Preparation and characterization of some novel diphenylphosphine hydrazones and semicarbazones and their metal complex derivatives

Article abstract of DOI:10.1080/10426500802016778

Interaction of hydrazones and semicarbazones derivatives Ia - t with diphenylchlorophosphine II, gave new compounds IIIa-t, and their complexation ability towards various divalent metal acetates Mn(OAc)2. 4H2O, Co(OAc)2. 4H2O, Ni(OAc)2. 4H2O, and Cu(OAc)2. H2O, in organic solvents are described. The metal/ phosphorsemi-carbazones ratios are measured and the results discussed. All these complexes are insoluble in organic solvents and in water. The structures of the isolated products were proposed on the basis of microanalyical data, TGA, IR, (UV/ VIS), (MS), and 1H, 13C, and 31P-NMR spectroscopic analyses and magnetic susceptibility. The proposed structure of the complexes is based on a 1: 2 metal: ligand ratio. All of the complexes are found to have an octahedral geometry, with the exception of the square planar copper (II) complexes. The corrosion inhibition of aluminium and copper in 1 M HCl and chromium-nickel steel in crude oil using IIIn have been studied by weight loss method. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon
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Preparation and
Characterization of Some Novel
Diphenylphosphine Hydrazones
and Semicarbazones and Their
Metal Complex Derivatives
A. M. A. Alaghaz a & R. A. A. Ammar b
a Chemistry Department, Faculty of Science , Al-
Azhar University (Boys) , Nasr-City, Cairo, Egypt
b Chemistry Department, Faculty of Science , Al-
Azhar University (Girls) , Nasr-City, Cairo, Egypt
Published online: 10 Oct 2008.
To cite this article: A. M. A. Alaghaz & R. A. A. Ammar (2008) Preparation and
Characterization of Some Novel Diphenylphosphine Hydrazones and Semicarbazones
and Their Metal Complex Derivatives, Phosphorus, Sulfur, and Silicon and the Related
Elements, 183:11, 2827-2844
To link to this article: http://dx.doi.org/10.1080/10426500802016778
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Phosphorus, Sulfur, and Silicon, 183:2827–2844, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802016778
Preparation and Characterization of Some Novel
Diphenylphosphine Hydrazones and Semicarbazones and
Their Metal Complex Derivatives
A. M. A. Alaghaz1 and R. A. A. Ammar2
1Chemistry Department, Faculty of Science, Al-Azhar University (Boys),
Nasr-City, Cairo, Egypt
2Chemistry Department, Faculty of Science, Al-Azhar University
(Girls), Nasr-City, Cairo, Egypt
Interaction of hydrazones and semicarbazones derivatives Ia−t with
diphenylchlorophosphine II, gave new compounds IIIa−t
, and their com-
plexation ability towards various divalent metal acetates Mn(OAc)2. 4H2O,
Co(OAc)2. 4H2O, Ni(OAc)2. 4H2O, and Cu(OAc)2. H2O, in organic solvents are
described. The metal/ phosphorsemi-carbazones ratios are measured and the
results discussed. All these complexes are insoluble in organic solvents and in
water. The structures of the isolated products were proposed on the basis of
microanalyical data, TGA, IR, (UV/ VIS), (MS), and 1H, 13C, and 31P-NMR
spectroscopic analyses and magnetic susceptibility. The proposed structure of the
complexes is based on a 1: 2 metal: ligand ratio. All of the complexes are found
to have an octahedral geometry, with the exception of the square planar copper
(II) complexes. The corrosion inhibition of aluminium and copper in 1 M HCl and
chromium–nickel steel in crude oil using IIIn have been studied by weight loss
method.
Keywords Diphenylphosphate; magnetic susceptibility; phosphorsemicarbazones;
31P-NMR; (IR)
INTRODUCTION
Coordination chemistry of pentadentate bis-(thiosemicarbazone/
semicarbazone)-2,6-diacetylpyridine Schiff base ligands has been in-
tensively studied due to the versatility of the molecular chain in order
to obtain very different geometries, 1as well as their broad therapeutic
activity.2 Substitution at 4-N position of the thiosemicarbazone arms
has been probed to affect the biological activity of the complexes,3 but
not much structural information about them has been provided. The
Received 11 December 2007; accepted 27 February 2008.
Address correspondence to A. M. A. Alajhaz, Chemistry Department, Faculty of Sci-
ence, Al-Azhar University (Boys), Nasr-City, Cairo, Egypt. E-mail: aalajhaz@hotmail.com
2827

2828
A. M. A. Alaghaz and R. A. A. Ammar
present work was planned to investigate new route for the synthesis
of novel diphenylphosphine hydrazones and diphenylphos-phine semi-
carbazones derivatives with potential biological activities.
RESULTS AND DISCUSSION
The reactions of diphenylchlorophosphine with different hydrazone and
semicarbazone derivatives containing aliphatic and/ or aromatic alkyl
groups may be represented by the Equations (1)–(3).
where G Ph N, NO2C6H4N, or HNCONH.
where n = 2, m = 2 for Mn, Co and Ni while m = 0, n = 0, for Cu.
The reactions are quite facile and could be completed within 5−12
hours of refluxing in toluene. The resulting products of complexes are
colored solids and insoluble in common organic solvents but soluble in
DMSO, THF, and DMF. Phosphorus metal complexes are quite stable.
The molecular weight determinations indicate their monomeric nature
in Eqs. (1, 2) but dimeric nature in Eq. (3). The low molar conductance
values (4.85–16.30 ꢀ−1 mol−1 cm2) of the prepared complexes in DMF at
10−3 M concentrations show them to be nonelectrolytes. The analytical
of both the ligand and its metal complexes are listed in Tables I and II.

Novel Diphenylphosphine Hydrazones and Semicarbazones
2829
Infrared Spectra
The IR spectra of hydrazone and semicarbazone derivatives show bands
–1
–1
at 1630–1654 cm and 1295-1310 cm attributed to ν (C N) and
ν (P N).5ν (P NH), observed at 2600−2622 cm
. Two bands at
–1 5
1690−1720 cm–1and 3280−3315 cm–1 appear in the IR spectra of semi-
carbazone derivatives assignable to ν (C O) and ν NH.
To investigate the mode of coordination, the IR spectra of
AcetophenoneN4 diphenylphosphine semicarbazone (IIIn) as one of
semicarbazone derivatives and its Mn(II), Co(II), Ni(II), and Cu(II)
complexes are compared. Acetophenone N4 diphenylphosphine semicar-
bazone can exist either as keto or enol form or an equilibrium mixture
of the two forms since it has an amide NHC O function. However, the
IR and NMR spectra of IIIn indicate that it remains in a keto form in
solid state. The IR spectra of the Ni(II), Co(II), Cu(II), and Mn(II) com-
plexes do not show any intense absorption band at around1705 cm−1
,
due to the carbonyl stretching of the semicarbazone moiety. This shows
that IIIn converts to enol form in solution and coordinate to the metals
in an enolate form. IIIn behaves as a bidentate ligand via azomethine
nitrogen and oxygen atom in a deprotonated enolic form—forming a
five-membered ring. This structure is supported by disappearance of ν
(C O) band, as well as a new band appearing at ∼545 cm–1 due to M-O
bond.6 The IR spectra of the metal complexes do not show a broad band
–1
at 3434 cm for O-H stretching mode of the phenolic oxygen. Sharp
band at 1635 cm–1 in the spectrum of IIIn is shifted to lower wavenum-
–1
ber by 10–15 cm in the spectra of the metal complexes support the
coordination through azomethine nitrogen. This band is abroad and
intense compared to that of the ligand and can be attributed to over-
lapping of the bands of newly formed N C bond stretching. The band
due to ν (P−aryl) and modes in the spectra of the ligands are observed
at 1450–1410 cm–1. In addition to the attributed to M-O, a new band
–1
appears at about 280 cm assigned to M-N,7 Table III and IV.
1H, 13C-, and 31P-NMR Spectra
1H-NMR (Table III) of all prepared compounds show peaks assigned to
aliphatic and aromatic protons as well as peak at 7.8−8.6 ppm in case
of semicarbazone attributed to NH proton. The 13C-NMR (Table III)
spectral data also support the authenticity of the proposed structures.
The considerable shifts in the positions of carbon atoms adjacent to the
imine nitrogen [C N (δ 160.12−162.79 ppm)], enolic oxygen [C O (δ
164.32−168.84 ppm)] support the proposed coordination in the com-
plexes. Thus the shifts in the position of carbon atoms adjacent to the

2830

2831

2832

2833

2834

Novel Diphenylphosphine Hydrazones and Semicarbazones
2835
aryl
TABLE IV IR Spectral Data of the Ligands III(m−t) and Its Metal
Complexes
NH
P
N
P
NH
)
M
N
)
M
O
)
C
N
P
No.
(cm−1
)
(cm−1
)
(cm−1
(cm−1
(cm−1
(cm−1
)
(cm−1
)
IIIm
3283(br) 1184(m) 2600(w)
—285(s)
—543(w) 1634(m) 1453(m)
1625(m) 1447(m)
MnIIIm 3234(br) 1212(m) 2589(v.w)
CoIIIm 3254(br) 1221(m) 2591(v.w)
NiIIIm
CuIIIm 3237(br) 1215(m) 2686(v.w)
IIIn 3280(br) 1186(m) 2617(w)
MnIIIn 3215(br) 1214(m) 2604(v.w)
283(m)
280(w)
280(w)
540(w)
553(s)
554(w)
1622(m) 1442(m)
1623(m) 1447(m)
1624(m) 1432(m)
3245(br) 1215(m) 2592(v.w)
—285(w)
—544(s) 1635(m) 1450(m)
1223(m) 1447(m)
CoIIIn
NiIIIn
CuIIIn
IIIo
3220(br) 1220(m) 2604(v.w)
3225(br) 1215(m) 2601(v.w)
3220(br) 1215(m) 2600(v.w)
3269(br) 1184(m) 2615(w)
283(w)
280(m)
280(w)
542(m)
551(s)
550(w)
1224(m) 1445(m)
1226(m) 1449(m)
1226(m) 1432(m)
—285(m) —540(m) 1635(m) 1450(m)
1222(m) 1443(m)
MnIIIo 3235(br) 1214(m) 2600(v.w)
CoIIIo
NiIIIo
CuIIIo
IIIp
3240(br) 1222(m) 2600(v.w)
3230(br) 1213(m) 2600(v.w)
3230(br) 1214(m) 2602(v.w)
3275(br) 1178(m) 2613(w)
282(w)
282(m)
280(w)
543(w)
555(w)
555(m)
1225(m) 1445(m)
1223(m) 1442(m)
1223(m) 1430(m)
—286(m) —543(m) 1648(m) 1453(m)
1224(m) 1444(m)
MnIIIp 3219(br) 1201(m) 2602(v.w)
CoIIIp
NiIIIp
CuIIIp
IIIq
3244(br) 1200(m) 2601(w)
3234(br) 1205(m) 2600(w)
3236(br) 1205(m) 2602(v.w)
3276(br) 1182(m) 2619(w)
284(w)
283(m)
282(m)
542(m)
551(s)
556(w)
1223(m) 1442(m)
1222(m) 1445(m)
1225(m) 1433(m)
—288(w) —548(m) 1640(m) 1452(m)
1221(m) 1442(m)
MnIIIq 3213(br) 1213(m) 2605(v.w)
CoIIIq
NiIIIq
CuIIIq
IIIr
3227(br) 1202(m) 2602(v.w)
3228(br) 1212(m) 2601(w)
3226(br) 1211(m) 2601(w)
285(m)
284(w)
284(m)
544(m)
554(m)
1221(m) 1444(m)
1223(m) 1445(m)
555(v.w) 1224(m) 1433(m)
3278(br) 1168(m) 2615(w) —286(v.w) —550(m) 1635(m) 1458(m)
MnIIIr 3245(br) 1213(m) 2602(v.w)
1222(m) 1443(m)
1222(m) 1445(m)
1223(m) 1447(m)
1221(m) 1442(m)
CoIIIr
NiIIIr
CuIIIr
IIIs
3233(br) 1211(m) 2602(w)
3242(br) 1211(m) 2600(v.w)
3243(br) 1212(m) 2600(v.w)
3276(br) 1188(m) 2622(w)
286(m)
288(m)
280(w)
—287(s)
544(m)
553(m)
555(s)
—548(m) 1630(m) 1464(m)
1215(m) 1445(m)
MnIIIs 3245(br) 1210(m) 2606(v.w)
CoIIIs
NiIIIs
CuIIIs
IIIt
MnIIIt
CoIIIt
NiIIIt
CuIIIt
3243(br) 1221(m) 2607(v.w)
3242(br) 1217(m) 2605(w)
3242(br) 1216(m) 2600(v.w)
3282(br) 1188(m) 2618(w)
3213(br) 1211(m) 2606(v.w)
3262(br) 1222(m) 2604(w)
3264(br) 1202(m) 2602(v.w)
3269(br) 1205(m) 2602(v.w)
283(s)
282(s)
280(m)
—285(s)
544(m)
552(m)
550(s)
1214(m) 1442(m)
1226(m) 1444(m)
1224(m) 1446(m)
—542(s) 1654(m) 1452(m)
1223(m) 1447(m)
540(s)
550(m)
550(m)
283(m)
281(m)
280(m)
1224(m) 1445(m)
1222(m) 1449(m)
1223(m) 1431(m)

2836
A. M. A. Alaghaz and R. A. A. Ammar
coordinating atoms clearly indicate the bonding of the imine nitrogen
and amido oxygen to the manganese, cobalt, nickel or copper atom. The
31P- NMR chemical shifts for the phosphorus compounds ligands IIIa−t
adds further substantial evidence supporting the proposed structures.
The 31P-NMR (Table III) spectra showed one signals at δ = 21.84−25.57
ppm, corresponding to the one phosphorus environment (*) designated
in the above structure. The structure of these hydrazone and semicar-
bazone derivatives are supported by elemental analysis (C, H, N, P)
and confirmed by mass spectroscopy, which show a molecular ion peak
corresponding to the calculated molecular weight.
Electronic and Magnetic Properties
Electronic spectral data of phosphorus compounds IIIa−t, as well as
the ligand IIIn and its complexes are carried out in DMF and show
bands at 37,580−30,100 cm–1 assigned to π − π* electronic transitions
within the benzene ring. These bands remain almost unchanged in the
–1
spectra of the complexes. Another band is observed at 27,150 cm is
corresponding to n-π* transitions of the azomethine (> CH N) group.
However, in the spectra of the complexes the bands are found to be
broadened and can be explained as a combination of O → M and N →
M LCT transitions.
The electronic spectra and magnetic moment values for all complexes
are consistent with the proposed structures. The diffuse reflectance
spectrum of the Mn(II) complex displays two bands at 12,950 and 15,250
4
4
cm−1 assigned to the 6A1g (F) → T1(4G) (ν1) and 6A1g → T2g(4G) tran-
sitions, respectively, considering an octahedral symmetry.8 In addition,
the octahedral configuration is also supported by the measured mag-
netic moment of such complex, 5.34 B.M.
The diffuse reflectance spectrum of the Co(II) complex displays
4
three bands at 13,501, 18,250, and 22,953 cm−1 assigned to the T1g
4
4
4
4
4
(F) → T2g(F) (ν1), T1g (F) → A2g(F) (ν2), and T1g → T2g(P) (ν3)
transitions, respectively. The band observed at 26,520 cm−1 refers to
L→MCT band.9From the observed magnetic moment value (µeff = 5.11
B.M.) together with the band position in the solid reflectance spectra,
the Co(II) complex is octahedral with largely covalent bonds between
the organic ligand and Co(II) ion.
The Ni(II) complex reported herein is high spin with a room tem-
perature magnetic-moment value of 2.93 B.M., which confirms the oc-
tahedral structure of this complex. The solid reflectance spectrum of
the complex shows three bands at 14,993, 17,483, and 21,552 cm−1
,
3
3
which are assigned to the 3A2g → T1g(P) (ν1), 3A2g → T1g(F) (ν2), and

Novel Diphenylphosphine Hydrazones and Semicarbazones
2837
3
3A2g → T2g (P) (ν3) transitions, respectively, confirming the octahedral
geometry of the Ni(II) complex.10,11
The solid reflectance spectrum of the Cu(II) complex gave a band at
2
17,361 cm−1, was assigned to 2B2 → E transition. The bands observed
in the range 23,809−23,864 cm−1 were assigned to the charge transfer
via L→M (Cu2+). The observed magnetic moment of the Cu(II) com-
plex is 1.89 B.M., which confirms the square planner structure of this
complex.5
Solid-State Electrical Conductivity
The conductivity of the free ligands (IIIm−t) is increased on complexing
with transition metal ions. This behaviour is attributed to the inclu-
sion of the various metal cations in the π-electron delocalization of the
ligands.12 The observed conductivities follow the order Mn < Co < Ni
< Cu. Theoretically, if we consider the charge/radii, the stability of the
metal complexes increases as the size of the metal ion decreases or the
value of the ratio charge/ radii increases. This means that the stability
increases towards the copper complexes. It is apparent that increasing
stability of the complexes will increase the number of dislocated elec-
trons on the ligand molecule and then increase the conductivity13 as
given in (Table V). To explain the conduction mechanism of the ligand
and its complexes, it is necessary to determine the mobility of charge
carriers µ. If the density of charge carriers is known, then the mobility
can be calculated using the relation σ = eNm, eis the electron charge.
The charge carrier concentration was determined using the relation,
n = 2[2µm∗ kT/h2]1/2 exp(−E/kT),
(1)
where m∗is the effective mass of charge carrier. The calculated mobili-
ties are ranged from 10−5 to 10−9 cm2/V s suggesting that the conduction
of Acetophenone N4 diphenylphosphine semicarbazones (IIIm−t) ligands
and its metal complexes takes place by hopping mechanism.14
The Thermal Analyses of the Complexes
The thermogram of Co(II) complex of IIIn shows that there is two
water molecules as water of hydration, the decomposition range was
(70−110◦C). The initial mass loss observed for Ni(II) complex of
IIIo in the temperature range (80−120◦C) corresponds to two water
molecules attributed as water of hydration. In the temperature range
(180−210◦C). For Cu(II) complex of IIIt, the TGA analysis indicates the
complex contains two hydrated water molecules (60−115◦C), hence, the

2838
A. M. A. Alaghaz and R. A. A. Ammar
TABLE V Values of the Electrical Conductivity (σ) and Thermal
Activation Energy of the Ligands III(m−t) and Its Metal Complexes at
303 K
No.
σ(ꢀ−1cm−1
)
E (eV)
n(cm−3
)
µ(cm2/Vs)
IIIm
1.42 × 10−8
1.92 × 10−8
2.11 × 10−8
3.22 × 10−8
4.54 × 10−8
1.44 × 10−8
1.94 × 10−8
2.13 × 10−8
3.21 × 10−8
4.53 × 10−8
1.44 × 10−8
1.94 × 10−8
2.13 × 10−8
3.21 × 10−8
4.53 × 10−8
1.49 × 10−8
1.87 × 10−8
2.16 × 10−8
3.23 × 10−8
4.57 × 10−8
1.49 × 10−8
1.98 × 10−8
2.16 × 10−8
3.28 × 10−8
4.50 × 10−8
1.46 × 10−8
1.98 × 10−8
2.14 × 10−8
3.31 × 10−8
4.55 × 10−8
1.43 × 10−8
1.94 × 10−8
2.16 × 10−8
3.31 × 10−8
4.56 × 10−8
1.49 × 10−8
1.93 × 10−8
2.14 × 10−8
3.25 × 10−8
4.54 × 10−8
0.32
0.35
0.42
0.42
0.55
0.33
0.36
0.41
0.46
0.57
0.33
0.36
0.41
0.46
0.57
0.31
0.36
0.40
0.46
0.57
0.32
0.35
0.40
0.45
0.58
0.34
0.37
0.42
0.47
0.56
0.30
0.35
0.40
0.47
0.58
0.31
0.36
0.42
0.46
0.59
8.54 × 1019
12.32 × 1018
12.21 × 1018
12.41 × 1018
1.25 × 1016
8.56 × 1019
12.8 × 1018
12.0 × 1018
12.8 × 1018
1.28 × 1016
8.56 × 1019
12.84 × 1018
12.05 × 1018
12.83 × 1018
1.28 × 1016
8.53 × 1019
11.86 × 1018
12.08 × 1018
12.84 × 1018
1.28 × 1016
8.58 × 1019
12.82 × 1018
12.05 × 1018
12.86 × 1018
1.26 × 1016
8.55 × 1019
12.86 × 1018
12.02 × 1018
12.83 × 1018
1.31 × 1016
8.43 × 1019
12.92 × 1018
12.01 × 1018
12.82 × 1018
1.31 × 1016
8.62 × 1019
12.72 × 1018
12.32 × 1018
12.83 × 1018
1.34 × 1016
1.11 × 10−7
0.71 × 10−9
9.82 × 10−8
3.63 × 10−6
2.33 × 10−5
1.14 × 10−7
0.72 × 10−9
9.81 × 10−8
3.65 × 10−6
2.36 × 10−5
1.18 × 10−7
0.77 × 10−9
9.88 × 10−8
3.69 × 10−6
2.36 × 10−5
1.14 × 10−7
0.75 × 10−9
9.87 × 10−8
3.66 × 10−6
2.34 × 10−5
1.15 × 10−7
0.76 × 10−9
9.67 × 10−8
3.70 × 10−6
2.23 × 10−5
1.23 × 10−7
0.74 × 10−9
9.87 × 10−8
3.70 × 10−6
2.42 × 10−5
1.17 × 10−7
0.87 × 10−9
9.93 × 10−8
3.74 × 10−6
2.45 × 10−5
1.24 × 10−7
0.83 × 10−9
9.97 × 10−8
3.68 × 10−6
2.43 × 10−5
MnIIIm
CoIIIm
NiIIIm
CuIIIm
IIIn
MnIIIn
CoIIIn
NiIIIn
CuIIIn
IIIo
MnIIIo
CoIIIo
NiIIIo
CuIIIo
IIIp
MnIIIp
CoIIIp
NiIIIp
CuIIIp
IIIq
MnIIIq
CoIIIq
NiIIIq
CuIIIq
IIIr
MnIIIr
CoIIIr
NiIIIr
CuIIIr
IIIs
MnIIIs
CoIIIs
NiIIIs
CuIIIs
IIIt
MnIIIt
CoIIIt
NiIIIt
CuIIIt

Novel Diphenylphosphine Hydrazones and Semicarbazones
2839
synthesis of the complexes may be explained according to the equations:
M(CH3COO)2 + 2HL + 4H2O = ML2(CH3COO)2 for M
= Co(II), Ni(II), and
M(CH3COO)2 + 2HL + H2O = ML2 for M = Cu(II).
(2)
(3)
It should be indicated that the Co(II), Ni(II) and Cu(II) ions forms
2 : 1 ligand to metal ratio.
Corrosion Inhibition
The inhibitive action of IIIn on the dissolution of aluminium and cop-
per in 1 M HCl, as well as chromium–nickel steel in crude oil are in-
vestigated (Tables VI–VIII). IIIm is impracticable to study because the
precipitation occurred. Aluminium, copper, and chromium-nickel steel
were selected for this study due to their numerous industrial appli-
cations. The degree of surface coverage (θ), the percentage inhibition
effciency (η%) and the corrosion rate (R) were calculated as follows15:
θ = 1 − w/w0,
(4)
(5)
(6)
η% = [w0 − w/w0] × 100, and
R = weight loss (mg)/area(cm2) × time(h),
where w and w0 are the weight losses of the test specimens in ab-
sence and presence of the inhibitor. The inhibition efficiency of addi-
tive compound depends on many factors, which include the number of
adsorption sites and their charge density, molecular size, heat of hydro-
genation, mode of interaction with the metal surface, and formation of
metallic complexes. The weight loss data were determined and listed in
(Tables VI–VIII). Careful inspection of these results showed that, by
TABLE VI Corrosion Parameters of Copper in 1M HCl
at Different IIIn Concentrations
Inhibitor
conc. (M)
Wt. loss
(mg cm−2
)
R (mg cm−2h−1
)
θ
η%
Blank
0.04
0.03
0.026
0.024
0.020
0.011
0.035
0.025
0.022
0.020
0.012
0.010
—
—
31
37
44
65
82
1 × 10−5
5 × 10−5
1 × 10−4
5 × 10−4
1 × 10−3
0.31
0.37
0.44
0.65
0.82

2840
A. M. A. Alaghaz and R. A. A. Ammar
TABLE VII Corrosion Parameters of Aluminum in 1M
HCl at Different IIIn Concentrations
Inhibitor
conc. (M)
Wt. loss
(mg cm−2
)
R (mg cm−2h−1
)
θ
η%
Blank
0.11
0.10
0.09
0.06
0.05
0.01
0.09
0.08
0.07
0.05
0.04
0.01
—
—
12
15
41
52
86
1 × 10−5
5 × 10−5
1 × 10−4
5 × 10−4
1 × 10−3
0.12
0.15
0.41
0.52
0.86
increasing the inhibitor concentration, both (θ) and (η%) increased
while (R) reduced. So, the dissolution of aluminium, copper and
chromium–nickel steel in the presence of the investigated inhibitor can
be interpreted on the basis of interface inhibition mode, the inhibitor
acts effectively at the metal solution interface.16 Weight loss data deter-
mination after 70 min. yielded convincing evidence for the application
of IIIn as an active corrosion inhibitor (Tables VI–VIII). The maximum
efficiencies at higher IIIn concentration values are 88, 87, and 88% for
aluminum, copper, and chromium–nickel steel, respectively. These re-
sults indicate a reasonable corrosion inhibition for specimens.
EXPERIMENTAL
All melting points reported 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 gravimet-
rically as phosphoammonium molybdate using R. Voy method.17 The
mid-infrared and the Ultraviolet measurements have been carried out
TABLE VIII Corrosion Parameters of
Chromium-Nickel Steel in Crude Oil at Different IIIn
Concentrations
Inhibitor
conc. (M)
Wt. loss
(mg cm−2
)
R (mg cm−2h−1
)
θ
η%
Blank
0.07
0.04
0.02
0.01
0.06
0.04
0.02
0.01
—
—
37
67
87
1 × 10−5
1 × 10−4
5 × 10−4
0.37
0.67
0.87

Novel Diphenylphosphine Hydrazones and Semicarbazones
2841
at the chemistry Department, Faculty of Science, and Al-Azhar Univer-
sity. IR spectra recorded in (KBr disk) on a Bruker, vector 22, Germany,
or on a Shimadzu FT- 8201 PC spectrophotometer. Ultraviolet spectra
were recorded on Perkin EImer Lambda-3B Ultraviolet-Visible spec-
trophotometer using DMF as a solvent.1H and 13C-NMR spectra were
recorded in (CD3)2SO on a Varian Gemini 200 MHz or on a Varian Mer-
cury 300MHz Em-360-60 MHz spectrometer and shifts were expressed
in δ units using TMS as internal reference. Mass spectra were recorded
on Hewlett-Packard (HP) 5988A (EI, 15eV).31P NMR spectra were run,
relative to external H3PO4(85%), with a Varian FT-80 spectrometer at
365MHz. Magnetic measurements were recorded by the Gouy method
at room temperature using a magnetic susceptibility balance (Johanson
Mathey), Alfa product, Model No. (MK). The thermogravimetric analy-
ses (TGA) were recorded on a Shimadzu TGA –50 H. TGA was carried
out in a dynamic nitrogen atmosphere (20 mL min–1) at a heating rate
of 10◦C min–1. The conductometric measurements in solutions were
carried out using conductivity TDS model 72. Metal contents were de-
termined by titration against standard EDTA after complete decom-
position of the complexes with aqua regia in a Kjeldahl flask several
times.
Measurement of the Dark Conductivity
–16
–1
to 105(ohm cm–1), is
The dark conductivity, which ranges from 10
usually measured by the following cell arrangements: sandwich cells in
which the sample is arranged between two electrodes.
The electrical conductivity (dc) data were collected at different tem-
peratures, from room temperature up to near the melting point of each
sample in the ohmic region by using the potential probe method.18 The
samples were in the form of pellets pressed at 4 tons /cm2, diameter
∼
10 mm and thickness 1–2 mm, coated with silver paint (BDH) and
checked several times for good contact.
=
Synthesis of Ligand IIIa–t
The solid of hydrazone or semicabazone derivatives (Ia−t) (0.01
mmol) was added in small portions to a well stirred solution of the
diphenylchlorophosphine (II) (0.01 mmole) in 100 ml acetonitrile over
a half-hour period. After the complete addition, the reaction mixture
was heated under reflux for 4 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 temperature.
The obtained solid was filtered washed several times with acetonitrile,

2842
A. M. A. Alaghaz and R. A. A. Ammar
SCHEME 1

Novel Diphenylphosphine Hydrazones and Semicarbazones
2843
SCHEME 2 The proposed structure of the metal complexes.
diethylether and dried under vacuo to give the corresponding ligands
(IIIa−t) (Scheme 1).
Synthesis of the Solid Metal Complexes
A one molar equivalent (0.1 mol) of manganese (II), cobalt (II), nickel
(II), and copper (II) acetate dissolved in 50 ml absolute ethanol was
added to two molar equivalent (0.2 mol) of IIIm–t dissolved in 100 ml
absolute ethanol at room temperature with continuous stirring. The
reaction mixture was heated under reflux for 3 h. Then, the reaction
mixture was evaporated to give solids, which were recrystallized from
ethanol and diethylether and dried under vacuo. The analytical data of
both the ligands and their metal complexes are listed in Tables I and
II.
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A. M. A. Alaghaz and R. A. A. Ammar
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