ3ꢀMethylꢀ2ꢀmethylthioꢀ5ꢀ[4ꢀ(2,2´:6´,2ꢀterpyridinꢀ
4´ꢀyl)benzylidene]ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀone (3) was obꢀ
tained from compound 1 (0.20 g, 0.41 mmol), MeI (0.29 mL,
4.1 mmol), and metallic Na (0.01 g, 0.41 mmol). Yield 0.08 g
1
(42%), light brown powder, m.p. 257 C. H NMR (CDCl3),
: 8.81 (s, 2 H, H(3´), H(5´), tpy); 8.75 (d, 2 H, H(6), H(6 tpy,
J = 6 Hz); 8.70 (d, 2 H, H(3), H(3 tpy, J = 8 Hz); 8.32 (d, 2 H,

5ꢀ(Terpyridylbenzylidene)thiohydantoins
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 12, December, 2013
2633
HAr(2), HAr(6), J = 8 Hz); 8.00 (d, 2 H, HAr(3), HAr(5),
J = 8 Hz); 7.91 (td, 2 H, H(4), H(4 tpy, 1J = 8 Hz, 2J = 1 Hz);
7.37 (td, 2 H, H(5), H(5 tpy, 1J = 6 Hz, 2J = 1 Hz); 7.02 (s, 1 H,
=CH); 3.21 (s, 3 H, NMe); 2.80 (s, 3 H, SMe). IR (Nujol),
/cm–1: 1710 (C=O).
C62H40N10O2S2Cl7Rh3•5H2O. Calculated (%): C, 44.62;
H, 3.00; N, 8.49.
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos 13ꢀ03ꢀ00399
and 12ꢀ04ꢀ00988).
(5Z)ꢀ2ꢀMethylthioꢀ3ꢀphenylꢀ5ꢀ[4ꢀ(2,2´:6´,2ꢀterpyridinꢀ4´ꢀ
yl)benzylidene]ꢀ3,5ꢀdihydroꢀ4Hꢀimidazolꢀ4ꢀone (4) was obtainꢀ
ed from compound 2 (0.13 g, 0.254 mmol), MeI (0.18 mL,
2.54 mmol), and metallic Na (6 mg, 0.254 mmol). Yield 0.09 g
References
1
(67%), light brown powder, m.p. 210 C. H NMR (CDCl3),
1. V. Grosshenny, A. Harriman, F. M. Romero, R. Ziessel,
J. Phys. Chem., 1996, 100, 17472.
2. A. G. Majouga, R. B. Romashkina, A. S. Kashaev, E. K.
Beloglazkina, R. D. Rakhimov, N. V. Zyk, Khim. Geterotsikl.
Soedin., 2010, 1335 [Chem. Heterocycl. Compd. (Engl. Transl.),
2010, 46].
3. R. B. Romashkina, A. G. Majouga, E. K. Beloglazkina, D. A.
Pichugina, M. S. Askerka, A. A. Moiseeva, R. D. Rakhimov,
N. V. Zyk, Russ. Chem. Bull. (Int. Ed.), 2012, 61, 2265 [Izv.
Akad. Nauk, Ser. Khim., 2012, 2244].
4. A. G. Majouga, E. K. Beloglazkina, O. V. Shilova, A. A.
Moiseeva, N. V. Zyk, Russ. Chem. Bull. (Int. Ed.), 2009, 58,
1392 [Izv. Akad. Nauk, Ser. Khim., 2009, 1353].
: 8.86 (s, 2 H, H(3´), H(5´), tpy); 8.72—8.78 (m, 4 H, H(3),
H(3 H(6), H(6 tpy); 8.38 (d, 2 H, HAr(2), HAr(6), J = 8 Hz);
8.05 (d, 2 H, HAr(3), HAr(5), J = 8 Hz); 7.94 (t, 2 H, H(4),
H(4 tpy, J = 8 Hz); 7.35—7.57 (m, 7 H, H(5), H(5 tpy,
HPh); 7.12 (s, 1 H, =CH); 2.77 (s, 3 H, SMe). IR (Nujol), /cm–1
:
1725 (C=O).
Synthesis of metal complexes from (5Z)ꢀ3ꢀphenylꢀ5ꢀ[4ꢀ
(2,2´:6´,2ꢀterpyridinꢀ4´ꢀyl)benzylidene]ꢀ2ꢀthioxoimidazolidinꢀ
4ꢀone (general procedure). A solution of compound 2 and a metal
salt in a solvent (20 mL, see below) was refluxed for 48 h and
cooled to room temperature. The precipitate that formed was
filtered off, washed with cold ethanol and cold diethyl ether, and
dried in air.
5. E. K. Beloglazkina, A. G. Majouga, I. V. Yudin, N. A. Frolꢀ
ova, N. V. Zyk, V. D. Dolzhikova, A. A. Moiseeva, R. D.
Rakhimov, K. P. Butin, Russ. Chem. Bull. (Int. Ed.), 2006,
55, 1015 [Izv. Akad. Nauk, Ser. Khim., 2006, 978].
6. E. K. Beloglazkina, S. Z. Vatsadze, A. G. Majouga, N. A.
Frolova, R. B. Romashkina, N. V. Zyk, A. A. Moiseeva,
K. P. Butin, Russ. Chem. Bull. (Int. Ed.), 2005, 54, 2771 [Izv.
Akad. Nauk, Ser. Khim., 2005, 2679].
7. M. H. Chisholm, E. R. Davidson, J. C. Huffman, K. B.
Quinian, J. Am. Chem. Soc., 2001, 123, 9652.
8. S. V. Kryatov, B. S. Mohanraj, V. V. Tarasov, O. P. Kryaꢀ
tova, E. V. RybakꢀAkimova, Inorg. Chem., 2002, 41, 923.
Bis[(5Z)ꢀ3ꢀphenylꢀ5ꢀ[4ꢀ(2,2´:6´,2ꢀterpyridinꢀ4´ꢀyl)benzylꢀ
idene]ꢀ2ꢀthioxoimidazolidinꢀ4ꢀone]tricobalt(II) tetrachloride (5)
was obtained from compound 2 (0.115 g, 0.225 mmol) and CoCl2
(0.073 g, 0.563 mmol) in dry methanol. Yield 0.087 g (60%),
light green powder, m.p. > 300 C. IR (KBr), /cm–1: 1705
(C=O). Found (%): C, 55.25; H, 3.38; N, 10.31; S, 4.38.
C62H40N10O2S2Cl4Co3. Calculated (%): C, 55.56; H, 2.98;
N, 10.45; S, 4.78.
Bis[(5Z)ꢀ3ꢀphenylꢀ5ꢀ[4ꢀ(2,2´:6´,2ꢀterpyridinꢀ4´ꢀyl)benzylꢀ
idene]ꢀ2ꢀthioxoimidazolidinꢀ4ꢀone]trirhodium(III) heptachloride
pentahydrate (6) was obtained from compound 2 (0.022 g,
0.043 mmol) and RhCl3•H2O (0.037 g, 0.13 mmol) in ethaꢀ
nol—water (2 : 1). Yield 0.024 g (67%), light brown powder,
m.p. > 300 C. IR (KBr), /cm–1: 3300—3600 (O—H),
1768, 1720 (C=O). Found (%): C, 44.42; H, 3.03; N, 8.27.
Received July 1, 2013;
in revised form September 10, 2013