Nickel(II)-triphenylphosphine complexes of ONS and ONN chelating 2-hydroxyacetophenone thiosemicarbazones

Article abstract of DOI:10.1016/j.poly.2011.02.041

The complexes [Ni(L¹)(PPh₃)] (1) and [Ni(L ²)(PPh₃)]·HCl (2) were synthesized by the reaction of [Ni(PPh₃)Cl₂] and dibasic 2-hydroxyacetophenone-S-R-4- R¹-thiosemicarbazones (R/R¹: H/CH₃, L ¹H₂; CH₃/H, L²H₂). The ligands and the complexes were characterized using elemental analysis, IR and ¹H NMR spectra. In both complexes, the thiosemicarbazone ligands coordinate to nickel(II) by giving two protons. Complex 1 is formed through the phenolate oxygen, azomethine nitrogen and sulfur atoms of L¹ and the P atom of a triphenylphosphine ligand. In complex 2, L² is functional through an ONN donor set, containing a thioamide nitrogen instead of a sulfur atom. X-ray analysis indicated distorted square planar structures for the complexes, and the nickel atoms lie slightly above the planes structured by the donor atoms. In the crystal forms of 1 and 2, some phenyl ring protons of the phosphine ligand give intramolecular hydrogen bonds with the donor atoms of the thiosemicarbazone moiety, namely the phenolate oxygen (in complexes 1 and 2) and N⁴ nitrogen (in complex 2).

Full text of DOI:10.1016/j.poly.2011.02.041

Polyhedron 30 (2011) 1385–1388
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Nickel(II)–triphenylphosphine complexes of ONS and ONN chelating
2-hydroxyacetophenone thiosemicarbazones
⇑
Sßükriye Güveli, Bahri Ülküseven
Department of Chemistry, Istanbul University, 34320 Avcılar, Istanbul, Turkey
a r t i c l e i n f o
a b s t r a c t
The complexes [Ni(L1)(PPh3)] (1) and [Ni(L2)(PPh3)]ꢀHCl (2) were synthesized by the reaction of
[Ni(PPh3)Cl2] and dibasic 2-hydroxyacetophenone-S-R-4-R1-thiosemicarbazones (R/R1: H/CH3, L1H2;
CH3/H, L2H2). The ligands and the complexes were characterized using elemental analysis, IR and 1H
NMR spectra. In both complexes, the thiosemicarbazone ligands coordinate to nickel(II) by giving two
protons. Complex 1 is formed through the phenolate oxygen, azomethine nitrogen and sulfur atoms of
L1 and the P atom of a triphenylphosphine ligand. In complex 2, L2 is functional through an ONN donor
set, containing a thioamide nitrogen instead of a sulfur atom. X-ray analysis indicated distorted square
planar structures for the complexes, and the nickel atoms lie slightly above the planes structured by
the donor atoms. In the crystal forms of 1 and 2, some phenyl ring protons of the phosphine ligand give
intramolecular hydrogen bonds with the donor atoms of the thiosemicarbazone moiety, namely the phe-
nolate oxygen (in complexes 1 and 2) and N4 nitrogen (in complex 2).
Article history:
Received 26 December 2010
Accepted 16 February 2011
Available online 10 March 2011
Keywords:
Thiosemicarbazone
Nickel complex
Triphenylphosphine
Structural analysis
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
The ONS chelate structure is most common in metal–phosphine
complexes of 2-hydroxyarylidene-thiosemicarbazones having sul-
Transition metal complexes of phosphine derivatives have been
known since the 1950s. After the catalytic effective rhodium–tri-
phenylphosphine compound was described [1], a large number of
mixed-ligand complexes with various phosphines and classical
ligands have been studied [2–5]. Metal–phosphine complexes of
thiosemicarbazones have raised considerable interest because of
their possible roles in stereoselective synthesis [5–8]. Thiosemicar-
bazones and their transition metal complexes have a wide range of
biological activities, some of them are antiviral [9,10], antifungal
[11], antibacterial [12,13], antitumor [14,15], anticancerogenic
[16,17], antioxidant [18] and show insulin mimetic effects [19].
Thiosemicarbazones in metal–phosphine complexes behave
depending on the parent carbonyl compounds and the metal ion,
as in their common complexes. While N-heterocyclic thiosemicar-
bazones usually coordinate with a NNS donor set [20,21], some
thiosemicarbazones of heterocyclic and aryl-carbonyl derivatives
coordinate to the metals Cu(I) [22], Cu(II) [23], Ru(II) [24] and
Pd(II) [25] through the azomethine nitrogen and sulfur atoms.
2-Salicylidene-thiosemicarbazones have O, N, and S atoms as
donor sites, and they give five and six membered rings in the
1:1:1 complexes [M(L)PPh3] (where M = Ni(II) [26,27], Pt(II) [28],
Pd(II) [29], Ru(II) [30] and Ru(III) [31]).
fur as a terminal atom and one (or no) substituent on the N4-nitro-
gen of the thioamide group [(CS)-N4HR or (CS)-N4H2]. Differently,
an ONN chelate structure for S-methyl-5-bromo-salicylaldehyde-
thiosemicarbazone was reported in our previous paper [27].
Herein, we present two nickel(II)–triphenylphosphine com-
plexes of 2-hydroxyacetophenone thiosemicarbazones with ONS
and ONN coordination modes (Fig. 1). The ligands and complexes
were characterized by elemental analysis, IR and 1H NMR spectros-
copies. The structures of the complexes were determined by the X-
ray single-crystal diffraction method.
2. Experimental
2.1. Materials and physical measurements
All chemicals were of reagent grade and were used as commer-
cially purchased without further purification. The elemental
analyses were determined on a Thermo Finnigan Flash EA 1112
Series Elemental Analyser. Infrared spectra were recorded as KBr
discs on a Mattson 1000 FT-IR spectrophotometer in the 4000–
400 cmꢁ1 range at room temperature. Electronic spectra of the
compounds were recorded in a 10ꢁ5 M CHCl3 solution with an
ATI-Unicam spectrometer in the 800–200 nm range. The 1H NMR
spectra were recorded on a Bruker Avance-500 model spectrome-
ter relative to SiMe4, using CDCl3 as the solvent.
⇑
Corresponding author. Tel.: +90 212 473 70 35; fax: +90 212 476 71 80.
E-mail address: bahseven@istanbul.edu.tr (B. Ülküseven).
0277-5387/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2011.02.041

1386
Sß. Güveli, B. Ülküseven / Polyhedron 30 (2011) 1385–1388
Fig. 1. The ligands, R/R1: CH3/H (L1H2); CH3/H (L2H2). The complexes, X/Y/n: S/NH/0 (1); NH/S/1 (2).
Suitable crystals of 1 and 2 were mounted on an X-ray diffrac-
tomer, Rigaku RAXIS RAPID imaging plate area detector, with
(ppm, J in Hz, p–t are the symbols for the PPh3 protons) data of
the nickel complexes are given below:
0
graphite monochromated Mo K
a radiation (k = 0.71070 ÅA). The
unit cell dimensions and intensity data were measured at 293 K
(for 1) and 294 K (for 2). The data were corrected for Lorentz and
polarization effects, and the structures of [Ni(L1)(PPh3)] (1) and
[Ni(L2)(PPh3)]ꢀHCl (2) were solved by direct methods using the pro-
gram SIR92 [32]. Hydrogen atoms were refined using the riding
model and the non-hydrogen atoms were refined anisotropically.
All calculations were performed using the crystal structure crystal-
lographic software package [33,34].
2.3.1. Complex 1
Dark red; 199.2–199.6; 85. Anal. Calc. for C28H26N3OPSNi
(542.26 g): C, 62.02; H, 4.83; N, 7.75; S, 5.91. Found: C, 61.92; H,
4.75; N, 7.82; S, 5.98%. UV–Vis: 241 (85 600), 302 (35 300), 362
(20 900), 408 (12 200). IR:
1605, (ACSANH) 1547,
700,
(ACAS) 877. 1H NMR: 7.73 (ddd, J = 1.47, J = 8.79, 6H, p, t),
m m
(N4H) 3437, d(N4H) 1639, (C@N1)
m(PPh3) 1439, 1100, 1031, 1000, 754,
m
m
7.41 (m, 3H, r), 7.33 (t, J = 1.95, J = 7.81, 6H, q, s), 7.55 (dd,
J = 1.47, J = 8.30, 1H, d), 6.90 (ddd, J = 1.95, J = 6.83, 1H, b), 6.53
(ddd, J = 1.46, J = 8.30, 1H, c), 6.23 (d, J = 0.97, J = 8.29, 1H, a), 4.41
(s, 1H, N4H), 2.83 (s, 3H, N4ACH3), 2.69 (s, 3H, CACH3).
2.2. Synthesis of the ligands
L1H2 and L2H2 were prepared by the literature method [35]. The
colors, m.p. (°C), yields (%), elemental analysis (%), UV–Vis [kmax
(
e
),
2.3.2. Complex 2
nm (dm3 cmꢁ1 molꢁ1)], IR (cmꢁ1) and 1H NMR (ppm, J in Hz) data
Dark red; 156.2–157.2; 65. Anal. Calc. for C28H27N3OPSNiCl
(578.72 g): C, 58.11; H, 4.70; N, 7.26; S, 5.54. Found: C, 58.01; H,
4.65; N, 7.10; S, 5.50. UV–Vis: 241 (54 200), 297 (24 300), 377
of the ligands are as follows:
(16 600), 397 (14 000), 408 (7500). IR:
(C@N1) 1601,
(ACSANH) 1543, (PPh3) 1435, 1100, 1027, 1000,
750, 696,
(ACAS) 869. 1H NMR: 7.75 (ddd, J = 1.46, J = 8.78, 6H,
m
(N4H) 3434, d(N4H) 1635,
2.2.1. L1H2
m
m
m
Cream, 143.4–144.6; 75. Anal. Calc. for C10H13N3OS (223.3 g): C,
53.79; H, 5.87; N, 18.82; S, 14.36. Found: C, 53.74; H, 5.82; N,
18.79; S, 14.30%. UV–Vis: 241 (26 500), 260 (shoulder), 304
m
p, t), 7.45 (t, J = 6.34, J = 7.32, 3H, r), 7.38 (t, J = 6.34, J = 6.83, 6H,
q, s), 7.65 (dd, J = 1.46, J = 8.84, 1H, d), 6.93 (t, J = 7.32, 1H, b),
6.61 (t, J = 7.32, 1H, c), 6.55 (dd, J = 1.46, J = 8.78, 1H, a), 5.23 (s,
1H, N4H), 2.85 (s, 3H, SACH3), 2.15 (s, 3H, CACH3).
(26 100), 316 (shoulder), 333 (25 300). IR:
3303,
(N2H) 3272, d(N4H) 1643, d(N2H) 1620,
(ACSANH) 1538, 1292,
m
(OH) 3514,
(C@N1) 1601,
m
(AC@S) 1231. 1H NMR: 10.63 (s, 1H,
m
(N4H)
m
m
m
OH), 8.58 (s, 1H, N2H), 6.76 (br s, 1H, N4H), 7.41 (dd, J = 1.46,
J = 7.81, 1H, d), 7.25 (ddd, J = 1.47, J = 7.42, 1H, b), 6.92 (dd,
J = 1.46, J = 8.30, 1H, a), 6.88 (ddd, J = 1.47, J = 7.32, 1H, c), 3.20 (s,
3H, N4ACH3), 2.31 (s, 3H, CACH3).
3. Results and discussion
3.1. Some physical properties of the compounds
2.2.2. L2H2
The thiosemicarbazones L1H2 and L2H2 separated with precipi-
tation from the reaction mixture in the form of powder crystals.
The ligands are soluble in common solvents. The reactions of the
thiosemicarbazones with [Ni(PPh3)2Cl2] in a 1:1 molar ratio in a
mixture of dichloromethane and ethanol (1:1) yielded solid com-
plexes corresponding to the formulas [Ni(L1)(PPh3)] (1) and
[Ni(L2)(PPh3)]ꢀHCl (2) (Fig. 1). The compositions of the complexes
are stable for at least 4 weeks in air, but the brightness of the crys-
tals decreases within 1–2 weeks.
Yellow; 100.7–100.9; 72. Anal. Calc. for C10H13N3OS (223.3 g): C,
53.79; H, 5.87; N, 18.82; S, 14.36. Found: C, 53.76; H, 5.84; N,
18.78; S, 14.31%. UV–Vis: 242 (29 400), 256 (shoulder), 283
(29 100), 315 (shoulder), 324 (16 900). IR:
3414, 3306, d(N4H) 1647, (C@N1) 1601,
(CAS) 846. 1H NMR: 13.28, 13.16 (cis/trans ratio 2/1, 1H, OH),
m
(OH) 3422,
m
(N4H)
m
m
(ACSANH) 1562,
m
7.46 (d, J = 1.46, J = 7.81, 1H, d), 7.20 (ddd, J = 1.46, J = 7.32, 1H,
b), 6.89 (ddd, J = 0.98, J = 8.30, 1H, a), 6.81 (ddd, J = 0.97, J = 6.83,
J = 7.32, 1H, c), 4.88, 4.66 (cis/trans ratio 2/1, 2H, N4H), 2.46 (d,
J = 5.37, 3H, SACH3), 2.41 (s, 3H, CACH3).
3.2. Spectral data
2.3. Synthesis of the complexes
UV–Vis spectra of the ligands showed p ?
p⁄ and n ? p⁄ bands
at 241–260 and 283–333 nm, respectively [36]. The n ? p⁄ transi-
tions of the complexes were observed at lower wavelengths, 362
(for 1) and 377 nm (for 2). The spectra of 1 and 2 show broad CT
bands in the range 362–408 nm, which can be attributed primarily
to a S(N) ? nickel(II) charge-transfer transition. The d–d transi-
tions related to the square planar structure of the nickel structure
could not be clearly observed because of quite low band
intensities.
A solution of 2-hydroxy-acetophenone-4-methyl-thiosemicar-
bazone (L1H2) (2.23 g, 1 mmol) in dichloromethane (10 ml) was
added dropwise to a solution of [Ni(PPh3)2Cl2] (6.54 g, 1 mmol)
in 10 ml of absolute ethanol. The mixture was stirred for 4 h at
room temperature and left to stand for 6 days. The crystals of the
complex [Ni(L1)(PPh3)] (1) were filtered off and washed with n-
hexane (10 cm3) (yield: 85%).
The complex [Ni(L2)(PPh3)]ꢀHCl (2) was prepared in a similar
manner. The colors, m.p. (°C), yields (%), elemental analysis (%),
The infrared spectra of the ligands distinctly showed the
stretching vibrations of the OH, NH, C@N1 and N2@C groups. The
structuring of the ONS and ONN chelate rings can be easily
UV–Vis [kmax (e
), nm (dm3 cmꢁ1 molꢁ1)], IR (cmꢁ1) and 1H NMR

Sß. Güveli, B. Ülküseven / Polyhedron 30 (2011) 1385–1388
1387
monitored by means of IR spectra due to the fact that the m(OH)
and N2H bands are absent in the spectra of the complexes. Further-
more, a series of medium and weak bands belonging to PPh3 are re-
corded between 696 and 1439 cmꢁ1 in the complex spectra.
Coupling results of the aromatic and aliphatic protons on the
ligand molecules were recorded at the expected chemical shift val-
ues. Because the complex spectra do not contain signals of hydroxy
and one of the thioamide moiety protons, complex formation can
also be confirmed from the 1H NMR spectra. Separation of the thi-
oamide protons occurs through the sulfur atom (in 1) and the N4
atom (in 2).
There are some considerable differences in the chemical shift
values of equivalent complex protons. The N4 proton of 1 was re-
corded at 4.41 ppm, but the N4H signal of 2 was observed in the
higher field (at 5.23 ppm) due to the d+ effect of the nickel atom
bonded to N4. Depending on the coordinated atom, S or N4, the
CACH3 protons of complex 1 were recorded with a shift of approx-
imately 0.38 ppm to higher field compared to the free ligand, while
those of complex 2 shifted to lower field by ca. 0.26 ppm.
The spectral results indicate the ONS and ONN coordination
modes of L1H and L2H, respectively. In these chelation modes,
the thiosemicarbazone ligands act as dianionic ligand structures
which are formed by the separation of two protons from the OH
and SH (in L1) or N3H2 (in L2) groups.
Fig. 2. A view of complex 1 with displacement ellipsoids at the 50% level. The
intramolecular hydrogen bond is indicated by broken lines. For clarity, hydrogen
atoms (except H8 and H12) are excluded, and labeled atoms are as mentioned in the
text.
3.3. Crystallography
Single crystals of complexes 1 and 2, suitable for X-ray diffrac-
tion studies, were grown by crystallization from ethanol–dichloro-
methane (1:2). Data collection conditions and the parameters of
the refinement process are given in Table 1. Ellipsoidal plots of
the complexes are shown in Figs. 2 and 3.
Complex 1 is formed by the chelation of the doubly deproto-
nated thiosemicarbazone ligand to a nickel atom with one PPh3
group attached (Fig. 1). The chelate structure of complex 1 consists
Table 1
Crystal data and structure refinement parameters for complexes 1 and 2.
[Ni(L1)(PPh3)] (1)
[Ni(L2)(PPh3)]ꢀ
HCl (2)
Empirical formula
Formula weight
T (K)
C
28H26N3NiOPS
C28H27N3NiOPSCl
578.73
294
542.27
293
Wavelength (Å)
Crystal dimensions (mm)
Crystal system
Space group
Unit cell
a (Å)
b (Å)
c (Å)
0.71070
0.71070
0.40 ꢂ 0.20 ꢂ 0.10 0.70 ꢂ 0.30 ꢂ 0.10
monoclinic
triclinic
ꢀ
P21/c
Fig. 3. A view of complex 2 with displacement ellipsoids at the 50% level. The
intramolecular hydrogen bond is indicated by broken lines. For clarity, hydrogen
atoms (except H11, H12, and H21) are excluded, and labeled atoms are as
mentioned in the text.
P1
16.2610(7)
8.8505(4)
19.4604(9)
90
113.277(2)
90
2572.7(2)
4
1.400
8.76050
12.49440
13.80760
78.597(6)
72.531(5)
72.858(5)
1367.67(5)
2
1.405
0.968
600.0
ꢁ12 ꢃ h ꢃ 12
ꢁ17 ꢃ k ꢃ 17
ꢁ19 ꢃ l ꢃ 19
1 07 570
8056
a
(°)
b (°)
of two rings, NiOC3N1 and NiN1N2CS, through the O, N1 and S
atoms of L1. The PPh3 ligand coordinates to nickel(II), and the
fourth coordination site of the central atom is completed by the
phosphorus atom (Fig. 2). The donor atoms of the complex 1 are
placed in the corners of a slightly deformed square plane, like in
the nickel–triphenylphosphine complex obtained from 5-bromo-
salicylaldehyde-thiosemicarbazone [27]. The coordination bonds
of both complexes are of approximately the same lengths, although
the Ni1AO1 bond of complex 1 is slightly shorter than the equiva-
lent bond of the other complex by approximately 0.03 Å. Addition-
ally, the intramolecular bond between the phenolate oxygen and
one of phenyl rings of the phosphine ligand in complex 1 is
longer. The relevant geometrical parameters are: C12AH12ꢀ ꢀ ꢀO1,
c
(°)
V (Å3)
Z
Dcalc (g/cm3)
k (Mo K
a
) (mmꢁ1
)
0.924
1128.0
F(0 0 0)
h, k, l Range
ꢁ23 ꢃ h ꢃ 23
ꢁ12 ꢃ k ꢃ 12
ꢁ27 ꢃ l ꢃ 27
1 48 978
8046
0.039
0.038[I > 2
0.045[I > 2
Reflections collected
Unique reflections
Rint
R
Rw
0.028
r
r
(I)]
(I)]
0.053[I > 3
0.044[I > 3
1.053
r
r
(I)]
(I)]
Goodness-of-fit (GOF) on indicator 1.074

1388
Sß. Güveli, B. Ülküseven / Polyhedron 30 (2011) 1385–1388
Table 2
5. Supplementary data
The nickel centered bond distances (Å) and angles (°) of 1 and 2.
Distance (Å)
Angles (°)
CCDC 776732 and 728255 contain the supplementary crystallo-
graphic data for complexes 1 (C28H26N3NiOPS) and 2 (C28H27Cl1N3-
NiOPS). These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Complex 1
Ni1–O1
Ni1–N1
Ni1–P1
Ni1–S1
1.821(2)
1.896(2)
2.1948(4)
2.1198(7)
O1–Ni1–S1
P1–Ni1–N1
O1–Ni1–N1
O1–Ni1–P1
P1–Ni1–S1
N1– Ni1–S1
173.20(6)
175.38(6)
95.26(8)
81.21(5)
94.66(2)
89.14(6)
Acknowledgements
Complex 2
Ni1–O1
Ni1–N1
Ni1–P1
1.811(1)
1.883(1)
2.12082(4)
1.842(2)
O1–Ni1–N3
P1–Ni1–N1
O1–Ni1–N1
O1–Ni1–P1
P1–Ni1–N3
N1–Ni1–N3
177.67(6)
173.74(5)
94.97(6)
90.18(4)
92.01(5)
82.79(7)
This present work was supported by the Research Fund of Istan-
bul University. Project No. T-4156.
Ni1–N3
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The molecular structure of complex 2 has two intramolecular
hydrogen bonds involved protons of PPh3. Geometrical parameters
of these interactions, C12AH12ꢀ ꢀ ꢀO1 and C22AH21ꢀ ꢀ ꢀN3, leading
[23] T.S. Lobana, P. Kumari, R.J. Butcher, Inorg. Chem. Commun. 11 (2008) 11.
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0
to the formation of six-membered rings, are CAH@ 0.95 ÅA, Hꢀ ꢀ ꢀO@
0
0
0
2.565 ÅA, Cꢀ ꢀ ꢀO@ 2.940 ÅA, CAHꢀ ꢀ ꢀO@ 103.77° and CAH@ 0.95 ÅA,
0
0
Hꢀ ꢀ ꢀN@ 2.687 ÅA, Cꢀ ꢀ ꢀN@ 3.451 ÅA, CAHꢀ ꢀ ꢀO@ 138.02°, respectively.
There are no hydrogen-bonds or significant intermolecular interac-
tions in the crystal structures of complexes 1 and 2.
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Inorg. Chim. Acta 360 (2007) 691.
4. Conclusion
There is a limited number of nickel–phosphine complexes with
thiosemicarbazones [26,27,37]. In these complexes, except a nickel
complex in our previous paper [27], the thiosemicarbazone ligands
having a sulfur as a terminal atom are functional with the ONS coor-
dination mode. In this study, new nickel(II)–triphenylphosphine
complexes with 2-hydroxyacetophenone thiosemicarbazones with
ONS and ONN coordination modes were characterized. By describ-
ing the ONN chelate complex of L2, we have shown this time using
acetophenone thiosemicarbazones that the nitrogen atom (N3) of
the thioamide moiety can react with nickel(II).
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