First example of a vic-dioxime and its homo- and heteropentanuclear complexes containing a macrobicyclic moiety

Article abstract of DOI:10.1039/b004624h

The novel N,N'-substituted diaminoglyoxime (H₂L) containing a diazadioxadithiacyclo macrobicycle has been synthesized from an aromatic primary amine containing a cryptand unit and (E,E)-dichloroglyoxime. The homopentanuclear nickel(II) and hete

Full text of DOI:10.1039/b004624h

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First example of a vic-dioxime and its homo- and heteropentanuclear
complexes containing a macrobicyclic moiety
YasÓ ar Gok,* U mmuhan Ocak and H. Basri SÓ enturk
Ž Ž Ž
Department of Chemistry, Karadeniz T echnical University, 61080 T rabzon, T urkey
L e t t e r
Received (in Montpellier, France) 8th June 2000, Accepted 3rd January 2000
First published as an Advance Article on the web 14th February 2001
The novel N,Nº-substituted diaminoglyoxime (H L) containing
crystallization, the desired product was isolated from a
mixture of chloroformÈacetone (1 : 1) and characterized. The
1H NMR spectrum of 3 showed new signals due to methylene
and aromatic protons at d 4.22 and 7.90, respectively, which
conÐrms the formation of 3. The disappearance of the NÈH
stretching vibrations seen in the IR spectrum of the starting
material 1 also suggests the formation of 3. Compound 3
displays the expected molecular ion peak in its FAB mass
spectrum (m/z 537). Proton-decoupled 13C NMR of this com-
pound clearly suggests that macrobicyclic formation has
occurred.
2
a diazadioxadithiacyclo macrobicycle has been synthesized
from an aromatic primary amine containing a cryptand unit
and (E,E)-dichloroglyoxime. The homopentanuclear nickel(II)
and heteropentanuclear complexes of dioxime were obtained.
Due to the presence of mildly acidic hydroxy groups and
slightly basic azomethine groups, vic-dioximes are amphoteric
ligands that form corrin-type square-planar, square-pyramidal
and octahedral complexes with transition metal ions such as
nickel(II), copper(II), palladium(II), cobalt(II) and cobalt(III) as
the central atoms.1 The exceptional stability and unique elec-
tronic properties of these complexes can be attributed to their
structure which is stabilized by intramolecular hydrogen
bonding.2 The complexes prepared from (E,E)-dioximes have
been extensively used for various purposes, including model
compounds to mimic biofunctions such as reduction of
and as analytical reagents for trace element
Reduction of the nitro-substituted macrobicycle 3 using hot
10% palladiumÈactivated charcoal and hydrazine hydrate
(100%) in dioxane, as previously utilized,12 gave the amine-
substituted macrobicycle 4. In the 1H NMR spectrum of 4,
there is a broad peak at d 4.60 due to the primary aromatic
amine protons, which conÐrms the structure. The 13C NMR
spectrum for 4 is also consistent with the proposed formula-
tion. In the IR spectrum of 4, NÈH stretching and bending
vibrations are observed at ca. 3448 and 1617 cm~1, respec-
tively. The mass spectrum of 4, which shows a molecular ion
peak at m/z 507, conÐrms the formula of this compound.
The Ðrst example of a vic-dioxime containing a macro-
bicyclic moiety was synthesized in good yield according to the
previously reported procedure13 involving the reaction of 2
equiv. of 4 with 1 equiv. of cyanogen-di-N-oxide9 in dichloro-
vitamin B1
2
analysis.3 They have also been examined as compounds with
columnar stacking, which is thought to be the reason for their
semiconducting properties.4 Recently, the two hydrogen
bridges have been substituted with metal complexes to obtain
polynuclear compounds in order to investigate the magnetic
interactions.5
Cryptand, which contain two macrocycles, show an extraor-
dinary selectivity for metal ion complexation in aqueous and
organic solutions, more so than do macrocyclic polyethers.
The formation of cryptates with alkali metal or alkaline earth
metals involves the inclusion of a cation into the molecular
cavity of a cryptand. This cryptate e†ect, which leads to a high
complexation stability, is greater than the macrocyclic e†ect.6
The optimal cryptates for alkali or alkaline earth cations have
stabilities several orders of magnitude higher than those of
either the natural ionophores or synthetic macrocyclic ligands.
Suitable structural modiÐcations allow control over the
M2`/M` selectivity, from a preference for alkaline earth
metal cations to a preference for alkali metal cations.6,7 On
the other hand, owing to their architectural structure and
functional plasticity, macropolycyclic systems are attractive
for designing both biomimetic and abiotic receptor molecules
for inorganic and organic substrates.8
We report here the synthesis and structural properties of an
unusual vicinal dioxime containing a macrobicyclic unit,
a†orded in high yield by the 1 : 2 reaction of cyanogen-di-N-
oxide9 and an aromatic primary amine containing a diazadi-
thiadioxa mixed-donor macrobicyclic moiety (Scheme 1).
Then, the mono Ni(II), penta-nuclear Ni(II) and hetero-
pentanuclear complexes of the dioxime have been isolated
methane (Scheme 1). In the 1H NMR spectrum of H L, the
2
deuterium exchangeable protons of the NÈOH and NH
groups appear as two singlets at d 10.38 and 7.93, respectively.
This result indicates that the structure of H L has the S-trans
2
form.14 The resonances due to the azomethine carbon atoms
in the 13C NMR spectrum of this compound are found
at lower Ðelds (d 148.24) compared to other vic-dioximes
reported in the literature.15 The equivalent carbon resonances
of the hydroxyimino groups also conÐrm the S-trans form of
the vic-dioxime.16 The disappearance of the NH stretching
2
vibrations, along with the appearance of new absorptions at
3242 [l(OÈH)] and 1044 [l(NÈO)] cm~1, are in agreement
with the proposed structure. Analysis by mass spectrometry
(FAB), shows a molecular ion peak at 1098.4, conÐrming that
a vicinal dioxime has been formed, consistent only with the
formation of H L.
2
The reaction of H L with nickel(II) chloride hexahydrate
2
(Scheme 1) gave the 1 : 2 (metal : ligand) complex 5 in 81.9%
yield, and its composition was deÐned by elemental analysis,
1H NMR, IR and MS spectral data. In the 1H NMR spectra
however, only slight di†erences between those of H L and 5
2
were observed. For 5, the presence of intramolecular OÈ
(
Scheme 2).
HÉ É ÉO bands at around d 16.92 identify the complexation
The synthesis of the macrobicyclic compound 3 was per-
formed by starting from the 14-membered diazadithia
macrocycle10 1 and 2 using Cs` cations as promotors.11 After
product. In the IR spectrum, the C2N stretching vibration
(1637 cm~1) in H L is shifted to a lower wavenumber com-
2
pared with that of 5 (1611 cm~1), and l(OÈHÉ É ÉO) of 5
364
New J. Chem., 2001, 25, 364È368
DOI: 10.1039/b004624h
This journal is ( The Royal Society of Chemistry and the Centre National de la Recherche ScientiÐque 2001

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Scheme 1 Reagents and conditions: (i) Cs O in dry acetonitrile under argon at 60 ¡C; (ii) NH ÈNH É H O, 10% Pd/C in dry dioxane at 60 ¡C;
2
3
2
2
2
(
iii) cyanogen di-N-oxide in CH Cl at [15 ¡C; (iv) NiCl É 6H O in EtOH at 65 ¡C.
2
2
2
2
appears at 1723 cm~1, whereas H L shows an absorption
(58.5%). The FAB mass spectrum of this complex exhibited an
intense peak at m/z 2764.3 [M]`, which is in accord with the
proposed structure. Compound 7 shows signiÐcant IR absorp-
tions at 1715 and 841 cm~1, which may be assigned to the
stretching and out-of-plane deformation modes of the
hydrogen-bonded OÈHÉ É ÉO groups, respectively.18 The disap-
pearance of the OÈH stretching vibrations and the shifts of the
C2N bands to lower frequencies in the IR spectrum of 7 can
be attributed to N,N@-chelation.19 This homopentanuclear
Ni(II) complex is paramagnetic. The magnetic susceptibility
2
band at 3242 cm~1 for the OÈH groups. These results suggest
coordination of the nitrogen atoms of the azomethine groups.
The fast atom bombardment mass spectrum of 5 exhibits
a molecular ion peak at m/z 2252.2, which supports the
structure.
YellowÈorange crystals of 6 were prepared in 53.3% yield
by the reaction of the mononuclear Ni(II) complex 5 with
[
Cu(CH CN) ]PF in reÑuxing ethanolÈDMF. In contrast to
3
4
6
the literature,10 the copper(I) complex of the dithiadiaza
macrocycle was successfully derived using rigorously anhy-
drous and inert reaction conditions. 1H NMR and IR spectral
and elemental analysis data conÐrm the formulation of the
heteropentanuclear complex. In the IR spectrum of this com-
pound many of the bands arising from characteristic groups
such as NÈH, OÈHÉ É ÉO, C2N are very similar to those of the
precursor Ni(II) complex 5, as expected. This complex contains
Cu(I) cations in the macrobicyclic cavities; the resonances at
(k \ 12.46 BM) is very similar to the value obtained from
tot
the spin-only formula calculated for four Ni(II) ions located in
octahedral coordination environments, consisting of the N S
2
2
donor atoms of the macrobicylic cavities in an approximately
square-planar array and two chloride ions in axial sites, while
one of the Ni(II) forms a diamagnetic structure with the
dioxime moieties. When the magnetic moment of this complex
is calculated per Ni the result is about 3.12 BM, comparable
with values given for high-spin octahedral Ni(II) complexes.20
This complex is a non-electrolyte, consistent with the pro-
posed formulation. This observation can be attributed to the
fact that the chloro groups are in the coordination sphere.
8
49 and 557 cm~1, assigned to [PF ]~, support a structure in
6
which the hexaÑuorophosphate ions are not coordinated to
the copper(I) atoms.17 The 1H NMR spectra of 5 and 6 are
largely similar, but the expected shifts due to complexation
with Cu(I) ions belonging to macrobicyclic moieties such as
CH ÈS and CH ÈN are signiÐcant.
The synthesis of the homopentanuclear complex of vic-
dioxime was accomplished in one step (Scheme 2). The desired
complex 7 which has a metal : ligand ratio of 5 : 2 according
to its elemental analysis, can be obtained in good yield
2
2
Experimental
Reagent grade chemicals were used as received. THF was dis-
tilled from sodium benzophenone ketyl under oxygen-free
nitrogen, prior to use. Other solvents were puriÐed according
New J. Chem., 2001, 25, 364È368
365

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Scheme 2 Reagents and conditions: (i) [Cu(CH CN) ]PF in dry DMFÈEtOH under argon, reÑux; (ii) NiCl É 6H O in EtOH at 60 ¡C; NEt
3 in
3
4
6
2
2
EtOH at reÑux.
to standard methods21 before use. Silica gel (70È230 mesh)
was used for chromatographic separations. The structures of
novel compounds were identiÐed by using elemental analysis,
magnetic susceptibility and conductance measurements, 1H,
three times with argon and connected to a vacuum line.
Under argon, the Ñask was charged with 6,7,8,9,15,16,17,18-
octahydrodibenzo[ f,m][1,4,8,11]dithiadiazacyclotetradecine10
(1; 1.65 g, 5 mmol) and Ðnely ground anhydrous Cs CO (3.26
g, 10 mmol) and the mixture was stirred at room temperature.
A solution of 2 (2.3 g, 5 mmol) in dry acetonitrile (50 mL) was
added to this mixture and the reaction mixture was heated
and stirred at 60 ¡C for 92 h. The reaction was monitored by
thin layer chromatography [chloroformÈacetoneÈpetroleum
ether (4 : 6 : 1)]. At the end of this period, the mixture was
cooled to room temperature and the product Ðltered o†,
washed with water and then dried in vacuo. The solid product
was re-crystallized from chloroformÈacetone. Yield: 1.67 g,
2
3
13C NMR, IR and MS spectral data.
Syntheses
2. 4-Nitro-1,2-bis(2-chloroethoxy)benzene (12.3 g, 43 mmol)
was dissolved in dry acetone (250 mL) containing anhydrous
NaI (39.5 g, 260 mmol) under an argon atmosphere and
reÑuxed for 27 h. After a while, the solution turned cloudy and
then the solid product precipitated. At the end of this period,
the reaction mixture was evaporated to dryness and treated
with ethyl acetate (100 mL). The reaction mixture was Ðltered
and washed with ethyl acetate and then dried over Na SO
6
2.3%, mp 220 ¡C. Anal. calc. for C H N O S : C, 62.56;
2
8 31 3 4 2
H, 5.77; N, 7.82%. Found: C, 62.41; H, 5.96; N, 7.60%. IR
2
4
(KBr pellets, cm~1): 3087 (ArÈH), 3056 (ArÈH), 2948È2787
overnight. After removal of the drying agent, the Ðltrate was
evaporated to 15 mL, then the residue was placed in a
refrigerator. The pale yellow crystals were separated by Ðl-
tration and dried in vacuo at room temperature. Yield: 14.3 g,
(
CÈH), 1337 (NO ), 1278È1218 (ArÈOÈC). 1H NMR (CDCl )
2
3
d: 7.90 (d, 1H, ArH), 7.67 (s, 1H, ArH), 7.24È6.93 (m, 8H,
ArH), 6.82 (d, 1H, ArH), 4.22 (t, 4H, CH O), 3.68 (s, 4H,
2
ArCH ), 3.37 (m, 8H, NCH ), 2.74 (t, 4H, SCH ). 13C NMR
7
0.2%, mp 81È82 ¡C. Anal. calc. for C
H
NI O : C, 25.92;
0 11 2 4
H, 2.37; N, 3.02%. Found: C, 25.80; H, 2.21; N, 3.23%. IR
2
3
2
2
1
(CDCl ) d: 148.04, 140.385, 134.72, 134.36, 132.03, 131.85,
1
27.74, 126.97, 126.78, 117.53, 110.66, 107.31, 66.22, 59.77,
(
1
1
KBr pellets, cm~1): 3085 (ArÈH), 2993 (CÈH), 1346 (NO ),
2
52.88, 46.45, 33.32. MS (FAB) m/z: 537 [M]`.
261È1227 (ArÈOÈC), 660 (CÈI). 1H NMR (CDCl ) d: 7.84 (d,
3
H, ArH), 7.71 (s, 1H, ArH), 6.83 (d, 1H, ArH), 4.32 (t, 4H,
CH O), 3.41 (t, 4H, CH I). MS (FAB) m/z: 461 [M]`.
4. Compound 3 (1.5 g, 2.8 mmol) was dissolved in dry
dioxane (120 mL) by heating at 60 ¡C. Palladium (10%)/
activated carbon (1.2 g) was added to the solution at the same
temperature and allowed to stand at the same temperature for
2
2
3. A 300 mL round-bottom Ñask containing dry acetonitrile
(
100 mL) and Ðtted with a condenser was evacuated, reÐlled
366
New J. Chem., 2001, 25, 364È368

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1
0 min; 5 ml of hydrazine hydrate (100%) was then added
the mixture was reÑuxed and stirred for 4 h. The end of the
reaction was determined by thin layer chromatography [n-
butanolÈacetic acidÈwater (4 : 1 : 5)]. After cooling to room
temperature the reaction mixture was concentrated under
reduced pressure to 8 mL. The crude product was allowed to
stand at [18 ¡C overnight whereupon the compound crys-
tallized from the solution. The yellowÈorange crystallized
product was collected by Ðltration, washed with cold ethanol
and acetonitrile and then dried in vacuo. Yield: 0.16 g, 53.3%,
dropwise. The reaction mixture was heated and stirred for 8 h
at 60 ¡C and then Ðltered and washed with dioxane (25 mL).
The extent of the reaction was monitored by using TLC
[petroleum etherÈacetone (1 : 2)]. The pale yellow solution
was concentrated on an evaporator to 20 mL and the solid
formed was Ðltered o†, washed with diethyl ether and then
dried in vacuo. Yield: 1.18 g, 83.6%, mp 195È196 ¡C. Anal.
calc. for C28 33 3 2 2
H N O S : C, 66.27; H, 6.50; N, 8.28%. Found:
C, 66.40; H, 6.44; N, 8.42%. IR (KBr pellets, cm~1): 3448È
mp [ 300 ¡C. Anal. calc. for C
H
N O S F P NiCu :
1
16 130 16 12 8 24 4
4
3
1
7
6
3
365 (NH ), 3050 (ArÈH), 3024 (ArÈH), 2920È2787 (CÈH),
617 (NH ), 1289È1219 (ArÈOÈC). 1H NMR (DMSO-d ) d:
.22È6.96 (m, 8H, ArH), 6.67 (d, 1H, ArH), 6.27 (s, 1H, ArH),
.10 (d, 1H, ArH), 4.60 (s, 2H, NH ), 4.18 (t, 4H, ArOCH ),
.62 (s, 4H, ArCH ), 3.46 (m, 8H, NCH ), 2.96 (t, 4H, SCH ).
C, 45.10; H, 4.21; N, 7.25; Ni, 1.90; Cu, 8.22%. Found: C,
44.83; H, 4.02; N, 7.42; Ni, 2.15, Cu, 8.02%. IR (KBr pellets,
cm~1): 3411 (NÈH), 3044 (ArÈH), 2933È2811 (CÈH), 1710 (OÈ
2
2
6
HÉ É ÉO), 1622 (C2N), 1598 (AÈH), 1276È1220 (ArÈOÈCH ),
2
2
2
2
1009 (NÈO), 849, 557 (PF )~. 1H NMR (DMSO-d ) d: 17.00
2
2
6
6
1
3C NMR (DMSO-d ) d: 145.31, 142.42, 138.25, 134.04,
(s, 2H, OÈHÉ É ÉO), 8.17 (br, 4H, NH), 7.51È7.10 (m, 32H, ArH),
6.88È6.67 (m, 8H, ArH), 6.42 (m, 4H, ArH), 4.36 (m, 16H,
ArOCH ), 3.80 (m, 16H, ArCH ), 3.66 (m, 32H, NCH ), 2.88
6
1
6
32.10, 128.13, 127.41, 126.15, 125.52, 114.90, 106.97, 100.10,
5.78, 58.20, 52.26, 45.21, 33.76. MS (FAB) m/z: 507 [M]`.
2
2
2
(
m, 16H, SCH ).
2
H L. A solution of cyanogen di-N-oxide in dichloro-
2
methane (20 mL), which was prepared from (E,E)-dichloro-
glyoxime (0.157 g, 1 mmol) and an aqueous solution of
Na CO (10 mL, 0.5 M), was added to a cold solution
7. An excess solution of nickel(II) chloride hexahydrate (0.20
g, 0.85 mmol) in dry ethanol (30 mL) was added in small por-
tions to a stirred solution of H L (0.33 g, 0.3 mmol) in dry
2
3
2
([15 ¡C) of 4 (1.01 g, 2 mmol) in dichloromethane (50 mL).
ethanol (80 mL) at 60 ¡C over a period of 10 min; a distinct
The reaction was continued for 10 h at this temperature and
the yellow product formed separated by Ðltration, washed
with cold dichloromethane and diethyl ether and then dried in
vacuo. The Ðltrate was removed in vacuo and the oily product
was puriÐed by column chromatography [silica gel (70È230),
dioxane]. Yield: 0.83 g, 75.6%, mp 212 ¡C (dec.). Anal. calc.
change in colour from colourless to blue and a decrease in the
pH of the solution was observed. While heating the mixture to
reÑux temperature, a stoichiometric amount of triethylamine
(0.03 g, 0.3 mmol) in ethanol (1 mL) was added and the
resulting mixture was reÑuxed with stirring for 6 h. After
cooling to room temperature, the solution was concentrated
to 20 mL and diethyl ether (4 mL) was added. A dark-blue
crystalline product of the homopentanuclear complex depos-
ited from the solution overnight which was Ðltered o†, washed
with cold ethanol and diethyl ether and then dried in vacuo.
Yield: 0.24 g, 58.5%, mp [ 300 ¡C. Anal. calc. for
for C
H
N O S : C, 63.38; H, 6.01; N, 10.20%. Found: C,
8 66 8 6 4
3.53; H, 5.88; N, 9.97%. IR (KBr pellets, cm~1): 3378 (NÈH),
5
6
3
242 (OÈH), 3053 (ArÈH), 2917È2792 (CÈH), 1637 (C2N), 1607
(
NÈH), 1277È1220 (ArÈOÈC), 1044 (NÈO). 1H NMR (DMSO-
d ) d: 10.38 (s, 2H, OH), 7.93 (s, 2H, NH), 7.31È6.98 (m, 16H,
ArH), 6.76 (d, 2H, ArH), 6.62 (s, 2H, ArH), 6.33 (d, 2H, ArH),
6
C
H
N O S Cl Ni : C, 50.23; H, 4.69; N, 8.08; Ni,
1
16 130 16 12 8
8
5
4
.27 (m, 8H, ArOCH ), 3.77 (m, 8H, ArCH ), 3.55 (m, 16H,
10.59%. Found: 50.39; H, 4.41; N, 8.43; Ni, 10.38%. IR (KBr
pellets, cm~1): 3403 (NÈH), 3045 (ArÈH), 2912È2800 (CÈH),
1715 (OÈHÉ É ÉO), 1618 (C2N), 1603 (NÈH), 1292È1221
2
2
NCH ), 3.09 (t, 8H, SCH ). 13C NMR (DMSO-d ) d: 146.41,
2
2
6
1
1
43.65, 142.53, 138.49, 135.16, 132.31, 128.34, 127.66, 126.27,
25.71, 115.20, 107.35, 100.32, 67.58, 58.38, 52.60, 56.16, 33.87.
(ArÈOÈCH ), 996 (NÈO), 841 (OÈHÉ É ÉO. MS (FAB) m/z:
2
MS (FAB) m/z: 1098.4 [M]`.
2764.3 [M]`.
5
. A solution of nickel(II) chloride hexahydrate (0.077 g, 0.32
Acknowledgements
mmol) in ethanol (10 mL) was added to a solution of H L
(
2
0.71 g, 0.65 mmol) in ethanol (100 mL) at 60 ¡C, a distinct
change in colour from colourless to red and a decrease in the
pH of the solution was observed. While heating the mixture to
This work was supported by the Research Fund of Karadeniz
Technical University (Trabzon-Turkey). We are indebted to
Professor M. Hanack (Tubingen University, Germany) for
assistance with the mass spectral data.
6
5 ¡C an ethanolic solution of KOH (0.1 M) was added and an
orange precipitate of 5 formed. After heating the mixture for 4
h in a water bath, the precipitate was Ðltered o†, washed with
water, ethanol and diethyl ether and then dried in vacuo.
Yield: 0.59 g, 81.9%, mp 276 ¡C (dec.). Anal. calc. for
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1
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3
Ž

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2
6
2
6
1
2
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.92 (m, 16H, SCH ). MS (FAB) m/z: 2252.2 [M]`.
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[
Cu(CH CN) ]PF 22 (0.125 g, 0.05 mmol) in dry acetonitrile
3
4
6
(
25 mL) was added slowly to the stirred hot solution of 5 and
New J. Chem., 2001, 25, 364È368
367

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