Synthesis, characterization, and electrochemical properties of a novel macrocylic ligand and its transition metal complexes

Article abstract of DOI:10.1007/s007060200033

2,3-Dibromo-6,7,13,14,15,16,22,23-octahydro-14,15-bis-(hydroxyimino)-tribenzo [e,k,q] [ 1,4,7,10,13,16]tetraoxadiazacyclohexadecine (LH₄) was prepared by condensation of 1,2-bis-(2′-aminophenoxyethoxy)-4,5-dibromobenzene with cyanogen-di-N-oxid

Full text of DOI:10.1007/s007060200033

Monatshefte fuÈr Chemie 133, 609±622 ꢀ2002)
Synthesis, Characterization,
and Electrochemical Properties
of a Novel Macrocylic Ligand
and its Transition Metal Complexes
1;Ã
2
3
3
_
È
Ismail Yilmaz , Mehmet Kandaz , Ali Riza Ozkaya , and Atif Koca
1
_
Department of Chemistry, TechnicalUniversity of Istanbul, TR-80626 Maslak,
_
Istanbul, Turkey
2
3
Department of Chemistry, Sakarya University, TR-54100 Adapazarꢀ, Sakarya, Turkey
_

Department of Chemistry, Marmara University, TR-81040 Kadꢀkoy, Istanbul, Turkey
Summary. 2,3-Dibromo-6,7,13,14,15,16,22,23-octahydro-14,15-bis-ꢀhydroxyimino)-tribenzo
[e,k,q][1,4,7,10,13,16]tetraoxadiazacyclohexadecine ꢀLH4) was prepared by condensation of 1,2-
bis-ꢀ20-aminophenoxyethoxy)-4,5-dibromobenzene with cyanogen-di-N-oxide. Mono-, di-, and tri-
nuclear transition metal complexes of this ligand ꢀꢀLH3)2Ni, ꢀLH3)2Zn, ꢀLH3)2Co, ꢀLH3)2Cu,
ꢀLH3)2Fe, ꢀLH3)2ꢀUO2)2ꢀOH)2, ꢀLH)2Cu3, ꢀLH)2Co3) were synthesized under basic conditions. The
electrochemical properties of the mono- and dinuclear complexes were studied by cyclic voltammetry
in DMSO solution containing TBAP. The results showed that all redox processes are based on the
metal center and the oxime ligands stabilize the NiꢀIII), FeꢀIII), CoꢀIII), and CuꢀIII) species formed
during oxidation. The FeꢀII) and UꢀVI)O2 complexes displayed a different behaviour: a reduction
peak with the corresponding anodic signalduring the reverse scan was observed. The oxime moiety
also stabilizes UꢀV)O2 which forms during the reduction process of the uranylcompelx. CuꢀII)
was adsorbed on the electrode surface upon scanning cathodically.
Keywords. vic-Dioxime; Macrocycle; CoꢀII); UꢀIV); Electrochemistry.
Introduction
Oxime ligands are widely recognized for their physicochemical properties, reac-
tivity patterns, and potentialapplications in medicinalchemistry [1±4], bioorganic
systems [5±7] and the ®eld of electrochemical and electrooptical sensors [8±10].
The synthesis of purpose-designed macrocyclic ligands, which are capable of form-
ing multinuclear complexes, is of great interest for special applications. For these
purposes, the ligands need to carry multidonor groups to be able to bind more than
one metal ion simultaneously [11±14]. Various vic-dioximes and their mono-, di-,
and trinuclear complexes have been topics of recent research [15±18].
Ã
Corresponding author. E-mail: iyilmaz@itu.edu.tr

_
610
I. Yꢀlmaz et al.
Since the ®rst observations of the transition metal binding ability and selec-
tivity of secondary amine functions in macrocycles, considerable efforts have been
undertaken to incorporate these functionalgroups into new compounds. The main
interest in these compounds which contain both macrocycles and a vic-dioxime
moiety arises from an investigation of the transition metalion coordination of the
macrocycles [19±26].
We have previously reported on the synthesis of MN4-core containing com-
pounds [27±35]. Recently, we have also focused on monophthalocyanines and
double-decker phthalocyanines which have been the subject of extensive inves-
tigations with respect to their electrochromic properties and intrinsic semiconduc-
tivity [36].
The ability of oxime-containing ligands to stabilize reduced and oxidized
forms of metal ions is of vital importance in their application in electrochemical
and electrooptical sensors [8±10]. However, literature dealing with the electro-
chemistry of metal oximes, especially in organic solvents, is scarce [37±39].
Only the reduction of neutral and anionic benzaldoxime, different aldoximes and
ketoximes derivatives, and, more recently, the electrochemical properties of rhenium
ketoxime have been published [40, 41]. Thus, we concentrated our attention to the
investigation of the electrochemical properties of metal oximes in nonaqueous
media.
In the present work we introduce for the ®rst time a new generation of higher-
membered macrocyclic derivatives of a vic-dioxime ligand carrying an 18-mem-
bered N2O4 macrocycle and its complexes with Cu, Co, Ni, UO2, Fe, and Zn ions.
The electrochemical behaviour of mono- and dinuclear complexes was studied.
Results and Discussion
Synthesis
1,2-Bis-ꢀ20-nitro phenoxyethoxy)-4,5-dibromobenzene ꢀ2) was synthesized by re-
action of 2-nitrophenolwith 1,2- bis-ꢀiodoethoxy)-4,5-dibromobenzene ꢀ1) which
was obtained from a multi-step reaction sequence according to published methods
[42±45]. 2 was reduced to 1,2-bis-ꢀ20-aminophenoxyethoxy)-4,5-dibromobenzene
ꢀ3) by iron powder in a weakly acidic medium maintained below pH ˆ 7 by
addition of acetic acid [21]. 2,3-Dibromo-6,7,3,14,15,16,22,23-ocyahydro-14,15-
bis-ꢀhydroxyimino)-tribenzo[e,k,q],[1,4,7,10,13,16]tetraoxadiazacyclohexadecine
ꢀ4, LH4) was prepared in moderate yield by condensation of 3 with cyanogen-di-N-
oxide which was prepared by treatment of a suspension of anti-dichloro glyoxime in
CH2Cl2 with 1 N aqueous Na2CO3 at À20ꢀC ꢀScheme 1). The high-dilution tech-
nique was used to prevent polymer formation in CH2Cl2. Compound 4 is light
sensitive; therefore, its grey color gradually turns to red-brown. The mono-, bi-,
and trinuclear complexes ꢀLH3)2Ni ꢀ5), ꢀLH3)2Zn ꢀ6), ꢀLH3)2Cu ꢀ7), ꢀLH3)2Co ꢀ8),
ꢀLH3)2Fe ꢀ9), ꢀLH3)2ꢀUO2)2 ꢀ12), ꢀLH)2Cu3 ꢀ10), and ꢀLH)2Co3 ꢀ11) were syn-
thesized by reaction of 4 with nitrates of NiꢀII), ZnꢀII), CuꢀII), CoꢀII), FeꢀII), and
UO2ꢀVI). The mononuclear complexes have a metal:ligand ratio of 1:2, and the
ligand is coordinated only by the N,N0 atoms of the vic-dioxime moiety. In contrast,
two metalions are coordinated to the two nitrogen and two oxygen atoms of each

Complexes of an 18-Membered vic-Dioxime Macrocycle
611
Scheme 1. i: DMF, K2ꢀCO3); ii: Fe, CH3COOH; iii: cyanogen-di-N-oxide, CH2Cl2, À40ꢀC;
iv: THF, ML2 Á 6H2O ꢀL ˆ NO3, M ˆ Ni, Zn, Cu, Co, Fe, UO2), Et3N, DMF, KOH
macrocycle in trinuclear complexes, whereas the third metal ion is coordinated by
the N,N0 atoms of each oxime group in the two ligand molecules ꢀScheme 1). These
complexes have a metal:ligand ratio of 3:2.

_
612
I. Yꢀlmaz et al.
The new compounds were characterized by elemental analyses and spectro-
scopic techniques. The IR spectra of 2 and 3 exhibited characteristic frequencies at
3080, 3030 ꢀCH±Ar), 2930±2860 ꢀCH aliph.), 1350, 1150 ꢀ±SO2), 640 ꢀC±Br),
3460±3350 ꢀAr±NH2), 3055, 3030 ꢀAr±H), 2960, 2850, ꢀCH-Aliph), and 660 ꢀC±
Br) cmÀ1. The remainder of the spectrum of 2 was closely similar to that of 3. In
the spectrum of 4 the NH and OH stretching vibrations were observed at 3370 and
3240 cmÀ1 as slightly broadened absorptions in addition to the CˆN and N±O
stretching vibrations at 1640 and 950 cmÀ1. In the IR spectra of the mono- and
trinuclear complexes, weak O±HÁ Á ÁO deformation vibrations were observed at
1700±1710 cmÀ1, and the stretching vibration of the NH group in 10 and 11 dis-
appeared which also con®rmed the formation of trinuclear complexes. The
disappearance of the O±H band and the shift of peaks assigned to CˆN, CˆC, and
N±O frequencies in the IR spectra of mono- and dinuclear complexes could be
attributed to N,N0-chelating [25]. The appearance of weak O±HÁ Á ÁO bending
vibrations around 1700±1710 cmÀ1 indicated the coordination of the metalion by
two hydrogen bridges. In addition to the O±HÁ Á ÁO bending vibrations around
1700 cmÀ1, 10 and 11 showed two strong sharp bands at around 1230 and
950 cmÀ1 which could be assigned to ꢀꢀC±O±C) and ꢀꢀN±OÁ Á Á). The IR spectrum
of 12 was also consistent with the dimeric formula ꢀFig. 1). A strong band around
900 cmÀ1 was characteristic for ꢀꢀOˆUˆO) vibrations; NH and OH stretching
vibrations of the oxime groups still appeared as broad bands at 3370 and
3250 cmÀ1.
The 1H NMR spectra of 2, 3, and 4 were consistent with the proposed formulae.
For 2 and 3, the signals of all aromatic protons could be assigned. The aliphatic
protons of these compounds appeared at 4.26 ꢀt), 3.99 ꢀt), 4.17 ꢀt), and 3.90 ꢀt) ppm.
1
In the H NMR spectrum of 3, the primary aromatic amine protons were also ob-
served at 5.36 ppm as a singlet, easily identi®ed by deuterium exchange. In the 1H
NMR spectrum of 4, the singlet assigned to the NH2 protons in 3 disappeared, and
signals at 10.74 and 8.66 ppm were observed due to the exchangeable NOH and NH
protons. These singlets indicated the ꢀE,E)-con®guration of the vic-dioxime [15]
Fig. 1. Binuclear uranyl complex 12

Complexes of an 18-Membered vic-Dioxime Macrocycle
613
ꢀScheme 1). The chemicalshifts of the aromatic and methylene protons of 4 were in
accordance with those of the macrocyclic compounds described in Refs. [21, 25].
1
The H NMR spectrum of 4 indicated the anti-isomer of the vic-dioxime by the
presence of only one singlet for the NOH protons at low ®eld ꢀ10.74 ppm). The
signals corresponding to aromatic and aliphatic protons of 4 were slightly shifted
compared to those of 2 and 3.
The 1H NMR spectra of the diamagnetic complexes 5 and 6 were characterized
by the disappearance of the NOH signalat 10.74 ppm, and the formation of an
intermolecular hydrogen bond was observed ꢀsignals at 16.40 and 16.78 ppm in
addition to those of the NH protons at 8.61 and 8.63 ppm). The bridge protons
could also easily be identi®ed by deuterium exchange. The signals of NH, aromatic
protons, and aliphatic protons were similar to what was observed for 4 except for a
slight shift.
1
The H NMR spectrum of 12 showed two chemicalshifts for the deuterium-
exchangeable NOH protons at 10.90 and 10.35 ppm and the NH protons at 8.44 and
8.15 ppm, which could be attributed to the magnetic anisotropy of the uranyl ion as
discussed previously in relation to some carboxylate and amine complexes [12, 21,
23]. It is known that the uranylion enhances the chemicalshift difference between
non-equivalent protons.
In the UV=Vis spectrum of 12 a strong absorption at 400 nm, which was
assigned to a charge transfer transition from the ꢁ-orbitals of the donor atoms to the
5f and 6d orbitals of uranium, appeared as reported previously for similar com-
pounds [12, 21]. The mass spectra of 2, 3 ꢀEI), and 4 ꢀFAB) showed the proper
‡
molecular ion peaks in addition to major fragments at m=z ˆ 552.0 [M-46] , 506.1
‡
‡
‡
‡
[M-93] , 459.0 [M-139] , and 324.0 [M-278] for 2, m=z ˆ 458.2 [M-80] ,
‡
‡
‡
430.1 [M-108] , 403 [M-135] , 323.1 [M-216] , 136.1, 108.0, 92.0, and 80.0 for
3, and m=z ˆ 707 [M ‡ cyanogen-di-N-oxide ‡ 1] , 606 [M -17] , 522 [M -
‡
‡
‡
‡
‡
‡
101], and 323.2 [M -300] for 4.
In the mass spectra of the complexes, fragment ions corresponding to [M-Ni] ,
‡
‡
‡
‡
‡
[M-Co-1] , [M-Cu-1] , and [M-Zn] ꢀmononuclear compounds) and [M-2Cu-
1] and [M-2Co ‡ Cl] ꢀtrinuclear compounds) were easily identi®ed.
‡
Electrochemical Measurements
The electrochemical properties of complexes 5±9 and 12 were investigated using
voltammetric techniques. The cyclic voltammograms of all complexes are pre-
sented in Figs. 2 and 4±7; the results are summarized in Table 1. Compound 6 did
not display any peak within the available potential scale. CPC ꢀcontrolled poten-
tials coulometry) measurements showed that the number of electrons transferred is
1 for the redox processes of all complexes.
A one-electron reduction and a one-electron oxidation peak were recorded for
all complexes except for 12 which exhibited only a one-electron reduction within
the accessible potential range of the DMSO=TBAP solvent=electrolyte system.
Scanning the potential to the positive side, all complexes gave an oxidation couple
within the positive potentialwindow, which was attributed to the MꢀII)=MꢀIII)
process. These redox couples have reversible character with peak separation values
ꢀÁEp) between 55 and 80 mV at a scan rate of 10 mV Á sÀ1. ÁEp values of all

_
I. Yꢀlmaz et al.
614
Fig. 2. Cyclic voltammogram of 1.0 Â 10À4 M ꢀLH3)2Ni ꢀ5) in DMSO=0.1 M TBAP at 100 mV Á sÀ1
vs. SCE
Fig. 3. Peak current ratio ꢀIp,a=Ip,c for reduction, Ip,c=Ip,a for oxidation) vs. scan rate ꢀv) for the redox
couples of all complexes
complexes increased with the scan rate but remained in the range for quasi-
reversible systems ꢀTable 1). As shown in Fig. 7, 7 gave an oxidation couple of
different character: it is located at less positive potentials than the reduction signal
and has a shoulder. Moreover, the anodic peak current is directly proportional to
the scan rate. These results indicate that 7 is adsorbed on the electrode surface.
Upon scanning cathodically, each of 5, 7, and 8 displayed a reduction peak
without the corresponding anodic waves on the reverse scan, whereas both 9 and 12
gave a couple. These processes cannot be due to the oxime moieties because in the
highly polar solvent DMSO polarization of the hydroxyl groups of the oxime
moiety occurs and this causes an increase in negative charge in the coordinated
oxime moieties which become harder to reduce. Thus, these peaks could be
assigned to FeꢀII)=FeꢀI) for 9 and UꢀVI)O2=UꢀV)O2 for 12. The absence of the

Complexes of an 18-Membered vic-Dioxime Macrocycle
615
Fig. 4. Cyclic voltammogram of 1.0 Â 10À4 M ꢀLH3)2Fe ꢀ9) in DMSO=0.1 M TBAP at 100 mV Á sÀ1
vs. SCE
Fig. 5. Cyclic voltammogram of 1.0 Â 10À4 M ꢀLH3)2Co ꢀ8) in DMSO=0.1 M TBAP at 100 mV Á sÀ1
vs. SCE
anodic signalfor 5, 7, and 8 indicated that the charge transfer step was followed by
a fast chemical reaction, and instable electrochemically generated MꢀI) species
were formed. @Ep=@logv values given in Table 1 indicate that these reduction peaks
are not totally irreversible, although they deviate from reversibility. The absence of
an anodic signaleven at high scan rates resutls from the fast chemicalreaction
following the electron transfer reactions. Differently, both 9 and 12 gave a reduc-
tion couple within the range of quasi-reversible electron transfer processes ꢀÁEp ˆ
65 and 75 mV at 10 mV Á sÀ1; 240 and 280 mV at 100 mV Á sÀ1).
The variations of peak current ratios with scan rate for redox couples of all
complexes are presented in Fig. 3. The Ip,c=Ip,a ratios deviated from unity and
increased with increasing scan rate. This indicated the existence of a chemical
reaction following the electron transfer reaction for each complex.

_
I. Yꢀlmaz et al.
616
Fig. 6. Cyclic voltammogram of 1.0 Â 10À4 M ꢀLH3)2Cu ꢀ7) in DMSO=0.1 M TBAP at 100 mV Á sÀ1
vs. SCE
Fig. 7. Cyclic voltammogram of 1.0 Â 10À4 M ꢀLH3)2ꢀUO2)2ꢀOH)2 ꢀ12) in DMSO=0.1 M TBAP at
100 mV Á sÀ1 vs. SCE
The voltammetric results obtained in this study showed that oxime-containing
ligands stabilize NiꢀIII), FeꢀIII), CoꢀIII), and CuꢀIII), since in these cases oxidation
peaks with the corresponding cathodic signals were observed. Higher oxidation
states of the complexes appeared to be accessible in systems with oximato-nitrogen
donors, probably as a result of the coulombic in¯uence of the negative charge on
the HOMO energy and of ꢂ-donation effects [46]. Complexes 9 and 12 behaved
differently; a reduction peak with the corresponding anodic signal during the return
scan was observed only for 9 and 12. This indicated that both FeꢀIII) and FeꢀI)
species are stable because the oxime containing ligands tend to stabilize only one
of the oxidized forms of the metal center of the complexes. The stabilization of

Complexes of an 18-Membered vic-Dioxime Macrocycle
617
‡
Table 1. Cyclic voltammetric parameters of complexes vs. SCE ꢀFc=Fc ); values in parentheses:
‡
vs. Fc=Fc
Redox process
E1a=2 ꢀV)
@Epb=@logv ꢀV)
ÁEpc ꢀV)
Peak ratiod
5
7
Oxidation
Reduction
0.875 ꢀ0.375)
0.056
0.050
0.075
±
0.97
±
À0.850 ꢀÀ1.350)
Oxidation
Reduction
0.220 ꢀÀ0.280)
0.020
0.135
À0.035e
0.88
±
À1.090 ꢀÀ1.590)
±
8
Oxidation
Reduction
0.110 ꢀÀ0.390)
0.044
0.079
0.080
±
0.90
±
À1.125 ꢀÀ1.625)
9
Oxidation
Reduction
0.270 ꢀÀ0.230)
0.035
0.055
0.078
0.065
0.30
0.94
À0.920 ꢀÀ1.420)
12
Reduction
Oxidation
À0.975 ꢀÀ1.475)
0.040
±
0.075
±
0.52
±
±
a
E1=2 ˆ ꢀEpa ‡ Epc)=2 for redox couple, Epc for irreversible peaks at a scan rate of 0.010 V Á sÀ1
;
b
c
d
Epc for reduction, Epa for oxidation; ÁEp ˆ Epa À Epc at 0.010 V Á sÀ1
;
Ip,a=Ip,c for reduction,
the cathodic peak potentialis more negative than the anodic
Ip,c=Ip,a for oxidation at 0.010 V Á sÀ1
;
e
one due to adsorption
both MꢀI) and MꢀIII) by the same ligand is quite uncommon. It was generally
observed that larger numbers of imino oxime nitrogen donors stabilize the
formation of NiꢀIII), FeꢀIII), CoꢀIII), and CuꢀIII), whereas ethoxy groups may
stabilize FeꢀI). In the case of 12, the lowest oxidation state of the complex ꢀUꢀV)O2
species) was stable.
Experimental
ꢀE,E)-Dichloroglyoxime and 1,2-bis-ꢀ20-iodoethoxy)-4,5-dibromobenzene were prepared by a known
1
procedure [15]. H NMR spectra were recorded on a Bruker 200 MHz spectrometer using TMS as
internalstandard. Mass spectra were obtained with a VG Zabspec GS-MS spectrometer. IR spectra
were run on a Mattison 1000 FTIR spectrophotometer ꢀKBr pellets), UV=Vis spectra on an unicam
UV2 spectrophotometer. Elemental analyses were performed by the instrumental laboratory of the
Tubꢀtak Marmara Research Center; their results were in good agreement with the calculated values.
The metalcontent of the compelxes were determined with a Hitachi 180±80 atomic absorption
spectrometer from solutions prepared by decomposition of the compounds in concentrated HCl and
concentrated HNO3 ꢀ3:1) followed by dilution with water. The homogeneity of the products was
tested at each step by TLC ꢀSiO2, CHCl3=MeOH).
Cyclic voltammetric and controlled potential coulometric ꢀCPC) measurements were carried out
with a Princeton Applied Research Model 273 potentiostat controlled by an external PC using the
computer program HEADSTRT and utilizing a three-electrode con®guration at 25ꢀC. The Origin 5.0
graph program was used to evaluate the HEADSTRT data, to draw voltammograms, and to analyze
them. A Pt wire served as the counter electrode. A saturated calomel electrode ꢀSCE) was employed
as the reference electrode and was separated from the bulk of the solution by a glass bridge. The
‡
ferrocene=ferrocenium couple ꢀFc=Fc ) was used as internalstandard. The working eelctrode was
a Pt plate with an area of 1.0 cm2. A solution of 0.1 mol Á dmÀ3 tetrabutylammoniumperchlorate
ꢀTBAP) in extra pure DMSO was employed as the supporting electrolyte. High purity N2 was used
for deaeration at least 15 minute prior to each run. For CPC studies, a Pt gauze working electrode
ꢀ10.5 cm2 surface area), a platinum wire counter electrode separated by a glass bridge, a saturated
calomel reference electrode, and a model 377=12 synchronous stirrer were used.

_
I. Yꢀlmaz et al.
618
All reagents and solvents were of reagent-grade quality obtained from commercial suppliers. All
solvents were dried and puri®ed as described by Perrin and Armarego [47]. The solvents were stored
Ê
over molecular sieves ꢀ4 A). 1,2-Bis-ꢀ2-iodoethoxy)-4,5-dibromobenzene [43] and anti-dichloro-
glyoxime [48] were prepared by reported procedures.
1,2-Bis-)20-nitrophenoxyethoxy)-4,5-dibromobenzene ꢀ2; C22H18Br2N2O6)
To 20 cm3 of a solution of 1.93 g ꢀ13.88 mmol) 2-nitrophenol and 1.91 g anhydrous K2CO3 in DMF
which was stirred at room temperature for 1 h under an N2 atmosphere, 20 cm3 of a solution of 4.00 g
ꢀ6.94 mmol) 1 in DMF was added dropwise. After the mixture was kept at 30ꢀC for 24 h with
stirring, the yellow solution was slowly poured into 200 cm3 ice water. The precipitated white nitro
compound was collected by ®ltration, washed successively with cold H2O, cold EtOH, and diethyl
ether, and ®nally dried in vacuo.
Yield: 2.24 g ꢀ54%); m.p.: 158ꢀC; IR ꢀKBr): ꢀ ˆ 3080, 3030 ꢀAr±CH), 2930±2860 ꢀCH-aliph.),
1350, 1150 ꢀNO2), 1260, 1240 ꢀC±O±C), 640 ꢀC±Br) cmÀ1; 1H NMR ꢀ250 MHz, ꢃ, DMSO-d6): 7.74
ꢀs, 2H, Ar±H), 7.37 ꢀdd, 3J ˆ 7.5 Hz, 4J ˆ 1.6 Hz, 2H, phenyl-H3), 7.12 ꢀdt, 3J ˆ 7.7 Hz, 4J ˆ 1.5 Hz,
2H, phenyl-H5), 6.90 ꢀdt, 3J ˆ 7.8 Hz, 4J ˆ 1.7 Hz, 2H, phenyl-H4), 6.62 ꢀdd, 3J ˆ 7.5 Hz, 4J ˆ
3
1.5 Hz, 2H, phenyl-H6), 4.26 ꢀt, J ˆ 6.5 Hz, 4H, Ar±O±CH2CH2), 3.99 ꢀs, 4H, CH2CH2±O±Ar)
‡
‡
‡
‡
ppm; MS ꢀEI): m=z ꢀ%) ˆ 598 ꢀ90) [M ], 552.0 [M-46] , 506.1 [M-93] , 459.0 [M-139] , 324.0
‡
[M-278] .
1,2-Bis-)20-aminophenoxyethoxy)-4,5-dibromobenzene ꢀ3; C22H18Br2N2O6)
1.00 g ꢀ1.67 mmol) 2 and 0.80 g Fe powder ꢀ14.28 mmol) were suspended in 100 cm3 EtOH:
H2O ˆ 2:1, and the mixture was heated at re¯ux for about 1 h. Then, glacial acetic acid was added
dropwise. Heating of the mixture was continued for further 18 h, and the hot mixture was ®ltered.
White cream colored crystals were formed after cooling which were ®ltered off, washed with cold
EtOH, and dried over P2O5.
Yield: 0.55 g ꢀ61%); m.p.: 134ꢀC; IR ꢀKBr): ꢀ ˆ 3460±3350 ꢀAr±NH2), 3055±3030 ꢀAr±CH),
2960, 2850 ꢀaliph.-CH), 1615 ꢀNH-bend.), 1540±1450 ꢀAr), 1240, 1260 ꢀAr±O-aliph. and aliph-O±
Ar), 660 ꢀC±Br) cmÀ1; 1H NMR ꢀ250 MHz, ꢃ, DMSO-d6): 7.37 ꢀs, 2H, Ar±H), 7.27 ꢀdd, 3J ˆ 7.5 Hz,
4J ˆ 1.5 Hz, 2H, phenyl-H3), 7.07 ꢀdt, 3J ˆ 7.8 Hz, 4J ˆ 1.7 Hz, 2H, phenyl-H5), 6.73 ꢀd, 3J ˆ 7.2 Hz,
2H, phenyl-H4), 6.53 ꢀt, 3J ˆ 7.2 Hz, 2H, phenyl-H6), 5.36 ꢀs, 4H, Ar±NH2), 4.17 ꢀt, 3J ˆ 6.4 Hz, 4H,
3
Ar±O±CH2CH2), 3.90 ꢀt, J ˆ 6.2 Hz, 4H, CH2CH2±O±Ar) ppm; MS ꢀEI): m=z ꢀ%) ˆ 538.1 ꢀ100)
‡
‡
‡
‡
‡
[M ], 458.2 [M-80] , 430.1 [M-108] , 403 [M-135] , 323.1 [M-216] .
5,6,17,18-Dibenzo-11,12-dibromobenzo-2,3-bishydroxyimino-1,4-diaza-
7,10,13,16-tetraoxa-2,3,8,9,14,15-hexahydrocyclodecine ꢀ4; C24H22Br2O6N4)
Compound 3 ꢀ1.00 g, 1.85 mmol) was dissolved in 200 cm3 of dry CH2Cl2 and cooled to À40ꢀC.
This solution was added dropwise to a solution of cyanogen di-N-oxide in 50 cm3 CH2Cl2 which was
obtained by treating a suspension of 0.70 g ꢀ4.45 mmol) dichloroglyoxime in CH2Cl2 with 25 cm3
1 N Na2CO3 cooled to À40ꢀC. The mixture was stirred at À40ꢀC for another 4 h. When the mixture
was allowed to warm slowly to room temperature a white precipitate occurred which was separated
by ®ltration, washed with cold CH2Cl2 and diethylether to remove any unreacted starting materials,
and dried in vacuo. Finally, the creamy product was recrystallized from EtOH.
Yield: 0.44 g ꢀ38%); m.p.: 164ꢀC; IR ꢀKBr): ꢀ ˆ 3370 ꢀNH), 3240 ꢀbr, OH), 3050±3020 ꢀAr±H),
2980±2850 ꢀaliph.-H), 1640 ꢀCˆN), 1595 ꢀw), 1250±1240 ꢀC±O±C), 950 ꢀN±O), 640 ꢀC±Br) cmÀ1
;
1H NMR ꢀ250 MHz, ꢃ, DMSO-d6): 10.74 ꢀs, 2H, ˆN±OH, D-exchangeable), 8.66 ꢀs, 2H, Ar±NH,

Complexes of an 18-Membered vic-Dioxime Macrocycle
619
3
D-exchangeable), 7.70±7.27 ꢀs, 2H, Ar±H superimposed by phenyl-H3), 7.07 ꢀdt, J ˆ 8.5 Hz, 4J ˆ
1.8 Hz, 2H, phenyl-H5), 6.80 ꢀdd, 3J ˆ 7.7 Hz, 4J ˆ 1.6 Hz, 2H, phenyl-H4), 6.68 ꢀd, 3J ˆ 7.2 Hz, 2H,
3
3
phenyl-H6), 4.25 ꢀt, J ˆ 6.8 Hz, 4H, Ar±O±CH2CH2), 4.02 ꢀt, J ˆ 6.2 Hz, 4H, O±CH2CH2) ppm;
UV=Vis ꢀDMSO): ꢄmax ꢀ") ˆ 307 ꢀ9840) ꢀsh), 290 ꢀ12500) nm; MS ꢀpositive FAB, matrix: p-
‡
‡
‡
‡
nitrobenzylalcohol): m=z ꢀ%) ˆ 622 ꢀ54) [M ], 707 [M ‡ cyanogen-di-N-oxide ‡ 1] , 606 [M -
‡
‡
‡
17] , 522 [M -101], 323.2 [M -300].
Bis-)5,6,17,18-dibenzo-11,12-dibromobenzo-2,3-bishydroxyiminato-
1,4-diaza-7,10,13,16-tetraoxa-2,3,8,9,14,15-hexahydrocyclodecine)-Ni)II)
ꢀ5; C48H42Br4N8O12Ni)
A solution of 0.01 g NiꢀNO3)2 Á 6H2O ꢀ0.05 mmol) in 20 cm3 THF was added dropwise to a solution
of 0.05 g ꢀ0.09 mmol) 4 in 20 cm3 THF at room temperature. The color of the solution turned into
dark brown, and the pH dropped to ꢁ 4±5; it was raised to ꢁ 7 by addition of triethylamine under
stirring. The reaction mixture was heated to 60±70ꢀC for 2 h and then brought to room temperature.
The precipitate formed was ®ltered off, washed with cold THF, H2O, EtOH, and diethylether to
remove metalsatls and unreacted organic impurities, and dried in vacuo.
Yield: 0.04 mg ꢀ58%); m.p.: >200ꢀC; IR ꢀKBr): ꢀ ˆ 3360 ꢀNH), 3085 ꢀAr±H), 2963±2840
ꢀaliph.-H), 1710 ꢀO±HÁ Á ÁO), 1610 ꢀCN), 1590, 1560±1440 ꢀAr), 1260, 1210 ꢀAr±O-aliph., aliph.-O±
1
Ar), 1100, 1010, 1000 ꢀN±O), 710, 650 ꢀC±Br) cmÀ1; H NMR ꢀ250 MHz, ꢃ, DMSO-d6): 16.40 ꢀs,
2H, O±HÁ Á ÁO, D-exchangeable), 8.61 ꢀs, 4H, NH, D-exchangeable), 7.70±7.55 ꢀs, 2H, Ar±H
3
4
superimposed by dd, 4H, phenyl-H3), 7.15 ꢀdt, J ˆ 7.8 Hz, J ˆ 1.5 Hz, 4H, phenyl-H5), 7.03 ꢀdt,
3J ˆ 7.2 Hz, 4J ˆ 1.5 Hz, 4H, phenyl-H4), 6.55 ꢀdd, 3J ˆ 7.5 Hz, 4J ˆ 1.6 Hz, 4H, phenyl-H6), 4.20 ꢀt,
3J ˆ 6.2 Hz, 8H, Ar±O±CH2CH2), 3.92 ꢀt, 3J ˆ 6.1 Hz, 8H, Ar±O±CH2CH2); UV=Vis ꢀDMSO): ꢄmax
ꢀ") ˆ 350 ꢀ6700), 321 ꢀ11090), 303 ꢀ13030) nm; MS ꢀpositive FAB, matrix: p-nitrobenzylalcohol):
‡
‡
.
m=z ꢀ%) ˆ 1301 ꢀ9) [M ], 1242 [M-Ni]
Bis-)5,6,17,18-dibenzo-11,12-dibromobenzo-2,3-bishydroxyiminato-
1,4-diaza-7,10,13,16-tetraoxa-2,3,8,9,14,15-hexahydrocyclodecine)-Zn)II)
ꢀ6; C48H42Br4N8O12Zn)
6 was prepared following the same procedure as described for 5 starting from 0.05 g ꢀ0.09 mmol) 4
and 0.01 g ꢀ0.05 mmol) ZnꢀNO3)2 Á 6H2O.
Yield: 0.019 g ꢀ31%); m.p.: >200ꢀC; IR ꢀKBr): ꢀ ˆ 3370 ꢀNH), 3070, 3030 ꢀAr±H), 2970, 2850
ꢀaliph.-H), 1710, 1620 ꢀCN), 1590 ꢀw), 1515±1450, 1270±1240 ꢀC±O±C), 1030 ꢀN±O), 695, 660
ꢀC±Br) cmÀ1; 1H NMR ꢀ250 MHz, ꢃ, DMSO-d6): 16.78 ꢀs, 2H, O±HÁ Á ÁO, D-exchangeable), 8.63 ꢀs,
4H, NH, D-exchangeable), 7.44±7.38 ꢀs, 2H, Ar±H superimposed by dd, 4H, phenyl-H3), 7.12 ꢀdt,
3J ˆ 7.2 Hz, 4J ˆ 1.5 Hz, 4H, phenyl-H5), 6.78 ꢀdd, 3J ˆ 7.8 Hz, 4J ˆ 1.7 Hz, 4H, phenyl-H4), 6.55 ꢀd,
3
3
3J ˆ 7.2 Hz, 4H, phenyl-H6), 4.11 ꢀt, J ˆ 6.5 Hz, 8H, Ar±O±CH2CH2), 3.90 ꢀt, J ˆ 6.1 Hz, 8H,
CH2CH2±O±Ar) ppm; UV=Vis ꢀDMSO): ꢄmax ꢀ") ˆ 328 ꢀ1150, sh), 319 ꢀ1460), 303 ꢀ9100) nm; MS
‡
‡
.
ꢀpositive FAB, matrix: p-nitrobenzylalcohol): m=z ꢀ%) ˆ 1307 ꢀ15) [M ], 1242 [M-Zn]
Bis-)5,6,17,18-dibenzo-11,12-dibromobenzo-2,3-bishydroxyiminato-
1,4-diaza-7,10,13,16-tetraoxa-2,3,8,9,14,15-hexahydrocyclodecine)-Cu)II)
ꢀ7; C48H42Br4N8O12Cu)
7 was prepared following the same procedure as described for 5 starting from 0.05 g ꢀ0.09 mmol) 4
and ꢀ0.05 mmol) 0.01 g CuꢀNO3)2 Á 6H2O.
Yield: 0.03 g ꢀ53%); m.p.: >200ꢀC; IR ꢀKBr): ꢀ ˆ 3365 ꢀNH), 3075 ꢀAr±H), 2980, 2870±2830
ꢀaliph.-H), 1710, 1650 ꢀCN), 1590, 1520±1460, 1270±12550 ꢀC±O±C), 1000 ꢀN±O), 700, 650

_
I. Yꢀlmaz et al.
620
ꢀC±Br) cmÀ1; UV=Vis ꢀDMSO): ꢄmax ꢀ") ˆ 348 ꢀ2240) ꢀsh), 302 ꢀ10500) nm; MS ꢀpositive FAB,
‡
‡
.
matrix: p-nitrobenzylalcohol): m=z ꢀ%) ˆ 1304.3 ꢀ20) [M -1], 1242 [M-Cu-1]
Bis-)5,6,17,18-dibenzo-11,12-dibromobenzo-2,3-bishydroxyiminato-
1,4-diaza-7,10,13,16-tetraoxa-2,3,8,9,14,15-hexahydrocyclodecine)-Co)II)
ꢀ8; C48H42Br4N8O12Co)
8 was prepared following the same procedure as described for 5 starting from 0.05 g ꢀ0.09 mmol) 4
and 0.014 g ꢀ0.05 mmol) CoꢀNO3)2 Á 6H2O.
Yield: 0.03 g ꢀ50%); m.p.: >200ꢀC; IR ꢀKBr): ꢀ ˆ 3365 ꢀNH), 3075 ꢀAr±H), 2980, 2870±2830
ꢀaliph.-H), 1710, 1650 ꢀCN), 1590, 1520±1460, 1270±12550 ꢀC±O±C), 1010 ꢀN±O), 700, 650 ꢀC±
Br) cmÀ1; UV=Vis ꢀDMSO): ꢄmax ꢀ") ˆ 350 ꢀ1550) ꢀsh), 305 ꢀ4670) nm; MS ꢀpositive FAB, matrix:
‡
‡
p-nitrobenzylalcohol): m=z ꢀ%) ˆ 1301 ꢀ17) [M ], 1243 [M-Co-1] .
Bis-)5,6,17,18-dibenzo-11,12-dibromobenzo-2,3-bishydroxyiminato-
1,4-diaza-7,10,13,16-tetraoxa-2,3,8,9,14,15-hexahydrocyclodecine)-Fe)II)
ꢀ9; C48H42Br4N8O12Fe)
9 was prepared following the same procedure as described for of 5 starting from 0.05 g ꢀ0.09 mmol)
4 and 0.01 g ꢀ0.05 mmol) FeꢀNO3)2 Á 6H2O.
Yield: 0.03 g ꢀ51%); m.p.: >200ꢀC; IR ꢀKBr): ꢀ ˆ 3360 ꢀN±H), 3060 ꢀAr±H), 2975, 2860, 2830
ꢀaliph.-H), 1700 ꢀO±H±O), 1650 ꢀCˆN), 1520±1460, 1430, 1260±1240 ꢀC±O±C), 1080, 1030, 1010
ꢀN±O), 720, 660 ꢀC±Br) cmÀ1; UV=Vis ꢀDMSO) ꢄmax ꢀ") ˆ 437 ꢀ2350, sh), 307 ꢀ5600), 291 ꢀ12800)
‡
nm; MS ꢀpositive FAB, p-nitrobenzylalcohol): m=z ꢀ%) ˆ 1298 ꢀ12) [M ].
Bis-)5,6,17,18-dibenzo-11,12-dibromobenzo-2,3-bishydroxyiminato-
1,4-diaza-7,10,13,16-tetraoxa-2,3,8,9,14,15-hexahydrocyclodecine)-tricopper)II)
ꢀ10; C48H38Br4N8O12Cu3)
0.05 g ꢀ0.04 mmol) of 7 were dissolved in 10 cm3 DMF with heating and stirring. A solution of 0.12 g
ꢀ0.07 mmol) CuCl2 Á 2H2O in 10 cm3 DMF was added, and the mixture was stirred for 3 h at 40ꢀC.
The pH of the solution decreased and was raised to 7 by the addition of KOH. After the solvent was
removed under reduced pressure to about dryness, the precipitate was ®ltered off, washed with H2O,
EtOH, and diethylether, and dried in vacuo. 10 is slightly soluble in DMF, DMSO, and pyridine.
Yield: 0.017 g ꢀ29%); m.p.: >200ꢀC; IR ꢀKBr): ꢀ ˆ 3070±3030 ꢀAr±H), 2930±2850, ꢀaliph.-H),
1700 ꢀO±H±O), 1610 ꢀCˆN), 1510, 1460, 1240 ꢀC±O±C), 1120, 1100, 950 ꢀN±O), 670, 640,
540 cmÀ1; UV=Vis ꢀDMSO): ꢄmax ꢀ") ˆ 375 ꢀ1940), 310 ꢀ8820) nm; MS ꢀpositive FAB, p-
‡
nitrobenzylalcohol): m=z ꢀ%) ˆ 1431.3 ꢀ5) [M ‡ 3] .
Bis-)5,6,17,18-dibenzo-11,12-dibromobenzo-2,3-bishydroxyiminato-
1,4-diaza-7,10,13,16-tetraoxa-2,3,8,9,14,15-hexahydrocyclodecine)-tricobalt)II)
ꢀ11; C48H38Br4N8O12Co3)
11 was prepared following the same procedure as described for 10 starting from 0.05 g ꢀ0.04 mmol) 8
and 0.02 g ꢀ0.08 mmol) CoCl2 Á 6H2O. The dark brown complex is moderately soluble in DMF,
DMSO, and pyridine.
Yield: 0.02 g ꢀ32%); m.p.: >200ꢀC; IR ꢀKBr): ꢀ ˆ 3080, ꢀAr±H), 2925, 2840 ꢀaliph.-H), 1705
ꢀO±HÁ Á ÁO), 1595 ꢀCN), 1230, 1210 ꢀAr±O-aliph., aliph.-O±Ar), 1100, 960 ꢀN±O), 685, 650 ꢀC±Br)
cmÀ1; UV=Vis ꢀDMSO): ꢄmax ꢀ") ˆ 390 ꢀ2400, sh), 350 ꢀ6700), 302 ꢀ12350) nm; MS ꢀpositive FAB,
‡
p-nitrobenzylalcohol): m=z ꢀ%) ˆ 1416 ꢀ8) [M ‡ 1] .

Complexes of an 18-Membered vic-Dioxime Macrocycle
621
Bis-)5,6,17,18-dibenzo-11,12-dibromobenzo-2,3-bishydroxyiminato-1,
4-diaza-7,10,13,16-tetraoxa-2,3,8,9,14,15-hexahydrocyclodecine-ꢅ-hydroxo-uranyl)
ꢀ12; C48H44Br4N8O18U2)
A solution of 0.04 g ꢀ0.09 mmol) UO2ꢀNO3)2 Á 2H2O in 30 cm3 dry THF was added portion wise to a
solution of 0.05 g ꢀ0.09 mmol) 4 in 30 cm3 dry THF at room temperature. The color of the solution
turned orange. The mixture was heated for 20 min under stirring. The pH of the solution rose to ꢁ 7.
After the volume of the reaction mixture was reduced to ꢁ 15 cm3, an orange precipitated formed
which was ®ltered off, washed with H2O, EtOH, and diethyl ether, and ®nally dried in vacuo.
Yield: 0.040 g ꢀ47%); m.p.: >200ꢀC; IR ꢀKBr): ꢀ ˆ 3370 ꢀN±H), 3250 ꢀOH), 3060, 3040 ꢀAr±H),
2930±2840 ꢀCH-aliph.), 1630 ꢀCˆN), 1580 ꢀN±H), 1500±1450 ꢀAr), 1260, 1210 ꢀAr±O±C), 1010
1
ꢀN±O), 900 ꢀOˆUˆO), 635 ꢀC±Br) cmÀ1; H NMR ꢀ250 MHz, ꢃ, DMSO-d6): 10.90 ꢀs, 1H, N±
OH, D-exchangeable), 10.35 ꢀs, 1H, N±OH, D-exchangeable), 8.44 and 8.15 ꢀs, s, 4H, NH, D-
exchangeable), 7.53±7.45 ꢀs, 4H, Ar±H superimposed by phenyl H3), 7.20 ꢀdt, 3J ˆ 7.2 Hz,
4J ˆ 1.5 Hz, 4H, phenyl-H5), 6.89 ꢀdt, 3J ˆ 7.8 Hz, 4J ˆ 1.6 Hz, 4H, phenyl-H4), 6.78 ꢀd, 3J ˆ 7.5 Hz,
3
4J ˆ 1.4 Hz, 4H, phenyl-H6), 4.35 ꢀt, J ˆ 12.0 Hz, 8H, Ar±O±CH2CH2), 3.92 ꢀt, 8H, CH2CH2±O±
Ar) ppm; UV=Vis ꢀDMSO): ꢄmax ꢀ") ˆ 405 ꢀ4350), 321 ꢀ8900), 303 ꢀ11300) nm.
Acknowledgements
We thank the Research Fund of the TechnicalUniversity of Istanbulꢀproject No. 1404) and the
Sakarya University for ®nancialsupport.
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Received August 20, 2001. Accepted )revised) October 17, 2001