Preparation and biological activity of some novel tetrachlorocyclodiphosph (V) azane pyridazine derivatives and its metal complexes

Article abstract of DOI:10.1080/10426500801963624

1,3-diphenyl-2,2,4,4-tetrachloro-2,4-bis(4-Cyano-5,6-dimethyl-py-ridazin- 3(2H)-one) cyclodiphosph(V)azane(III), reacts with stoichiometric amounts of transition metal salts such as Mn(II), Fe(III), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and UO2(II) to afford colored complexes in a moderate to high yield. The complexes have been investigated in solution by the spectrophotometric molar ratio and conductometeric methods. The formula of the isolated complexes was suggested based on elemental analyses, IR, molar conductance, UV-Vis, 1H NMR, mass spectra, solid reflectance, and magnetic susceptibility measurements. From the elemental analyses data, 1: 2 (III : M) ratio is suggested and the complexes are found to have the general formula [(MXn)2(III)(H2O)m].yX where M = Mn(II) (X = OCOCH3, n = 2, m = 4, y = 0), Fe(III) (X = Cl, n = 2, m = 2, y = 2), Fe(II) (X = SO4, n = 1, m = 2, y = 0), Co(II) (X = OCOCH3, n = 2, m = 4, y = 0), Ni(II) (X = OCOCH3, n = 2, m = 4, y = 0), Cu(II) (X = OCOCH3, n = 2, m = 4, y = 0), Zn(II) (X = OCOCH3, n = 2, m = 4, y = 0), Cd(II) (X = Cl, n = 2, m = 4, y = 0), and UO2(II) (X = NO3, n = 1, m = 0, y = 2). The IR and 1H NMR spectral data revealed that III behaves as a neutral bidentate ligand coordinated to the metal ions through oxygen (O) and nitrogen N atoms. The UV-Vis, solid reflectance, and magnetic-moment data have shown that the ligands are coordinated to the metal ions in an octahedral manner. The molar conductance data show that the complexes are nonelectrolytes while the Fe(III) and UO2(II) complexes are 1:2 electrolytes. The in vitro-biological activity of some newly synthesized compounds against gram-positive and gram-negative bacteria was studied.

Full text of DOI:10.1080/10426500801963624

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Phosphorus, Sulfur, and Silicon
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Preparation and Biological
Activity of Some Novel
Tetrachlorocyclodiphosph (V)
Azane Pyridazine Derivatives
and Its Metal Complexes
Abdel-Nasser M. A. Alaghaz a
a Chemistry Department, Faculty of Science (Boys) ,
Al-Azhar University , Nasr-City, Cairo, Egypt
Published online: 26 Sep 2008.
To cite this article: Abdel-Nasser M. A. Alaghaz (2008) Preparation and Biological
Activity of Some Novel Tetrachlorocyclodiphosph (V) Azane Pyridazine Derivatives
and Its Metal Complexes, Phosphorus, Sulfur, and Silicon and the Related Elements,
183:10, 2373-2390, DOI: 10.1080/10426500801963624
To link to this article: http://dx.doi.org/10.1080/10426500801963624
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Phosphorus, Sulfur, and Silicon, 183:2373–2390, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500801963624
Preparation and Biological Activity of Some Novel
Tetrachlorocyclodiphosph (V) Azane Pyridazine
Derivatives and Its Metal Complexes
Abdel-Nasser M. A. Alaghaz
Chemistry Department, Faculty of Science (Boys), Al-Azhar University,
Nasr-City, Cairo, Egypt
1,3 - diphenyl-2,2,4,4-tetrachloro-2,4-bis(4-Cyano-5,6-dimethyl-py-ridazin-3(2H)-
one) cyclodiphosph(V)azane(III), reacts with stoichiometric amounts of transition
metal salts such as Mn(II), Fe(III), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and
UO2 (II) to afford colored complexes in a moderate to high yield. The complexes
have been investigated in solution by the spectrophotometric molar ratio and con-
ductometeric methods. The formula of the isolated complexes was suggested based
on elemental analyses, IR, molar conductance, UV-Vis, 1 H NMR, mass spectra, solid
reflectance, and magnetic susceptibility measurements. From the elemental analy-
ses data, 1: 2 (III : M) ratio is suggested and the complexes are found to have the
general formula [(MXn)2 (III)(H2 O)m].yX where M = Mn(II) (X = OCOCH3 , n = 2,
m = 4, y=0), Fe(III) (X = Cl, n = 2, m = 2, y=2), Fe(II) (X = SO4 , n = 1, m = 2,
y=0), Co(II) (X = OCOCH3 , n = 2, m = 4, y=0), Ni(II) (X = OCOCH3 , n = 2, m =
4, y=0), Cu(II) (X = OCOCH3 , n = 2, m = 4, y=0), Zn(II) (X = OCOCH3 , n = 2,
m = 4, y=0), Cd(II) (X = Cl, n = 2, m = 4, y=0), and UO2 (II) (X = NO3 , n =
1, m = 0, y=2). The IR and 1 H NMR spectral data revealed that III behaves as
a neutral bidentate ligand coordinated to the metal ions through oxygen (O) and
nitrogen N atoms. The UV-Vis, solid reflectance, and magnetic-moment data have
shown that the ligands are coordinated to the metal ions in an octahedral manner.
The molar conductance data show that the complexes are nonelectrolytes while the
Fe(III) and UO2 (II) complexes are 1:2 electrolytes. The in vitro–biological activity
of some newly synthesized compounds against gram-positive and gram-negative
bacteria was studied.
Keywords Cyclodiphosph(V)azane; electronic; infrared (IR); metal complexes; magnetic
moment
INTRODUCTION
Hetero-functional ligands containing soft and hard donor sites have
attracted considerable attention as they are expected to generate
Received 18 September 2007; accepted 14 December 2008.
Address correspondence to A. M. A. Alajhaz, Chemistry Department, Faculty
of Science (Boys), Al-Azhar University, Nasr-City, Cairo, Egypt. E-mail: aalajhaz@
hotmail.com
2373

2374
A. M. A. Alaghaz
transition metal complexes, which are efficient for various catalytic
transformations.1−4 Transition metal complexes bearing P, S-donor
ligands have been used as catalysts for hydroformylation2,3 and
hydrogenation4reactions. Heterofunctional diphosphazanes of the type
X2 PN(R)P(E)X2 containing phosphorus and other donor atoms such
as sulfur, oxygen or nitrogen would display interesting coordination
chemistry.5−8 Phosphazanes are an established class of P–N compounds
and are known for their stability and ease of synthesis.9−11 The na-
ture of the highly polar P–N bond with P–and N-donor sites makes
a compound of kind versatile in both coordination and organometal-
lic chemistry.12−15 Although a few phosph(V)azanes have been used
as ligands for transition elements, their coordination chemistry is
so far largely unexplored.12,13 In particular, the interaction between
cobalt, nickel, and copper atoms and P-containing ligands is not
well established.16 The aim of the present work is to prepare cy-
clodiphosph(V)azanes derivatives by the reaction of hexachlorocy-
clodiphosph(V)azanes (I)17,18 with nucleophilic reagents such as 4-
Cyano-5, 6-dimethylpyridazin-3(2H)-one (II),19 and the complexation
behavior of one of these derivatives with some transition metals was
studied as well as comparing the biological activity of these compounds
towards different microoganisms.
RESULTS AND DISCUSSION
The Ligand
The ligand (Figure 1) was found to be soluble in CHCl3, acetone,
ethanol, THF, methanol, DMSO, DMF, acetonitrile, ethyl acetate, insol-
uble in diethyl ether and water, and slightly soluble in benzene andn-
hexane. The formula of the ligand (L) was elucidated by elemental
analyses (Table I), IR, electronic, 1H and 31P NMR techniques.
IR Spectra
The assignments of the important bands of the free ligand are given
in Table II. The spectra reveal the characteristic bands of the ν(P-O-C)
stretching vibrations of the ligand at 1200, 1102, 1050, and 926 cm−1
,
which is similar to those assigned by Seiceira20 and Nakamoto.21 The
band observed at 2218 cm−1 is ascribed to the ν(C≡N) stretching vibra-
tion which appeared at 2197 cm−1in compound (II).19 The shift of this
band to higher frequency in the ligand is considered as an evidence for
the ligand formation. The ν(P-Cl) stretching vibration is observed at

Diphosph Pyridazine Derivatives and Its Metal Complexes
2375
H3C
CN
Cl
P
Cl
P
N
N
H3C
OH
Cl
Cl
2
+
N
N
Cl
Cl
reflux for
three hours
-2HCl
( II )
(I)
H3C
CN
NC
CH3
Cl
Cl
P
N
N
H3C
O
P
O
CH3
N
N
N
N
Cl
Cl
(III)
FIGURE 1 Formula of ligand (III): 1,3-diphenyl-2,2,4,4-tetrachloro-2,4-bis( 4-
Cyano-5, 6-dimethylpyridazin-3(2H)-one) cyclodiphosph(V)azane.
490 cm−1 22 The band at 1221 cm−1 was assigned to the ν(P-N) stretch-
.
ing vibration.22
Electronic Spectra
The fact that the expected band at 269 nm,22,23 characteristic for the
delocalization of the nonbonding electrons on the nitrogen atoms within
the phosphazo ring of the dimeric formula was observed in the spec-
trum of ligand (III), suggested the presence of the phosphazo ring. The
bathochromically shifted band observed at 288 nm for the ligand (III)

2376

2377

2378
A. M. A. Alaghaz
relative to that of the dimer (I) is explained to be due to the replace-
ment for one chlorine atom of each phosphorus atom by the 4-Cyano-5,
6-dimethylpyridazin-3(2H)-one (II). The new band observed at 349 nm
is attributed to the n-π∗ transition of attached compound (II), which
is absent in the corresponding dimer (I), and this is considered as an
evidence for the ligand formation.
Mass Spectrum
The mass spectrum of the ligand (III) shows the fragmentation pattern
in Figure 2. The spectrum showed the molecular ion m/e peak at 679
(abundance 0.30%) corresponding to molecular weight of the ligand
(III). The base peak was observed in the spectrum at 64.
1H-NMR Spectrum
The 1H-NMR spectrum of the ligand (III) showed the following charac-
teristic proton signals at: δ = 6.80–7.90 ppm is assigned for aromatic
protons Ar-H and two sharp singlet signal bands at δ = 2.50 and 2.80
ppm corresponding to the protons of CH3 group.
Spectrophotometric Measurements of Solution Stoichiometry
The absorption spectra of the Mn(II), Fe(III), Fe(II), Co(II), Ni(II),
Cu(II), Zn(II), Cd(II), and UO2(II) complexes IVa−i are shown in Figure
3. The diagrams in Figure 4, consist of two linear portions intersecting
at 1:2 [ligand]/[M2+ or M3+], where M3+ is Fe(III) and M2+ correspond-
ing to Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and UO2(II),
respectively, indicating the formation of 2M: 1L species. This is in agree-
ment with the elemental analyses and conductometric analyses data.22
Electronic Spectra and Magnetic Properties
The UV—Vis spectra of complexes in DMF solution showed absorp-
tion bands between 269 nm and 288 nm, which is characteristic of
phosphazo four-membered rings.24,25 However, the absorptions were
red shifted with respect to the ligands depending on the types of metal
ions present. The spectra of the Fe(III), Fe(II), and Cu(II) complexes
further display a band in the range 360–445 nm, which might be
assigned to charge transfer transition (most probably L→M CT).26 For
the Co(II) complex, however, a d–d bands are observed at 600 nm and
4
4
675 nm which may attributed to the transitions T1g (F) → T2g (P)

Diphosph Pyridazine Derivatives and Its Metal Complexes
2379
OH
P
Cl
N
Cl
Cl
Cl
N
H3C
H3C
CN
P
OH
OH
C12H12Cl4N2O2P2
m/z = 420 (f = 420 23.53%)
N
N
C7H7N3O
m/z =149 (f = 149 87%)
H3C
H3C
CN
C6H6
Cl Cl
m/z = 78 (f = 78 100%)
N
O
P
P OH
H3C
CN
NC
CH3
CH3
N
Cl Cl
N
N
Cl Cl
N
H3C
O
P
P O
N
N
N
N N
Cl Cl
C19H17Cl4N5O2P2
m/z = 551 ( f =551 8.2%)
C26H22Cl4N8O2P2
m/z=679 (f= 682 0.30%)
Cl Cl
H3C
H3C
CN
N
Cl
P
H3C
O
P
P
O
CH3
NH
N
N
N
N
N
O
Cl Cl
N
N
Cl
H3C
H3C
CN
CH3
CH3
C13H12Cl2N4OP
m/z = 342 (f = 342 11.8%)
Cl Cl
N
C22H20Cl4N6O2P2
m/z= 604 (f = 604 4.01)
O
P
P O
N
N
N
N N
Cl Cl
C25H23Cl4N7O2P2
m/z = 657 (f=657 2.6%)
Cl
P
O
CH3
N
N
Cl
C5H5Cl2N2OP
m/z = 210 ( f = 210 88.65%)
FIGURE 2 Possible fragmentation pathways of III ligand.
4
4
and T1g (F) → A2g (F), respectively, typical of octahedral structure
around Co(II) ion.26
The diffuse reflectance spectra of the complexes show bands at 240–
250 nm, which are associated with interligand transitions.
The diffuse reflectance spectrum of Mn(II) complex shows three
4
6
bands at 15,662, 22,235, and 26,432 cm−1 assignable to T1g → A1g,
6
4
6
4T2g (G)→ A1g and T1g (D)→ A1g transitions, respectively.27 The
magnetic moment value is 5.34 µB. which indicates the presence of
Mn(II) complex in octahedral structure.

2380
A. M. A. Alaghaz
FIGURE 3 Absorption spectra of Cu(II)-III Complex, molar ratio method.
It is observed from the diffuse reflectance spectra of the Fe(III) com-
plexes that they exhibit a band at 21,150–21,196 cm−1, which may
be assigned to the 6A1g→T2g transition in octahedral geometry.27 The
spectra also show spitted bands at 14,937–15,683 and 17,567–18,363
5
cm−1, which assigned to the 6A1g→ T1g transition. The observed
magnetic moment of the Fe(III) complex is 5.67 µB for III ligand,
respectively, which confirm the octahedral geometry.28 The bands ob-
served at 29,154 and 24,952–26,120 cm−1 can be attributed to ligand-
to-metal charge transfer band for the Mn(II) and Fe(III) complexes,
respectively.27
1
0.8
0.6
0.4
0.2
0
0
0.5
1
1.5
2
[C(II)]//[L]
FIGURE 4 Results of molar ratio method for Cu(II) Complex.

Diphosph Pyridazine Derivatives and Its Metal Complexes
2381
The diffuse reflectance spectrum of Fe(II) complex displays two ab-
sorption bands at 15,173 cm−1 and 22,224 cm−1, which are assigned to
5
5T2g→ Eg transitions.29Also, the band at 25,643 cm−1 is assigned to
L→M charge transfer.29 The observed magnetic moment of 4.98 B.M.
is consistent with an octahedral geometry.29
The electronic spectrum of the Co(II) complex displays two bands
4
4
at 15,314 cm−1 and 17,480 cm−1 assigned to the T1g→ T1g (P) and
4
4T1g→ T2g (F) transitions, respectively, which arise due to ligand
field transition of the pseudo octahedral component of the Co(II) com-
plex. The observed magnetic moment value is µeff = 5.04 B.M. at
room temperature which confirms the octahedral structure of this
cobalt complex.29 The band observed at 22,623 cm−1 refers to L→
M CT band.
The solid reflectance spectrum of the Ni(II) complex shows bands at
3
23,252, 17,484 and 18,918 cm−1, suggesting the existence of 3A2g→ T1g
3
3
3
3
(P), A2g→ T1g (F) and A2g→ T2g transitions, respectively, with an
octahedral spatial configuration. The observed magnetic moment of the
complex is 2.84 B.M., which confirms the octahedral structure of this
complex.30
The solid reflectance spectrum of the Cu(II) complex gave a band
2
2
at 16,800 cm−1, which may be assigned to Eg→ T2g.31 The observed
magnetic moment of the Cu(II) complex is 1.95 B.M., which confirms
the octahedral structure of this complex. The band observed at 22,935
cm−1 refers to L→MCT band.
The Zn(II) and Cd(II)complexes are diamagnetic as expected
and its geometry is most probably octahedral similar to the
Mn(II), Fe(III), Fe(II), Co(II), Ni(II), and Cu(II)complexes of the
ligand (III).32
The electronic spectrum of the yellow UO2(II) complex (IVi) arises
from the electronic transition of metal→ligand charge transfer. This is
an allowed transition and produces a broad, intense absorption band
at 20618 cm−1 for complex (IVi), tailing into the visible region. This
produces the intense yellow color, where the UO2(II) complexes are
diamagnetic as expected.33
Mo¨ ssbauer Measurements
¨
The Mossbauer spectra were measured at room temperature for iron
complexes. The spectra revealed the presence of Fe ions in [(FeCl2)2(L)-
(H2O)4] and [FeSO4)(L)(H2O)4] in ferric and ferrous state respectively
in octahedral coordination.34 The Mossbauer parameters are listed in
¨
Table III and Figure 5.

2382
A. M. A. Alaghaz
TABLE III Mo¨ssbauer Parameters for Iron Complexes of the III
Ligand
Isomer shift
(IS) (mm/s)
Quadrupole splitting
Complex
(QS) (mm/s)
[(FeCl2)2III(H2O)4].2Cl
[(FeSO4)2III(H2O4)]
0.46
1.8
0.74
4.2
IR Spectra
The most characteristic IR spectral bands of the metal chelates together
with those of the free ligand are collected in Table II. The results of IR
spectra of the metal complexes show absorption bands of both νC≡n and
νp−o−c at lower frequencies than those of the free ligand III, indicating
that the metal ions are coordinated to the nitrogen and oxygen atoms
of both C≡N and P-O-C20,21groups of the ligand III. In all of the metal
complexes, there are new medium to weak bands appearing at lower
frequencies between 440–480 cm−1 and 500–552 cm−1, which were as-
signed to ν(M–N) and ν(M–O) stretching modes, respectively.22,30 These
stretches were not present in the spectra of the ligand. The appearance
of bands at 3340–3444 cm−1 and 796–832 cm−1 is due to the stretching
vibration and out of plane bending of coordinated water molecules in
the spectra of the metal complexes.30
FIGURE 5 Mo¨ssbauer spectra of the iron complexes.

Diphosph Pyridazine Derivatives and Its Metal Complexes
2383
The bands observed at 1464–1461 and 1579–1602 cm−1 in com-
plexes (IVa, IVd-IVe) were assigned to ν(sym.OCO) and ν(asym. OCO),
respectively, which indicated that the acetate groups coordinate as
a monodentate to the central metal cation in (IVa, IVd-IVe) com-
plexes respectively.22This is supported with the observed characteristic
ν(M-O) band.
IR spectrum of the sulfato (IVc) complex of III shows bands at 1186,
1045 and lower frequency regions, which indicate bidentate nature of
this anion.
The spectra of nitrato complex (IVi) gave additional bands around
1230, 1040 and 870 cm −1, which are consistent with the monodentate
nature of this group.32 Theν(U=O) vibration in the uranyl complex (IVi)
is observed as expected as a very strong band at 928 cm−1 is a good
agreement with those known for many dioxouranium (IV) complexes.21
The characteristic bands corresponding to the ν(PNP), ν(P–N) and
ν(P–Cl) which were associated with all the investigated complexes are
collected in Table II.
Conductometric Titration
In order to follow up the behavior of the ligand III in solution with
Co(II), Ni(II), and Cu(II), we investigated these systems using conduc-
tometric titration method.
In this method, 25 ml (10−4 M) of M(II) or M(III), where M(III) is
Fe(III) and M(II) is Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II),
and UO2(II) solution in absolute ethanol was titrated with (10−3 M)
of III solution absolute ethanol at room temperature 25◦Cand repre-
sented in Figure 6. The curves were plotted between the conductance
of the solution and the volume of ligand added. The results show that
the break in the curve occurred when the 2:1 (M: L) species are formed
in solution. The conductance of the reaction mixture was increase con-
tinuously with increasing the amount of the ligand III added in all
the complexes under investigation. The reason for increase in con-
ductivity after 2:1 (M: L) complex forms may be due to the presence
of the ligand in ionic form in the medium (ethanol) which arises the
conductivity.22,35,36
Molar Conductance Data
The molar conductance (Table I) of Mn(II), Fe(III), Fe(II), Co(II),
Ni(II), Cu(II), Zn(II), Cd(II) and UO2(II) complexes were measured in
DMF solvent. It is expected that the complexes are neutral where the
nitrate groups are coordinated to the metal ions, and give low value
in conductivity. The measured values were 130 and 135ꢁ−1 cm2 mol−1
,

2384
A. M. A. Alaghaz
25
20
15
10
5
0
0
2
4
6
8
Volume of ligand (ml)
FIGURE 6 Conductometric titrations for Cu(II) complex.
for complexes Fe(III) and UO2(II), respectively, which are higher than
the expected value. This may be due to the fact that the DMF solvent
replaced the Cl− and NO3− anions in the complexes, which results in
the 1:2 electrolytes due to the uncoordinated chloride or nitrate ion.37
Structural Interpretation
From all of the above observations, the formulas of these complexes
may be interpreted in accordance with complexes of ligands with a
similar distribution of sites such coordination cyclodiphosph(V)azanes
of thiophene35 and pyrazole.36 The structural information from these
complexes is in agreement with the data reported in this article based
on the IR, molar conductance, 1H NMR, UV-Vis, mass, solid reflectance,
thermal analysis, and magnetic-moment measurements. Consequently,
the structures proposed are based on octahedral geometric structures.
III ligand always coordinates via the nitrogen (C≡N) and the oxygen
(P-O-C) forming two-binding chelating sites. The octahedral geometry
is brought by the two anions (CH3COO−, Cl− or NO3−) and two coor-
dinated water molecules. According to the above data and similar to
those proposed previously, the formulas of the complexes are shown in
Figures 7–10.
Bioactivity
The in vitro antimicrobial activity of the newly prepared compounds
III, (IVa–IVi) against two groups of microorganisms, including three
strains of gram-positive bacteria and three strains of gram-negative
bacteria, was investigated in comparison with ampicillin. The ten
tested compounds were capable of inhibiting the growth of both gram-
positive and gram-negative bacteria, and they could be considered as

Diphosph Pyridazine Derivatives and Its Metal Complexes
2385
H3C
CN
X
NC
R
CH3
X
R
R
X
M
O
Cl
P
Cl
P
M
O
N
N
R
X
H3C
CH3
N
N
N
N
Cl
Cl
No.
M
R
X
IVa
IVd
IVe
IVf
IVg
IVh
Mn
Co
Ni
H2O
H2O
H2O
H2O
H2O
H2O
OAc
OAc
OAc
OAc
OAc
Cl
Cu
Zn
Cd
FIGURE 7 The proposed formula of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), and
Cd(II) complexes of an octahedral structure of the ligand III.
H2O
CN
H3C
CH3
Cl
H2O
Cl
H2O
Cl
NC
Fe
O
Cl
P
Fe
Cl
O
N
N
Cl
2Cl
OH2
H3C
P
CH3
N
N
N
N
Cl
Cl
FIGURE 8 The proposed formula of Fe(III) complex IVb of an octahedral
structure of the ligand III.

2386
A. M. A. Alaghaz
O
O
O
O
S
S
H3C
CH3
O
O
CN
O
O
NC
OH2
Fe
Cl
Cl
H2O
Fe
N
N
H2O
OH2
H3C
O
P
P
O
CH3
N
N
N
N
Cl
Cl
FIGURE 9 The proposed formula of Fe(II) complex IVc of an octahedral struc-
ture of the ligand III.
promising antimicrobial agents. Table IV shows the results of the bioas-
say. In conclusion, we have reported here the importance of the tested
compounds as antibacterial agents. Further studies should be made to
elucidate their mechanism of action.
EXPERIMENTAL
Melting points were recorded on Griffen melting point apparatus, Eng-
land, and are uncorrected. Elemental analyses of C, H, and N were
carried out at the Microanalytical Research Center, Faculty of Science,
Cairo University and phosphorus was determined gravimetrically
as phosphoammonium molybdate using R. Voy method.38 The mid-
infrared and the Ultraviolet measurements have been carried out at
H3C
CN
O U O
H2O
NC
O U O
OH2
CH3
NO3
O3N
Cl
Cl
P
N
N
2NO3
H3C
O
P
O
CH3
N
N
N
N
Cl
Cl
FIGURE 10 The proposed formula of UO2(II) complex IVi of an octahedral of
the ligand III.

Diphosph Pyridazine Derivatives and Its Metal Complexes
2387
the chemistry Department, Faculty of Science, and Al-Azhar Univer-
sity. The infrared spectra are recorded on Shimadzu-440 infrared spec-
trophotometer using KBr technique. Ultraviolet spectra were recorded
on PerkinElmer Lambda-3B Ultraviolet-Visible spectrophotometer-
meter using dimethylformamide as a solvent.1H NMR spectra were
measured on Varian Em-360-60 MHz spectrophotometer using TMS as
internal standard, the chemical shift (δ) is in ppm. The mass spectra
were performed by Shimadzu-Ge-Ms-QP 100EX using the direct inlet
system, Cairo University. Metal contents were determined complex-
ometerically using standard EDTA titration.39 Mossbauer measure-
¨
ments were performed in the Physics Department, Faculty of Science,
Al-Azhar University, at room temperature in a transmission geometry
employing 57Co as a radioactive source. The spectra were analyzed us-
ing a computer program based on Lorentzian distribution. The isomer
shifts were expressed relative to a metallic iron absorber.
Preparation of 4-Cyano-5, 6-dimethylpyridazin-3(2H)-one (II)
4-Cyano-5, 6-dimethylpyridazin-3(2H)-one(II) has been prepared and
purified using the method described elsewhere.19
Preparation of 1,3-diphenyl-2,2,2,4,4,4,-hexachlorocyclodiph-
osph (V)azane (I)
Hexachlorocyclodiphosph(V)azane derivatives (I) have been prepared
and purified using the method previously.17,18,22,35,36
TABLE IV Antimicrobial Potentialities of the Tested Compounds
Expressed as Size (mm/mg Sample) of Inhibition Zone Compounds
Compounds
Test Organisms
IIIa IVa IVb IVc IVd IVe IVf IVg IVh IVi
Bacillus subtilis
16
16
15
15
16
15
+
12
12
11
12
12
13
+
13
12
13
13
12
13
+
15
13
14
16
15
14
+
16
13
12
12
13
12
+
14
14
14
13
12
11
+
15
14
13
15
14
14
+
15
14
14
13
14
16
+
12
13
13
12
12
13
+
12
11
11
12
12
12
+
Staphylococcus aureus
Streptococcus faeculis
Escherichia coli
Neisseria genorrhes
Pseudomonae aeruginosa
Ampicillin

2388
A. M. A. Alaghaz
Preparation of 1,3-diphenyl-2,2,4,4-tetrachloro-2,4-bis
( 4-Cya-no-5, 6-dimethylpyridazin-3(2H)-one)
cyclodiphosph(V)azane (III)
The solid of 4-Cyano-5, 6-dimethylpyridazin-3(2H)-one(II) (0.01 mmol)
was added in small portions to a well stirred solution of the hexachloro-
cyclodiphosph(V)azane (I) (0.005 mmol) in 100 ml acetonitrile over a
half-hour period. After the complete addition, the reaction mixture was
heated under reflux for 2 h with continuous stirring. After comple-
tion of the reaction (HCl gas ceased to evolve), the reaction mixture
was filtered, while hot and the filtrate was left to cool at room tem-
perature. The obtained solid was filtered washed several times with
acetonitril, diethylether, and dried in vacuo to give the corresponding
cyclodiphosph(V)azane pyridazine derivatives III the data obtained are
listed in Table I.
Preparation of Pyridazine-cyclodiphosph(V)azane Complexes
(IVa-i)
A solution of the metal salts (0.002 mol) in 50 mL dry ethanol was added
dropwise to a solution of pyridazine-cyclodiphosph(V)azane (0.002 mol)
in 100 mL absolute ethanol in a 2:1 metal to ligand molar ratio at room
temperature with continuous stirring. After complete addition of the
metal salt solution, the reaction mixture was heated under reflux for
about 2 h under dry conditions. The complexes obtained were washed
with dry ethanol then with dry diethyl ether and dried in vacuo. The
products obtained give elemental analyses consistent with the proposed
formula.
Bioassay: Measurement of Antimicrobial Activity Using the
Diffusion Disc Method
A filter-paper sterilized disc saturated with a measured quantity of
the sample was placed on a plate containing a solid bacterial medium
(nutrient agar broth), which was heavily seeded with the spore sus-
pension of the tested organism. After inoculation, the diameter of the
clear zone of inhibition surrounding the sample was taken as a mea-
sure of the inhibitory power of the sample against the particular test
organism.40−42
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