Coordination diversity of N-phosphoryl-N′-phenylthiourea (LH) towards CoII, NiII and PdII cations: Crystal structure of ML2-N,S and ML2-O,S chelates

Article abstract of DOI:10.1016/j.ica.2006.01.014

Thiourea, PhNHC(S)NHP(O)(OPrⁱ)₂ (LH) chelates of Co^II, Ni^II, and Pd^II ions have been obtained and investigated by single-crystal X-ray diffraction, UV, IR, NMR spectroscopy, and EI mass-spectrometry.

Full text of DOI:10.1016/j.ica.2006.01.014

Inorganica Chimica Acta 359 (2006) 2087–2096
www.elsevier.com/locate/ica
Coordination diversity of N-phosphoryl-N0-phenylthiourea
(LH) towards CoII, NiII and PdII cations: Crystal structure of
ML2-N,S and ML2-O,S chelates
a
a
a
a
Felix D. Sokolov , Nail G. Zabirov , Luiza N. Yamalieva , Valery G. Shtyrlin ,
a
a
a
a
Ruslan R. Garipov , Vasily V. Brusko , Alexander Yu. Verat , Sergey V. Baranov ,
Piotr Mlynarz b,1, Tadeusz Glowiak , Henryk Kozlowski
b
b,
*
a
Kazan State University, Department of Chemistry, Kremlevskaya Street 18, Kazan 420008, Russia
b
University of Wroclaw, Faculty of Chemistry, F. Joliot-Curie 14, 50-383 Wroclaw, Poland
Received 27 September 2005; received in revised form 2 January 2006; accepted 15 January 2006
Available online 28 February 2006
Abstract
Thiourea, PhNHC(S)NHP(O)(OPri)2 (LH) chelates of CoII, NiII, and PdII ions have been obtained and investigated by single-crystal
X-ray diffraction, UV, IR, NMR spectroscopy, and EI mass-spectrometry. The unusual 1,3-N,S-coordination via sulfur and NP(O)
nitrogen atoms has been found in the trans-square-planar NiL2 and PdL2 complexes, whereas the 1,5-O,S-coordination is realized in
the tetrahedral CoL2 complex. DFT calculations have revealed significant stabilization of the 1,3-N,S-structures due to stronger crystal
field and the NH–O@P hydrogen bonds.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Thiourea coordination; Substituent effects; CoII complexes; NiII complexes; PdII complexes; N,S-coordination; O,S-coordination
1. Introduction
RC(S)NHP(Y)(OR0)2 (Y = O,S) always proceeds on the
thiocarbonyl sulfur atom [1a,5].
b-Dicarbonyl compounds (N-acylureas 1, acetylaceto-
nates, etc.) and their phosphorus containing analogs (N-
acylamidophosphinates 2, imidodiphosphinates 3) (Fig. 1)
were found to be very attractive ligands for variety of metal
ions [1–4].
b-Bifunctional ligands 1–3 contain three potential donor
centers: X, Y and internal nitrogen atoms. Nucleophilic
ability of the latter donor is significantly reduced by the
two neighboring electron-withdrawing groups. That is
why the alkylation of N-thioacylamido(thio)phosphates-
There is a fair amount of the data concerning the struc-
tures of complexes of divalent transition metal ions of Ib,
IIb, VIIIb groups with N-thioacylamidothiophosphinates
(2) (X, Y = S) [1–5,7–10]. The 1,5-bidentate coordination
of deprotonated ligands through sulfur atoms takes place
in all these cases.
The substituents (or other factors) are hardly capable of
changing a coordination mode in the complexes of dithio-
derivatives of 2 with divalent cations of VIIIb group. Due
to the strong p-interactions, the formation of metal–sulfur
bonds is most energetically favorable in all these cases.
Replacement of one sulfur atom in conjugated
½RCðXÞNPðYÞR02ꢀðꢁÞ moiety to oxygen (X = S, Y = O or
X = O, Y = S) leads to appearance of the ambivalent coor-
dination modes and possible competition between the three
donor centers in the binding anion species. As a result, the
*
Corresponding author.
E-mail addresses: felix.sokolov@ksu.ru (F.D. Sokolov), henrykoz@
wchuwr.chem.uni.wroc.pl (H. Kozlowski).
1
Present address: Wroclaw University of Technology, Wybrzeze Wys-
pianskiego 27, 50-370 Wroclaw, Poland.
0020-1693/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.01.014

2088
F.D. Sokolov et al. / Inorganica Chimica Acta 359 (2006) 2087–2096
Ph
O
X
C
Y
P
X
P
Y
P
X
C
Y
C
O
P
N
R'
R'
R''
R''
Pr-n
N
R'
R'
Ph
O
C
O
R
Pr-n
NH
R
R'
NH
2
NH
Ph
P
H
O
C
S
R'
R'
S
R'
3
1
Ph
N
NH
P
N
Ni N
S
O
P
Pd
P
C
Ph
N
P
S
R'
S
Pd
H
Fig. 1. Schematic representation of the structures 1–3 (X, Y = O, S).
Pr-n
N
S
Ph
Cl
O
O
Pr-n
Ph
O
Ph
formation of the chelate isomers with 1,3-X, N (or 1,3-Y,
N) and 1,5-X,Y coordination becomes possible. This
ambivalent ligand behavior was practically not investigated
for compounds 2, neither for their analogs 1 and 3.
The numerous complexes of N-acylthiourea (1),
M[R2NC(S)NC(O)Ar]2 (I = NiII, PtII, PdII) [11] were
described; however, according to the X-ray data all of them
have shown the same square planar MO2S2-coordination
pattern.
Much less data are available for the coordination ability
of mixed-chalcogen ligands 2. The studied complexes,
Pd[PhC(O)NP(S)Ph2]2 [2], Cu(PPh3)[PhC(O)NP(S)Ph2]
[2], and M[PhC(S)NP(O)(OPri)2]2 (M = PdII [12], CuII
[13], HgII [10], and PbII [14]), exist as the 1,5-O,S-isomers.
N-thioacylamidothiophosphinate (2) complexes with the
CoIIO2S2 [15] and NiIIO2S2 [16] nuclei show a tendency to
increase the coordination number around the metal ion.
Two types of complexes were formed by the reaction of
thioamide PhC(S)NHP(O)(OPr-i)2 (HQ) potassium salt
with Co(II) nitrate: the blue complex CoQ2 with tetrahe-
dral CoO2S2 core and yellow Co(HQ)2Q2 complex with
square-bipyramidal Co(Oeq)2(Oax)2S2 core [15]. A square-
bipyramidal Co(Oeq)2(Oax)2S2 moiety was formed by two
1,5-O,S-coordinating ligands in the equatorial plane and
two neutral HQ molecules coordinated through phos-
phoryl oxygen atoms in the axial positions. The reaction
of this ligand with Ni(II) nitrate resulted in the square-
bipyramidal Ni(HQ)2Q2 complex [16].
4
5
6
Fig. 2. Coordination modes in complexes 4, 5 and 6.
square-planar complex Ni[nPrC(O)NC(S)NHPrn-N,S]2 (6)
[22].
As the possible reasons for the 1,3-S,N-chelate forma-
tion, the acceptor property of PhO at P(O)(OPh)2 groups
[20] and the stabilizing effect of the intramolecular hydro-
gen bonds [22] were suggested. However, attempts to esti-
mate the mutual stability of the appropriate 1,3-N,S- and
1,5-O,S-species and the importance of the different stabiliz-
ing structural factors were not discussed.
Here, we report the first example of competitions
between 1,3-N,S- and 1,5-O,S-coordination of thiourea
PhNHC(S)NHP(O)(OPri)2 (LH) in ML2 chelates for
M = CoII (7), NiII (8) and PdII (9).
2. Experimental
2.1. General information
Commercially available compounds M(NO3)2 Æ 6H2O
(M = Ni, Co) and Pd(PhCN)2Cl2 were used as supplied.
Infrared spectra were recorded in the range of 250–
4000 cmꢁ1 on a Specord M-80 spectrometer. Electronic
absorption spectra were recorded with a Perkin–Elmer
Lambda 35 spectrophotometer in CDCl3 solutions in the
10ꢁ2 M up to 10ꢁ6 M concentration range of the ligand.
The NMR 1H (300 MHz), 31P (122.4 MHz) and 13C
(75.4 MHz) spectra were obtained using a Varian Unity-
300 NMR spectrometer. The 31P chemical shifts were cali-
brated indirectly to the 85% H3PO4 peak (d 0.0 ppm).
Mass-spectra were obtained on a TRACE MS ‘‘Finnigan
MAT’’ instrument. Electron ionization energy was 70 eV.
The substance was injected directly into the ion source at
150 °C. Heating of vaporizer-ampoule of the direct injec-
tion energy was carried out in programmed mode from
35 to 200 °C with a speed of 35 °C per minute. M elec-
tro-spray ionization mass-spectra were recorded on
Thermo Finnigan LCQ mass-spectrometer for 10ꢁ6 M
solution in CHCl3/MeOH mixture (1:1 v/v), speed of a
sample submission was 3 lL/min, ionizing voltage was
4.10 kV, and capillary temperature was 210 °C.
The studies of the complexes of VIIIb group with imi-
dodiphosphinates (3), containing non-equivalent donor
atoms X and Y, were reported recently. The ligands
[Ph2P(O)NP(Y)Ph2]ꢁ (Y = S, Se) coordinate to PdII ion
by oxygen and Y atoms, giving the six-membered chelate
rings [17]. Ni(II) also forms complexes with the mixed-chal-
2
cogen imidodiphosphinates, Ni½Ph2PðOÞNPðSÞR2 -O; Sꢀ2
(R2 = Ph, Me) [18]. The latter complexes unusually have
the tetrahedral NiO2S2 coordination core.
Presently, only five reliably known examples of the
nitrogen atom involvement in the coordination with
VIIIB-group metal ions for ligands 1–3 are known. These
are PdII complexes with imidodiphosphinate ðPhOÞ2PðOÞ
NHPðSÞR02 with R0 = OPh [19], Ph [20], i-Pr [20], and
bis-thiophosphinate urea [Ph2P(S)NH]2CO [21]. The struc-
tures of these complexes were solved by X-ray as 4 and 5,
which is depicted in Fig. 2.
Strong p–p conjugation in –C(S)–N–C(O)– anion in com-
bination with electron-withdrawing properties of C = X
groups lowers the electron density on the nitrogen, making
it unlikely to be involved in the metal ion binding. However,
1,3-N,S-coordination was recently found in the trans-
2.2. X-ray crystallography
X-ray data were collected on a KUMA KM-4 diffrac-
tometer with graphite-monochromated Cu Ka radiation
using the x–2h technique at 100 K. Corrections were made

F.D. Sokolov et al. / Inorganica Chimica Acta 359 (2006) 2087–2096
2089
for Lorentz-polarization and adsorption effect. There was
no crystal decay as measured by three standard reflections.
The structure was solved by direct methods (SHELXS-97)
and refined by full-matrix least-squares (SHELXL-97) aniso-
tropically for all non-hydrogen atoms [23,24]. All figures
were made using the program PLATON [25]. Crystal data
are summarized in Table 1.
slowly added with vigorous stirring. The mixtures were
kept for 5–10 h at room temperature. The resulting com-
plexes were extracted with methylene chloride. After drying
under anhydrous MgSO4, the solvent was removed in vac-
uum. The residue was crystallized from a methylene chlo-
ride/n-hexane mixture 1:5 (v/v).
Bis-(N-diisopropoxyphosphinyl-N0-phenylthioureato-O,S)
cobalt(II). Co[PhNHC(S)NP(O)(OPr-i)2-O,S]2 (7). Blue
crystals. M.p. 117–118 °C. Yield 0.897 g, 1.30 mmol, 65%.
Anal. Calc. for C26H40CoN4O6P2S2C, 45.28; H, 5.85; N,
2.3. Ligand preparation
N-diisopropoxyphosphinyl-N0-phenylthiourea (LH) was
prepared according to the established literature method
[26]. M.p. 124 °C (from CH2Cl2 + C6H14 1:5) (Lit. [26],
124–125 °C from hexane). Anal. Calc. for C13H21N2O3PS:
C, 49.36; H, 6.69; N, 8.86. Found C, 49.38; H, 6.69; N,
8.96%. IR (KBr, mmax/cmꢁ1): 3300 w (PNH), 3096 br, s
(NHPh), 1626 m (Ph), 1572 s, 1502 vs (dS@C–NH), 1244
vs, 1210 m (P@O), 1018 br, vs (P–O–C). 1H NMR
8.12. Found C, 45.25; H, 5.70; N, 8.15%. IR (KBr, mmax/
cmꢁ1): 3304 (NH), 1554 s, 1522 vs (S'C'N), 1130 s
(P@O), 1000 vs (P–O–C), 364 w (Co–S). EI MS m/z,
I(%): 689 (M+, 0.11), 316 (5.50), 274 (2.00), 257 (0.44),
198 (73.10), 202 (0.50), 118 (100.00), 43 (56.74); calc. for
Co[PhNHC(S)NP(O)(OPr-i)2]2: m/z 689.
Bis-(N-diisopropoxyphosphinyl-N0-phenylthioureato-N,S)
nickel(II), Ni[PhNHC(S)NP(O)(OPr-i)2-N,S]2 (8). Violet
crystals. M.p. 106–107 °C (dec.). Yield 1.141 g, 1.66 mmol,
83%. Anal. Calc. for C26H40N4NiO6P2S2: C, 45.30; H, 5.85;
N, 8.13. Found: C, 45.36; H, 5.36; N, 7.86%. IR (KBr,
3
(CDCl3): d = 1.395 (broad d, JHH 7.0 Hz, 12H, CH3),
3
3
4.76 (d, sept, JPH 7.3 Hz, JHH 6.2 Hz, 2H, OCH), 6.93
2
(br, d, JPH 6.3 Hz, 1H, NHP), 7.20–7.26 (m, p-Ph + sol-
vent), 7.35–7.41 (m, 2H, m-Ph), 7.60–7.62 (m, 2H, o-Ph),
m
max/cmꢁ1): 3152 (NH), 1544 vs (S'C'N), 1196 s
10.77 (s, 1H, PhNH) ppm. 13C–{1H} NMR (CDCl3):
(P@O), 998 vs, broad (P–O–C), 380 w (Ni–S). EI MS m/
z, I(%): 688 (M+, 0.04), 656.5 (0.02); 375 (2.46), 316
(26.00), 231 (25.75), 198 (69.64), 118 (89.60), 43 (100) calc.
for Ni[PhNHC(S)NP(O)(OPr-i)2]2:m/z 688. ESI M+ MS,
m/z, I(%): 711 (70%) [M + Na]+, 339 (100%) [NaL + H]+.
3
3
d = 23.61 (d, JPC 4.9 Hz, CH3), 23.73 (d, JPC 4.9 Hz,
2
CH3), 74.05 (d, JPC 6.6 Hz, OCH), 124.26 (s, o-Ph),
126.39 (s, p-Ph), 128.70 (s, m-Ph), 138.25 (s, ipso-Ph),
180.65 (s, C–S) ppm. d31P (CDCl3): d =ꢁ5.3 (q,
2JPH + 3JPH 6.7 Hz) ppm.
1
ESI Mꢁ MS, m/z, I(%): 687 (100%) [M ꢁ H]ꢁ. H NMR
3
(CDCl3): d = 1.36 (d, JHH 6.2 Hz, 12H, CH3), 1.66 (d,
3
2.4. Complexes of LH with Co(II), Ni(II) and Pd(II) ions
3JHH 6.2 Hz, 12H, CH3), 4.65 (octet, JPH + 3JHH 6.6 Hz,
4H, OCH), 7.16–7.21 (m, 2H, p-Ph), 7.32–7.37 (m, 4H,
m-Ph), 7.41–7.43 (m, 4H, o-Ph), 10.6 (s, 2H, NH) ppm.
13C–{1H} NMR (CDCl3): d = 23.87–24.02 (m, CH3),
2.4.1. General procedure
To a suspension of LH (1.2654 g, 4.0 mmol) in 30 ml of
96% ethanol, a solution of potassium hydroxide (0.2244 g,
4.0 mmol) in 30 ml of the same solvent was added, and the
mixture was stirred until the ligand dissolved completely.
To the resulting potassium salt of LH, a solution of
M(NO3)2 Æ 6H2O (0.6403 g for M = CoII, 0.6397 g for
M = NiII, 2.2 mmol, 10% excess) in 50 ml of water was
2
72.00 (d, JP,C = 4.8 Hz, OCH), 122.52 (s, o-Ph), 125.82
(s, p-Ph), 129.00 (s, m-Ph), 135.65 (s, ipso-Ph), 185.45 (s,
C–S) ppm. 31P–{presup1H} NMR (CDCl3): d = 1.71 (s)
ppm.
Bis-(N-diisopropoxyphosphinyl-N0-phenylthioureato-N,S)
palladium(II). Pd[PhNHC(S)NP(O)(OPr-i)2-N,S]2 (9). A
Table 1
Crystal data and structure refinement for ML2 chelates 7–9
7
8
9
Empirical formula
M
C
689.61
26H40CoN4O6P2S2
C26H40N4NiO6P2S2
689.39
C26H40N4O6P2PdS2
737.08
Crystal system
Space group
triclinic
monoclinic
P21/n
10.555(2)
14.293(3)
21.741(4)
monoclinic
P21/n
10.752(2)
14.237(3)
21.661(4)
ꢀ
P1
˚
a (A)
12.294(3)
12.427(3)
13.551(3)
107.37(3)
106.94(3)
108.70(3)
1691.3(11)
2
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
98.94(3)
98.76(3)
3
˚
V (A )
3240.1(11)
4
0.871
3277.1(11)
4
0.835
Z
l (mmꢁ1
)
0.768
Reflections collected/unique [Rint
Final R1, wR2 [I > 2r(I)]
]
9563/5794 [0.1167]
0.0973, 0.2342
19699/6287 [0.0606]
0.0595, 0.0676
20722/7617 [0.0240]
0.0280, 0.0635

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F.D. Sokolov et al. / Inorganica Chimica Acta 359 (2006) 2087–2096
thiourea LH (1.2654 g, 4.0 mmol) in 30 ml of anhydrous
ethanol was converted to the potassium salt followed by
Section 2.4.1 and was added dropwise with vigorous stir-
ring to a solution of Pd(PhCN)2Cl2 (0,7671 g, 2.0 mmol)
in 100 ml of anhydrous ethanol. The mixtures were kept
for 20 h at room temperature. The solvent was removed
in vacuum. The residue was resolved in 10 ml of methylene
chloride and the insoluble KCl was filtered. The product
was precipitated by n-hexane and recrystallized from a
methylene chloride/n-hexane mixture 1:5 (v/v). Chelate 9
forms yellow crystals. M.p. 180–182 °C. Yield 1.01 g,
1.38 mmol, 68.8%. Anal. Calc. for C26H40N4O6P2PdS2: C,
42.37; H, 5.47; N, 7.60. Found: C, 42.34; H, 5.36; N,
7.78%. IR (nujol, mmax/cmꢁ1): 3160 (NH), 1540 (S'C'N),
1200 (P@O), 1008 (P–O–C) 370, 350 (Pd–S). EI MS: M+
not observed, calc. for Pd[PhNHC(S)NP(O)(OPr-i)2]2:m/z
736. ESI M+ MS, m/z, I(%): 759 (100%) [M + Na]+. ESI
Mꢁ MS, m/z, I(%): 735 (100%) [M ꢁ H]ꢁ. 1H NMR
The obtained compounds were investigated by UV, IR,
1
NMR H, 13C and 31P spectroscopy, EI and ESI mass-
spectrometry. Intensive [ML2 + Na]+ and [ML2 ꢁ H]ꢁ
peaks were found in ESI M+ and Mꢁ spectra of complexes
8 and 9. Crystal and molecular structures of complexes 7–9
were determined by single-crystal X-ray diffraction (Figs. 3
and 4). Selected bond lengths, valence and torsion angles
for complexes 7, 8, and 9 are presented in Tables 2 and 3.
Our experiments have shown that the coordination
mode of thiourea depends on the nature of the metal ion
(Scheme 1). The 1,3-coordination via sulfur and phospho-
rylimide nitrogen atoms was found in the Ni(II) and Pd(II)
complexes 8 and 9. Phosphoryl group does not participate
in the coordination in these complexes. This is the first
example of the four-membered chelate ring formation in
the complexes with ligands containing RCðSÞNHPðYÞR20
unit (Y = O, S).
The N,S-coordination is not realized in the CoII com-
plex 7. Compound 7 is a spirocyclic chelate with a distorted
tetrahedral CoO2S2-core.
3
(CDCl3): d = 1.34 (d, JHH 6.2 Hz, 12H, CH3), 1.50 (d,
3
3
3JHH 6.2 Hz, 12H, CH3), 4.79 (d, sept, JPH 7.4 Hz, JHH
6.2 Hz, 4H, OCH), 6.89–6.92 (m, 2H, p-Ph), 7.00–7.05
(m, 4H, m-Ph), 7.44–7.47 (m, 4H, o-Ph), 11.58 (s, 2H,
3.1. IR-spectroscopy investigations
3
NH) ppm. 13C–{1H} NMR (CDCl3): d = 23.96 (d, JPC
2
4.8 Hz, CH3), 72.31 (t, JPC 5.1 Hz, OCH), 122.80 (s, o-
The coordination of phosphoryl group results in the low
frequencies shift when compared to the free ligand value
(mas 1244 cmꢁ1). The shift of DmP@O 44–48 cmꢁ1 is observed
for the N,S-coordination (8, 9) and it increases up to
114 cmꢁ1 in O,S-complexes of Co(II) (7). The IR spectra
of thiourea LH clearly show the presence of the strong
intramolecular PhNHꢂ ꢂ ꢂO@P hydrogen bonds both in
the solid state and in solutions [27]. There is only one
strong band in the range of 3100–3160 cmꢁ1 for complexes
8 and 9 instead of two broad bands at 3300 (PNH) cmꢁ1
and 3096 cmꢁ1 (NHPh) in parent thiourea. The PhNH-
group absorption band in complex 7 is shifted to higher
frequency up to 3304 cmꢁ1 due to the breaking of intramo-
lecular PhNHꢂ ꢂ ꢂO@P hydrogen bonds. It is difficult to
Ph), 126.04 (s, p-Ph), 129.06 (s, m-Ph), 135.28 (s, ipso-
Ph), 187.93 (s, C–S) ppm. 31P–{1H} NMR (CDCl3):
d = 2.69 (s) ppm.
3. Results and discussion
Chelates of Co(II) (7) and Ni(II) (8) were obtained by
the reactions of M(NO3)2 Æ 6H2O aqueous solutions with
the potassium salt of N-diisopropoxyphosphinyl-N0-phen-
ylthiourea (LH) in aqueous ethanol. The Pd(II) (9) com-
*
plex was obtained by reacting PdCl2 2PhCN with the
potassium salt of the LH in ethanol. Complexes 7–9 were
obtained as color crystals, stable in the air.
Fig. 3. Crystal structure of the complex Co[PhNHC(S)NP(O)(OPr-i)2-O,S]2 (7). The atoms are shown as 50% probability of thermal vibrations.

F.D. Sokolov et al. / Inorganica Chimica Acta 359 (2006) 2087–2096
2091
Fig. 4. Crystal structure of the complex Ni[PhNHC(S)NP(O)(OPr-i)2-N,S]2 (8). The atoms are shown as 50% probability of thermal vibrations.
separate the specific band for the C–S and C–N groups
both for thiourea LH and complexes 7–9. The strong infra-
red absorption observed for all concerned complexes in the
region 1500–1570 cmꢁ1 was assigned to the group vibra-
tions of the conjugated SCN fragment. The weak M–S
vibration was observed at 350–380 cmꢁ1 range.
Table 2
Selected bond lengths (A), valence and torsion angles (°) for complex 7
˚
Co–S(11)
Co–S(21)
Co–O(11)
Co–O(21)
S(11)–C(11)
S(21)–C(21)
P(11)–O(11)
P(21)–O(21)
S(21)–Co–O(11)
S(11)–Co–O(21)
S(11)–Co–O(11)
S(21)–Co–O(21)
2.305(3)
2.319(3)
1.974(5)
1.960(5)
1.789(9)
1.779(8)
1.513(5)
1.526(5)
119.16(17)
118.25(18)
99.65(16)
100.03(17)
P(11)–N(11)
P(21)–N(21)
N(11)–C(11)
N(21)–C(21)
N(12)–C(11)
N(22)–C(21)
N(12)–C(12)
N(22)–C(22)
Co–S(11)–C(11)–N(11)
Co–S(21)–C(21)–N(21)
N(11)–P(11)–O(11)–Co
N(21)–P(21)–O(21)–Co
1.613(7)
1.625(7)
1.306(10)
1.305(11)
1.358(10)
1.370(10)
1.428(10)
1.427(9)
ꢁ9.0(9)
3.2. NMR studies
Redistribution of the electronic density after deprotona-
tion of the ligand molecules results in significant low-field
shifts of the signals in 31P spectra. The 31P signals of com-
plexes 8 and 9 are shifted by 6–7 ppm in comparison with
ꢁ8.9(9)
ꢁ13.9(6)
ꢁ14.2(6)
Table 3
˚
Comparative distances (A) and bond angles (°) computed at the PBE level with different basis sets and found from the X-ray crystal data for the
M[PhNHC(S)NP(O)(OPr-i)2-N,S]2 complexes 8 and 9
8
ECP-TZVP0
TZVP0
9
ECP-TZVP0
TZVP0
M–S(11)
M–S(21)
M–N(11)
M–N(21)
S(11)–C(11)
S(21)–C(21)
N(11)–C(11)
N(21)–C(21)
N(12)–C(11)
N(22)–C(21)
P(11)–O(11)
2.2209(13)
2.2203(13)
1.907(3)
1.906(3)
1.732(4)
1.737(4)
1.332(4)
1.342(4)
1.337(4)
1.329(4)
1.471(2)
1.471(2)
1.655(3)
1.647(3)
2.253
2.253
1.910
1.910
1.744
1.744
1.357
1.357
1.349
1.349
1.518
1.518
1.682
1.682
73.8
2.250
2.250
1.912
1.912
1.738
1.738
1.354
1.354
1.347
1.347
1.515
1.515
1.680
1.680
73.5
2.3323(8)
2.3306(8)
2.0284(15)
2.0307(15)
1.7382(19)
1.7347(18)
1.330(2)
1.332(2)
1.338(2)
1.337(2)
1.4664(14)
1.4713(14)
1.6548(16)
1.6459(16)
70.16(5)
70.18(5)
23.74(19)
16.00(19)
2.386
2.386
2.065
2.065
1.749
1.749
1.356
1.356
1.350
1.350
1.518
1.518
1.681
1.681
69.1
2.406
2.406
2.091
2.091
1.742
1.742
1.352
1.352
1.349
1.349
1.515
1.515
1.677
1.677
68.4
P(21)–O(21)
P(11)–N(11)
P(21)–N(21)
N(11)–M–S(11)
N(21)–M–S(21)
O(11)–P(11)–N(11)–C(11)
O(21)–P(21)–N(21)–C(21)
74.36(9)
74.50(9)
21.9(4)
16.6(4)
73.8
11.7
11.1
73.5
10.5
10.3
69.1
12.4
12.5
68.4
13.8
13.1

2092
F.D. Sokolov et al. / Inorganica Chimica Acta 359 (2006) 2087–2096
structure of complex 10 has been investigated by X-ray
˚
analysis [29] [bond lengths, A: CS 1.740(3), CNP 1.291(4),
O
HN Ph
N
O
CNAr 1.357(4), P–N 1.594(3), NiSC 2.2073(9)].
As expected, the P–N bonds in the six-membered ring of
complex 7 are shortened, and P–O bonds are lengthened in
comparison with the data of Ni(II) 8 and Pd(II) 9 com-
plexes (Table 3).
P
O
M
S
S
M = CoII (7)
N
O
P
O
Ph NH
O
H
Ph
S
1) KOH
2) M2+
N
O
P
O
The CS and intracyclic CNP bonds lengths in the S,S0-
chelate 10 are noticeably shorter than in complex 7 (Table
2). The P–N bonds in 7 are longer than those in the chelate
10. It suggests the lower degree of negative charge delocal-
ization in the chelate ring of 7.
N
O
H
H
O
P
N
M
N
O
O
Ph
M = NiII (8), PdII (9)
N
LH
S
S
The six-membered ring M–S1–P–N–C–S2 in the com-
plexes of N-thioacylamidophosphinates RCðS1ÞNHPðS2Þ
R02 usually has a distorted boat conformation [2,6,7,9,29].
On the contrary, the chelate rings in 7 are significantly flat-
tened (Table 2).
O
P
N Ph
H
O
O
Scheme 1. Coordination modes of the thiourea LH.
The hydrogen bonds in the crystal of complex 7 were not
found.
metal-free thiourea. The NMR signals are single narrow
lines, with the line-width Dm1/2 of 10.4 for 8 and 4.5 Hz
for 9. This strongly suggests the presence of only one com-
plex in the solutions studied.
3.3.2. Crystal structures of the NiII and PdII complexes 8 and
9
The metal center in 8 and 9 has a distorted square-
planar MN2S2 environment with trans-configuration of
ligands. Sums of valence angles around nickel and palla-
dium atoms in complexes 8 and 9 are close to 360°. Endo-
cyclic S–M–N angles are more than 30° smaller than the
exocyclic ones (Table 3).
The NMR 1H and 13C spectra of complexes 8 and 9 also
contain one set of signals.
The values of the chemical shifts and coupling constants
indicate the same coordination modes in solution as it was
found in the solid state.
1
Thus, S–M–N intracyclic angles (M = NiII, PdII) in four-
membered cycles do not exceed 70–78° in contrast with O–
Co–S angles in six-membered chelate ring of 7 (Table 2).
The formation of a six-membered chelate ring in the tet-
rahedral complex 7 is more tolerable by steric reasons. Ste-
ric requirements of N,S-chelates can make a strong
distortion of tetrahedral complex core. The average dis-
CH3-proton signals in H spectra of complexes 8 and 9
appear as two separate doublets with integral intensity cor-
responding to 24 protons. This is caused by the diastereo-
isomer formation upon coordination.
3.3. X-ray crystallography
3.3.1. Crystal structure of the CoII complex 7
˚
tances between NP and S donor centers are only 2.51 A
˚
Compound 7 is a spiro-cyclic chelate with a tetrahedral
CoO2S2-core (Fig. 3). Values of endocyclic S–Co–O angles
are reduced and exocyclic angles are increased in compari-
son with an ideal tetrahedron angle, 109.5° (Table 2).
The geometry of thiourea N–C–N fragments shows that
lone electron pairs of PhNH-group nitrogens [N(12) and
N(22)] are conjugated with endocyclic N–C bonds [torsion
angles C(12)N(12)C(11)N(11) – 1.9(13)° and C(22)N(22)
C(21)N(21) – 4.3(13)°]. The endocyclic C–N bonds in com-
for complex 8 and 2.52 A for complex 9. The average O–
˚
S distance in 1,5-O,S-complex 7 is 3.28 A. It is obvious that
significant distortion of tetrahedral metal geometry would
require to achieve similar distance in the case of 1,3-N,S-
coordination to CoII cation.
The C–S bond lengths are shorter, while the CNP bond
lengths in the four-membered rings 8 and 9 (Table 3) are
longer than those in the six-membered O,S-chelate of 7
(Table 2) and S,S0-chelate of 10. The P–N bonds in com-
plexes 8 and 9 are single and P@O bonds are double
according to their bond lengths [30].
˚
plex 7 are 0.052–0.065 A shorter than the exocyclic ones.
At the same time, C–N bond lengths (Table 2) in chelate
ring are appreciably lengthened in comparison with typical
The one of the exocyclic carbon–nitrogen bond N(22)–
C(21) in complex 8 is slightly shorter than the endocyclic
˚
C@N double bond values (1.255 A) [28], confirming the
˚
conjugation with PhNH-group nitrogen.
A similar
N(21)–C(21) by 0.013 A. In all the other cases, C–N bond
tendency is observed for the six-membered ring of N-thi-
ophosphinylthiourea S,S0-complexes: Ni[MeNHC(S)NP-
(S)Ph2]2 [6], Ni[n-Pr2NC(S)NP(S)(OPh)2]2 [7], Pt[H2NC(S)-
NP(S)Ph2]2 (Et2O) [2], Zn[H2NC(S)NP(S)Ph2]2 [2], and
Ni[PhNHC(S)NP(S)(OPri)2]2 (10). The trans-square-planar
complex 10 is formed by thiourea PhNHC(S)NHP(S)(O-
Pri)2, the nearest structure analog of the LH ligand. The
lengths in the thiourea group in complexes 8 and 9 are
practically identical (Table 3). Their values agree well with
the average values of the thiourea CN bond lengths in com-
˚
plex 7 (1.3348 A). The C–N bonds lengths in thiourea frag-
ments of 8 and 9 (in comparison with complex 7) indicate
the strengthening of conjugation between the electronic
pairs of N(12) and N(22) and intracyclic C–N bonds.

F.D. Sokolov et al. / Inorganica Chimica Acta 359 (2006) 2087–2096
2093
In both cases, the N–C–N–P–O moiety exhibits syn,syn
conformation because of H-bonding. The PhNH groups
are bonded by two weak H-bonds of NH–O@P type: first
is the intramolecular bond and the second one is of the
intermolecular type involving P@O group of the neighbor-
ing molecule (Fig. 5, Table 4). Molecules of the chelates 8
and 9 in the crystals form the infinite planar rows along the
a0c plane.
calculations. After that, all the calculations were refined
using all-electron basis set. In order to characterize the nat-
ure of the obtained stationary points (minima or saddle
points), the analytical calculations of the second derivatives
of energy with respect to coordinate (Hessian matrix) have
been performed. For all investigated species, a frequency
analysis has been carried out. All minima have been
checked for the absence of imaginary frequencies. Energies
of the lower-lying excited (singlet) states at the optimal
geometry were computed by single-point time-dependent
density functional theory (TD-DFT) calculation with the
PBE functional and the TZVP0 basis set.
3.4. Theoretical calculations of Ni(II) and Pd(II)
complexes with the PhNHC(S)NHP(O)(OPr-i)2 ligand
Quantum-chemical calculations have been performed
for vacuum using the density functional theory (DFT)
method within the generalized gradient approximation
(GGA) [31] for the exchange-correlation functional of Per-
dew, Burke and Ernzerhof (PBE) [32] as implemented in an
original program package ‘‘Priroda’’ developed by D.N.
Laikov [33]. We used 311-split basis set for main group ele-
ments with one additional polarization p-function for
hydrogen and two additional polarization d-functions for
other elements, referred to as TZVP0. At the first stage,
the fully unconstrained geometry optimization has been
carried out with relativistic Stevens–Basch–Krauss (SBK)
effective core potentials (ECP) [34] optimized for DFT-
Originally, the geometry of the possible isomers, trans-
M[PhNHC(S)NP(O)(OPr-i)2-O,S]2, cis-M[PhNHC(S)NP-
(O)(OPr-i)2-O,S]2, and trans-M[PhNHC(S)NP(O)(OPr-i)2-
N,S]2(MII = NiII, PdII), has been optimized. The values
of the optimized structure energies in the TZVP0 basis
(E) were found to be ꢁ4670.780196, ꢁ4670.781331, and
ꢁ4670.802593 a.u. (Hartree), respectively, for trans-
Ni[PhNHC(S)NP(O)(OPr-i)2-O,S]2, cis-Ni[PhNHC(S)NP-
(O)(OPr-i)2-O,S]2, and trans-Ni[PhNHC(S)NP(O)(OPr-i)2-
N,S]2 as well as ꢁ8102.408273, ꢁ8102.411100, and
ꢁ8102.433021 a.u., respectively, for trans-Pd[PhNHC(S)
NP(O)(OPr-i)2-O,S]2,
cis-Pd[PhNHC(S)NP(O)(OPr-i)2-
O,S]2, and trans-Pd[PhNHC(S)NP(O)(OPr-i)2-N,S]2. Thus,
Fig. 5. Structure of H-bonded chains in the crystal of Ni[L-N,S]2 complex 8.
Table 4
Parameters of hydrogen bonds for 8 and 9 (distances, d (A), and angles (°))
˚
D–Hꢂ ꢂ ꢂA
N(12)–H(12)ꢂ ꢂ ꢂO(11)
N(12)–H(12)ꢂ ꢂ ꢂO(21)a
N(22)–H(22)ꢂ ꢂ ꢂO(21)
N(22)–H(22)ꢂ ꢂ ꢂO(11)a
intramolecular
intramolecular
8
9
8
9
8
9
8
9
d(D–H)
0.93(4)
2.16(4)
2.876(4)
134(3)
83.3(13)
359(4)
0.77(2)
2.29(2)
2.906(2)
137(2)
78.4(7)
359(3)
0.93(4)
2.07(4)
2.856(4)
0.77(2)
2.17(2)
2.824(2)
0.83(3)
2.22(3)
2.854(4)
133(3)
78.7(11)
360(4)
0.80(3)
2.22(3)
2.866(2)
139(2)
78.4(8)
359(3)
0.83(3)
2.21(3)
2.945(4)
0.79(2)
2.25(2)
2.913(2)
d(Hꢂ ꢂ ꢂA)
d(Dꢂ ꢂ ꢂA)
\(DHA)
142(3)
144(2)
148(3)
142(2)
\Aꢂ ꢂ ꢂHꢂ ꢂ ꢂAa
P
H
a
Neighbor molecule.

2094
F.D. Sokolov et al. / Inorganica Chimica Acta 359 (2006) 2087–2096
the optimized forms trans-Ni[PhNHC(S)NP(O)(OPr-i)2-
N,S]2 and trans-Pd[PhNHC(S)NP(O)(OPr-i)2-N,S]2 are
most stable among the above-mentioned isomers of the
Ni(II) and Pd(II) complexes in agreement with the experi-
mental data obtained for 8 and 9. As can be seen from
Table 3, the distances and bond angles computed and
found by X-ray for both trans-Ni[PhNHC(S)NP(O)(OPr-
i)2-N,S]2 and trans-Pd[PhNHC(S)NP(O)(OPr-i)2-N,S]2 are
close to each other. Moreover, use of the ECP basis set
results in very quick convergence to the similar if not better
values than all-electron basis set. As expected, an agree-
ment between the calculated and X-ray data for Ni(II)
complex is much better than that for the Pd(II) complex.
The calculated O11–H12 and O21–H22 distances are
markedly shorter than those found experimentally in the
crystals and this may result from the fact that in isolated
complex molecule there are strong intramolecular hydro-
gen bonds, while there are weak intramolecular and inter-
molecular H-bonds of NHꢂ ꢂ ꢂO@P type in the crystals
(Fig. 6A). We have made the estimation of energetic contri-
bution of two intramolecular NHꢂ ꢂ ꢂO@P hydrogen bonds
by the following computation experiment (basis TZVP0
with ECP). Increasing two torsion angles for the energeti-
cally favorable forms C11–N11–P11–O11 and C21–N21–
P21–O21 (Table 3) up to 60° (Fig. 6B) and constraining
these values for geometry optimization caused loss of
57.3 and 52.9 kJ/mol energy, respectively, for trans-
Ni[PhNHC(S)NP(O)(OPr-i)2-N,S]2 and trans-Pd[PhNHC-
(S)NP(O)(OPr-i)2-N,S]2. Such assumption brings to the
most possible lengthening of two intramolecular
NHꢂ ꢂ ꢂO@P bonds. Hence, the estimated energy of the
hydrogen bonds is at least 25 kJ/mol (per each bond) as
demonstrated by our computational experiment. Further
increasing of the torsion angle values results in the local
minimum of energy due to the formation of two very weak
NHꢂ ꢂ ꢂ(OPr-i)P bonds (Fig. 6C) instead of NHꢂ ꢂ ꢂO@P
bonds.
The calculated energies of the four most intensive sin-
glet-singlet d–d electronic transitions are 15360 cmꢁ1 (kmax
651.0 nm), 17880 cmꢁ1 (kmax 559.3 nm), 18960 cmꢁ1 (kmax
527.4 nm), and 20330 cmꢁ1 (kmax 491.9 nm) for Ni[Ph-
NHC(S)NP(O)(OR)2-N,S]2 as well as 18492 cmꢁ1 (kmax
540.8 nm), 20840 cmꢁ1 (kmax 479.9 nm), 23580 cmꢁ1 (kmax
424.1 nm), and 25440 cmꢁ1 (kmax 393.1 nm) for Pd-
[PhNHC(S)NP(O)(OR)2-N,S]2. In the experimental elec-
tronic absorption spectra of the complex solutions
(Fig. 7), two bands at 615 and 487 nm for Ni[PhNHC(S)N-
P(O)(OPr-i)2-N,S]2 and two ‘‘shoulders’’ at ꢃ440 and
ꢃ390 nm for Pd[PhNHC(S)NP(O)(OPr-i)2-N,S]2 are
observed. High-energy transition in each case can be
assigned to the calculated one, but some of the calculated
transitions have small intensities and are practically unob-
served. Early [35,36] three bands in the absorption specꢁtr1a
of Ni[S2CNEt2-S,S0]2 (at 15900, 19000, and 21000 cm
)
[35] and Ni[PhC(S)NP(S)(OPr-i)2-S,S0]2 (at 16530, 18920,
and 21960 cmꢁ1) [36] were assigned, respectively, to the
1
1
transitions 1A1g ! B1g (dx2ꢁy2 ! dxy), 1A1g ! B3g
1
1
(dxz ! dxy), and A1g ! B1g (dz2 ! dxy) for the local D2h
symmetry. Thus, the calculated energies 15360, 17880,
and 20330 cmꢁ1 for Ni[PhNHC(S)NP(O)(OPr-i)2-N,S]2
with the same D2h symmetry can be related to the
1A1g ! B1g (dx2ꢁy2 ! dxy), A1g ! B3g (dxz! dxy), and
1
1
1
1A1g ! B1g (dz2 ! dxy) transitions, respectively. Similar
1
Ph
H
N
assignment is suitable for the analogous Pd(II) complex 9
(see, for example, Ref. [37]). The above spectral data indi-
cate rather strong crystal field splitting (10 Dq) in the
M[PhNHC(S)NP(O)(OPr-i)2-N,S]2 complexes because
O
A
P
N
S
O
O
Ni
1
1
R
2
energy of the A1g ! B1g (dx2ꢁy2 ! dxy) transition is equal
R
H
Ph
N
O
400
P
N
S
O
B
R
O
Ni
300
2
x0.005
R
200
Ph
H
N
R
O
O
C
100
x0.005
0
P
N
S
R
O
Ni
2
Fig. 6. Intramolecular NHꢂ ꢂ ꢂO hydrogen bonds in trans-M[PhNHC-
(S)NP(O)(OPr-i)2-N,S]2(M = Ni(II); Pd(II)) complexes: (A) NHꢂ ꢂ ꢂO@P
hydrogen bonds in crystal structure, (B) breaking of hydrogen bonds by
increasing the C–N–P@O torsion angles up to 60° (used in DFT
calculation), (C) NHꢂ ꢂ ꢂ(OPr-i)P bonds.
300
400
500
600
700
λ (nm)
Fig. 7. Electronic absorption spectra of the complexes Ni[L-N,S]2 (8)
(solid line) and Pd[L-N,S]2 (9) (dashed line) in CH2Cl2.

F.D. Sokolov et al. / Inorganica Chimica Acta 359 (2006) 2087–2096
2095
to 10 Dq-C (C is an interelectronic repulsion Racah
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plexes M[PhNHC(S)NP(O)(OPr-i)2-N,S]2 (MII = NiII,
PdII) are close to those observed for the NiIIS4 and PdIIS4
cores [37].
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isomer and particularly Pd[PhNHC(S)NP(O)(OPr-i)2-
N,S]2 isomer with low-spin d8 configuration in comparison
to the corresponding M[PhNHC(S)NP(O)(OPr-i)2-O,S]2
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two reasons for the higher stability of the M[PhNHC(S)-
NP(O)(OPr-i)2-N,S]2 isomers relatively to M[PhNHC(S)-
NP(O)(OPr-i)2-O,S]2 isomers (MII = NiII, PdII). One of
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hydrogen bonds. The other reason derives from the depro-
tonated NH group of PhNHCðSÞNPðOÞðOPr-iÞ2ðꢁÞ, which
is a powerful electron donor comparable to the deproto-
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sons: (i) as mentioned above, the steric hindrances associ-
ated with strong distortion of tetrahedral environment of
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Acknowledgements
This work was supported by the Russian Foundation
for Basic Research (Grant Nos. 03-03-32372-a, 03-03-
96225-r2003tatarstan_a), the joint program of CRDF and
the Russian Ministry of Education (BHRE 2004 Y2-C-
07-02), and grant of the Russian Ministry of Education
SPGA (Code A03-2.9-562). Felix Sokolov thanks Faculty
of Chemistry of University of Wroclaw for scholarship.
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