Thiosemicarbazone platinacycles with tertiary phosphines. Preparation of novel heterodinuclear platinum-tungsten complexes

Article abstract of DOI:10.1016/j.poly.2012.04.015

Treatment of thiosemicarbazones (R¹C₆H ₄)C(H)NN(H)C(S)NHR² [R¹,R²: 4-Me,H (a); 4-Me,Me (b); 4-Me,Et (c); 2-Me,H (d); 2-Me,Me (e); 2-Me,Et (f)] with cis-[PtMe₂(cod)] afforded the

Full text of DOI:10.1016/j.poly.2012.04.015

Polyhedron 41 (2012) 30–39
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Thiosemicarbazone platinacycles with tertiary phosphines. Preparation
of novel heterodinuclear platinum–tungsten complexes
Darío Lata a, M. Teresa Pereira a, Juan M. Ortigueira a, Javier Martínez a, Brais Bermúdez a,
Jesús J. Fernández b, José M. Vila a,
⇑
a Departamento de Química Inorgánica, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain
b Departamento de Química Fundamental, Universidad de A Coruña, 15071 A Coruña, Spain
a r t i c l e i n f o
a b s t r a c t
Treatment of thiosemicarbazones (R1C6H4)C(H)@NN(H)C(@S)NHR2 [R1,R2: 4-Me,H (a); 4-Me,Me (b); 4-
Me,Et (c); 2-Me,H (d); 2-Me,Me (e); 2-Me,Et (f)] with cis-[PtMe2(cod)] afforded the tetranuclear plati-
num(II) compounds [Pt{(R1C6H3)C(H)@NN@C(S)NHR2}]4 (1a–1f) with the ligand as terdentate [C,N,S]
after C–H activation and NH deprotonation. The reaction of 1a–1f with PPh3 in 1:4 M ratio gave the
mononuclear compounds [Pt{(R1C6H3)C(H)@NN@C(S)NHR2}(PPh3)] (2a–2f). Treatment of 1a–1f with
large-bite diphosphines Ph2P(CH2)nPPh2 (n = 2, dppe; n = 3, dppp; n = 4, dppb) afforded the dinuclear
Article history:
Received 27 February 2012
Accepted 14 April 2012
Available online 4 May 2012
Keywords:
Platinum
Metallation
compounds [{Pt[(R1C6H3)C(H)@N–N = C(S)NHR2]}2{
l-Ph2P(CH2)nPPh2}], (3a–3f, 4a–4f, 5a–5f), with the
diphosphine in a bridging mode. Similar reactions with the short-bite diphosphines Ph2PCH2PPh2 (dppm)
and Ph2PC(@CH2)PPh2 (vdpp) yielded the mononuclear compounds [Pt{(R1C6H3)C(H)@NN@C(S)NHR2}-
(Ph2PR3PPh2-P)] (R3 = CH2, 6a–6f; R3 = C = CH2, 7a–7f) with the diphosphine in a monodentate coordina-
tion. Treatment of 1a–1f with [W(CO)5(Ph2CH2PPh2)] gave the heterodinuclear species
[{Pt[(R1C6H3)C(H)@NN@C(S)NHR2]}{Ph2CH2PPh2W(CO)5}] (8a–8f). The molecular structures of com-
pounds 3e and 5c have been determined by X-ray crystal structure analysis.
Thiosemicarbazone
Phosphorus ligands
Tungsten
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
new ground, a challenge to be achieved by changing the nature
of the metal, modifying the metallated ligand and/or the ancilliary
The cyclometallation reaction, i.e. the intramolecular activation
of aromatic C–H bonds by transition metals in coordinated ligands,
has been extensively researched, especially in the case of metallat-
ed phenyl rings [1]. The main interest in this type of compounds
stems from their noteworthy applications in organic and organo-
metallic synthesis [2], as active catalysts [3], liquid crystals [4],
for the design of potential biologically active materials [5] or for
their photochemical properties [6]. In particular, platinacycles con-
taining nitrogen, phosphorus or sulfur donor atmos [7] also offer
attractive applications as catalysts in Michael and Diels–Alder
reactions for C–C bond formation [8]. Recently, platinum species
have represented an important class of complexes particularly
from the point of view of their luminescent properties, and the
usage of the phosphorescent complexes as emitters in light-emit-
ting diodes (LEDS) [9]. These findings strongly bring forth the need
to advance in the search for novel complexes which may be suit-
able for any of the above mentioned applications. This enhances
the importance of the processes leading to the design, preparation
and characterization of innovative metallacycles which will break
ligands, or the three altogether. In particular, thiosemicarbazones
and semicarbazones have been known to form stable complexes
with many transition metal ions [10]. Treatment of the appropriate
ligands with Li2[PdCl4] or K2[PtCl4] usually gives chloro-bridged
dinuclear complexes, although mononuclear species with terminal
halogen ligands are also known [11]. Our interest in cyclometallat-
ed compounds has been, in part, focused on the study of complexes
derived from [C,N,S] terdentate ligands such as thiosemicarbazones
or Schiff base ligands with additional sulfur donor atoms, which re-
act readily with M2[PdCl4] (M = Li, K), Pd(OAc)2 or K2[PtCl4] to give
mono- or tetra-nuclear compounds [12]. We have shown that in
thiosemicarbazone palladacycles the organic ligand binds tightly
to the metal as terdentate [C,N,S] in a tetranuclear [13] structure
through M–Schelating and M–Sbridging bonds. The strength of the for-
mer bond is put forward in reactions with nucleophiles, where
even treatment with strong chelating tertiary diphosphines yields
complexes with the ligand in a [C,N,S] fashion and a mono-coordi-
nated diphosphine, to render bidentate [P,S] palladacycle metallo-
ligands: they are starting materials for the preparation of dinuclear
assemblies [14]. Similar cycloplatinated species which were hith-
erto unknown are describe herein, together with heterodinuclear
platinacycles where the second metal binds solely through the
⇑
Corresponding author. Tel.: +34 881814255; fax: +34 981595012.
E-mail address: josemanuel.vila@usc.es (J.M. Vila).
0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.04.015

D. Lata et al. / Polyhedron 41 (2012) 30–39
31
phosphorus atom, as opposed to the [P,S] coordination mode men-
tioned above.
systems, AA0XX0 a–c, and ABCD d–f. Thus, for a–c two apparent
doublets ca. d7.5 and d7.2 were assigned to H2/H6 and H3/H5,
respectively; and for d–f a doublet of doublets ca. d7.6 and a mul-
tiplet ca. d7.3 were assigned to H6 and to H3/H4/H5, also respec-
tively. A singlet ca. d8.0 was assigned to the HC@N resonance in
2. Results and discussion
each case. The IR spectra showed broad
NH groups ca. 3200–3150 cmꢀ1 [16]. Distinctive
(C@S) stretches appeared in the ranges 1608–1593 and 829–
801 cmꢀ1, respectively [17].
Reaction of a–f with [cis-PtMe2(cod)] in refluxing n-octane gave
the cyclometallated complexes [Pt{(4-MeC6H3)C(H)@NN@
m
(N–H) bands due to the
For the convenience of the reader the compounds and reactions
are shown in Scheme 1. The compounds described in this paper
were characterized by elemental analysis (C, H, N, S), and by IR
and 1H, 31P–{1H} and (in part) 13C–{1H} NMR spectroscopy.
Thiosemicarbazones derived from aromatic aldehydes are less
prone to cyclometallation as opposed to the analogous ketone
derivatives, with few examples having been hitherto reported
[15]; to the best of our knowledge the corresponding platinacycles
with short bite diphosphines remained outstanding. We first
sought out to prepare the ligands by the classical condensation
method. Thus, a–f were obtained accordingly as air-stable solids
by the reaction of 4-methylbenzaldehyde or 2-methylbenzalde-
hyde with the compound methyl-thiosemicarbazide or ethyl-thio-
semicarbazide (complexes a and d), as appropriate and were fully
characterized (see Section 4). The ensuing ligands were metallated
in good yield by treatment with [cis-PtMe2(COD)], as opposed to
the K2[PdCl4] salt used in previous preparations; this greatly re-
duces the reaction times.
m
(C@N) and
m
C(S)NHR2}]4, (1a, R = H; 1b, R = Me; 1c, R = Et) and [Pt{(2-
MeC6H3)C(H)@NN@C(S)NHR2}]4, (1d, R = H; 1e, R = Me; 1f,
R = Et), respectively, and as orange air-stable solids, with the ligand
in the Z configuration, which were fully characterized (preparative
details, characterizing microanalytical, mass spectra, IR and 1H
NMR data are in Section 4). The elemental analyses were consistent
with the proposed formulations, but the FAB mass spectra only
showed peaks at low values of m/z, probably due to a fast fragmen-
tation of the compounds. Nevertheless, the electrospray mass spec-
tra showed the corresponding peaks assigned to the molecular ion,
[M+], after consideration of the platinum isotopes, in accordance
with the tetrameric structure [Pt(L-2H)]4 (L-2H: thiosemicarba-
zone ligand after C–H activation and NH deprotonation) [19]. A
similar trend has been observed by us [13,12a] and others [5,18]
for other thiosemicarbazone Pd(II) and Pt(II) cyclometallated
compounds.
The 1H NMR spectra of ligands a and d showed two broad sig-
nals assigned to the NH2 group, ca. d7.20 and d6.40, the higher fre-
quency resonance is attributable to the formation of a hydrogen
bond between this group and the imine nitrogen atom which re-
stricts the rotation of the NH2 group about the C(@S)NH2 bond axis.
In the case of ligands b, c, e and f only one broad signal ca. d7.3 was
detected and assigned to the NHMe or the NHEt resonances. The
aromatic region showed resonances in accordance with 4H spin
The IR data were in agreement with deprotonation of the ligand
at the hydrazynic nitrogen on complex formation [18,19], and also
showed the
m(C@N) band shifted to lower wavenumbers [19a,20],
contrary to the trend for other thiosemicarbazone complexes were
Scheme 1. (i) cis-[PtMe2(cod)], n-octane; (ii) PPh3 (1:4), CHCl3; (iii) Ph2(CH2)nPPh2 (n = 2, 3, 4) (1:2), CHCl3; (iv) Ph2PR3PPh2 (R3 = CH2, C@CH2), (1:4), CHCl3; (v)
[W(CO)5(Ph2PCH2PPh2)], CHCl3; (vi) [W(CO)5(THF)], CHCl3.

32
D. Lata et al. / Polyhedron 41 (2012) 30–39
shift to higher wavenumbers was observed [16]; likewise, the
(C@S) band disappeared in agreement with loss of the double
bond character upon deprotonation of the NH group.
showed two doublets assigned to the two inequivalent phosphorus
nuclei, with the one at lower field showing the platinum satellites,
1J(Pt–P) ca. 3800 Hz, i.e., the coordinated donor. The 1H NMR spec-
tra showed an apparent doublet for the PCH2P resonance (ABXY
spin system); whereas two doublets of doublets ca. d6.9 and d5.9
were assigned to the vinylidene protons. The ‘‘long-bite’’ diphos-
phines failed to give analogous mononuclear species.
Treatment of 1a–1f with [W(CO)5(Ph2PCH2PPh2)] gave the new
heterodinuclear platinacycles [Pt{(R1C6H3)C(H)@NN@C(S)NHR2}
{Ph2PCH2PPh2W(CO)5)}] 8a–8f, which were fully characterized
(see Section 4). The 31P NMR data showed two doublets assigned
to the two non-equivalent phosphorus resonances with the corre-
sponding platinum and tungsten satellites (1J(Pt–P) ca. 3900 Hz
and 1J(W–P) ca. 250 Hz.). The complexes could also be obtained
by treatment of 6a–6f with [W(CO)5(THF)] after stirring in dichlo-
romethane for 2 h, in which case the resonance for the non-coordi-
nated phosphorus nucleus was shifted to higher frequency by ca.
30 ppm. Either way the compounds lack coordination of the second
metal to the sulfur atom, contrary to similar species reported by us
recently where related palladacycles are bidentate-[P,S] [24], thus
further widening the scope of these metalloligands to new homo-
and hetero-bimetallics.
m
The 1H NMR spectra showed absence of the NH resonance, in
agreement with deprotonation as observed in other coordination
and organometallic compounds of similar ligands [18]. A singlet
signal in the range d7.28–8.17 was assigned to the HC@N reso-
nance. Metallation of the ligands was clear from the absence of
the 4H spin system of the unsubstituted phenyl ring; accordingly,
for 1a–1c two doublets and one singlet were assigned to the H2, H3
and H5 resonances, respectively, and for 1d–1f two doublets and
one triplet were assigned to the H3, H5 and H4 resonances, also
respectively (see Section 4). The NH2, NHMe and NHEt moieties
gave rise to a broad signal shifted to higher field by ca.1.5–
2.5 ppm. Coupling of the HC@N and H5 resonances with the 195Pt
nucleus was observed in some cases, following the trend shown
in related cycloplatinated complexes [21].
2.1. Reactivity of the complexes
Treatment of 1a–1f with tertiary phosphines produced opening
of the tetranuclear structure with cleavage of the Pt–Sbridging bond,
in a similar fashion as observed in the related cyclometallated thi-
osemicarbazone Pd4 cluster complexes [13].
2.2. Molecular and crystal structures 3e and 5c
Thus, the reaction of 1a–1f with PPh3 in 1:4 M ratio or with
‘‘long-bite’’ diphosphines Ph2P(CH2)nPPh2 (n = 2–4) in 1:2 M ratio,
gave the mononuclear [{Pt[(R1C6H3)C(H)@NN@C(S)NHR2]}(PPh3)]
Suitable crystals were grown by slowly concentrating a deuter-
ated chloroform solution of the complexes. The molecular struc-
tures are illustrated in Figs. 1 (3e) and 3 (5c). Crystal data and
selected bond lengths and angles with estimated standard devia-
tions are given in Tables 1 and 2.
The asymmetric unit comprises in both cases one half molecule
of the corresponding complex with an inversion centre located on
the middle point of the methylene chain of the diphosphine ligand
and one molecule of CDCl3. The structure consists of dinuclear mol-
ecules in which two cyclometallated moieties are bridged by a
dppe (3e) or a dppb (5c) ligand. The platinum atoms are coordi-
nated four different donors, a terdentate thiosemicarbazone ligand
through the ortho-carbon atom of the phenyl ring, C(1), the imine
N(1) atom, the S(1) sulfur atom, and to the P(1) phosphorus atom
of the coordinated diphosphine in a slightly distorted square-pla-
nar geometry.
(2a–2f) or dinuclear [{Pt[(R1C6H3)C(Me)@NN@C(S)NHR2]}2{
l-
Ph2P(CH2)nPPh2}] (n = 2, 3a–3f; n = 3, 4a–4f; n = 4, 5a–5f) com-
plexes, respectively (see Scheme 1), as pure air-stable solids, which
were fully characterized (see Section 4). Treatment of the starting
material with excess diphosphine did not yield compounds with
the latter ligand in a chelating mode, and uncoordinated phosphine
was recovered, as opposed to the behavior of related cyclometallat-
ed complexes derived from [C,N,S] terdentate Schiff base ligands
[12b] and semicarbazones [22], where the M–Schelating and M–Oche-
bonds, respectively, were easily cleaved.
lating
The 31P–{1H} NMR spectra showed a singlet, downfield shifted
from its position in the free ligand (see Section 4), in accordance
with phosphorus coordination to the platinum atom, in a phospho-
rus trans to nitrogen disposition [23] with 1J(Pt–P) ca. 3800 Hz. For
the dinuclear compounds, 3a–5f, the singlet resonance was indic-
ative of equivalent phosphorus environments, thus pointing to-
wards a symmetric nature of the complexes. This was confirmed
by the existence of only one set of signals in the 1H NMR spectra
for the two equivalent cyclopalatinated moieties. The 1H NMR
spectra showed the H5 proton resonance shifted to lower frequen-
cies by ca. 1.0 ppm, as a result of the shielding effect of the phos-
The angles between adjacent atoms in the coordination sphere
of the platinum atom are close to the expected value of 90°, with
the most noticeable strain in the somewhat reduced ‘‘bite’’ angle
of the metallated moiety consequent upon double C,N and N,S
phine phenyl rings in agreement with
a trans P to N
arrangement; satellites for the H5 and HC@N resonances from cou-
pling to the platinum nucleus could be assigned with 4J(PtH5) and
3J(PtH) ca. 50 and 70 Hz, respectively.
Reaction of 1a–1f with the short-bite diphosphines
Ph2PCH2PPh2 (dppm) and Ph2PC(@CH2)PPh2 (vdpp) yielded the
mononuclear
compounds
[Pt{(R1C6H3)C(H)@NN@C(S)NHR2}
(Ph2PR3PPh2-P)] (R3 = CH2, 6a–6f; R3 = CCH2, 7a–7f) as air-stable
solids. Characteristic microanalytical and spectroscopic data are gi-
ven in Section 4. Even when excess diphosphine was used, only
cleavage of the Pt–Sbridging bonds was produced, and contrary to
the case with the ‘‘long-bite diphosphines’’, species with coordina-
tion of the phosphine to the metal atom only through one phos-
phorus atom were obtained; also, excess phosphine did not yield
the ligand in the chelating mode and splitting the Pd–Schelating bond
was not achieved in any case; in the present complexes the
strength of the Pd–Schelating bond prevents the chelating mode of
the diphosphine ligand [12a,13]. The 31P–{1H} NMR spectra
Fig. 1. Molecular structure of complex 3e, with labelling scheme. Hydrogen atoms
have been omitted for clarity.

D. Lata et al. / Polyhedron 41 (2012) 30–39
33
Table 1
Crystal data and structure refinement data for compounds 3e and 5c.
3e
5c
Empirical formula
Formula weight
Temperature
Crystal system
Space group
Unit cell dimensions
a (Å)
C
48H48Cl6N6P2Pt2S2
C52H56Cl6N6P2Pt2S2
1493.97
293(2)
1437.86
293(2)
triclinic
triclinic
ꢀ
ꢀ
P1
P1
10.713(5)
11.715(5)
12.026(5)
87.636(5)
64.652(5)
77.976(5)
1332.1(10)
1
10.419(2)
11.813(3)
13.165(3)
78.741(4)
73.605(4)
69.634(4)
1448.8(6)
2
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
Volume (Å3)
Z
DCalc (mg/m3)
1.790
5.724
696
1.710
5.267
728
Absorption coefficient (mmꢀ1
F(000)
)
Crystal size (mm3)
h range for data collection (°)
Index ranges
0.36 ꢂ 0.21 ꢂ 0.16
0.37 ꢂ 0.30 ꢂ 0.17
Fig. 2. Hydrogen bond interactions in complex 3e. The involved atoms have been
labelled.
1.78–26.40
1.62–26.41
ꢀ11/h/13, ꢀ14/k/14, ꢀ12/h/13, ꢀ14/k/14,
0/l/15
0/l/16
Reflections collected
Independent reflections
Maximum and minimum
transmission
15173
5434 (0.026)
0.415 and 0.210
16376
5899 (0.0347)
0.2381 and 0.246
Goodness-of-fit on F2
Final R indices
1.072
1.047
R1 = 0.0290
wR2 = 0.0834
1.699 and ꢀ1.238
R1 = 0.0335
wR2 = 0.0863
1.193 and ꢀ1.518
wR2 (all data)
Largest difference in peak and
hole (eÅꢀ3
)
planes are as follows: 1/2: 2.02° (3e) and 0.90° (5c); 2/3: 1.47°
(3e) and 1.01° (5c).
The structure of complex 3e shows intermolecular hydrogen
bonding between the NHMe hydrogen atom and the sulfur atom
with the following distances: N(3)ꢁ ꢁ ꢁS(1)#1 3.452 Å and
H(3)ꢁ ꢁ ꢁS(1)#1 2.970 Å, and with an angle N(3)–H(3)ꢁ ꢁ ꢁS(1)#1 of
117.42° (Fig. 2).
Fig. 3. Molecular structure of complex 5c, with labelling scheme. Hydrogen atoms
have been omitted for clarity.
Table 2
Selected bond distances (Å) and angles (°) for 3e and 5c.
3e
5c
chelation: the requirements of the five-membered rings force the
bond angles N(1)–Pt(1)–C(1) and N(1)–Pt(1)–S(1) to 80.8(2)° and
82.3(1)°, respectively (3e), and N(1)–Pt(1)–C(1) and N(1)–Pt(1)–
S(1) to 81.4(2)° and 81.8(1)°, also respectively (5c). The sum of
the angles around the platinum atoms is ca. 360°. The Pt–N bond
lengths in the metallacycle (2.025(4) Å, 3e; 2.040(4) Å, 5c are long-
er than the predicted single bond value of 1.981 Å, based on the
sum of covalent radii for nitrogen(sp2) and platinum, 0.701 and
1.28 Å, respectively [25] and reflect the trans influence of the phos-
phorus atom [21]. The shorter than expected Pt–P bond lengths
(2.226(1) Å, 3e; 2.235(1) Å, 5c) suggest partial multiple-bond char-
acter [26,27]. The S(1)–C(9) (1.760(5) Å, 3e; 1.773(6) Å, 5c) and
N(2)–C(9) (1.291(7) Å, 3e; 1.291(7) Å, 5c) distances in the cyclo-
metallated ring are consistent with increased single- and double-
bond character, respectively, in the deprotonated form of the thio-
semicarbazone ligand.
Pt(1)–C(1)
Pt(1)–N(1)
Pt(1)–S(1)
Pt(1)–P(1)
C(7)–C(1)
C(7)–C(8)
N(1)–C(8)
N(1)–N(2)
2.046(5)
2.025(4)
2.322(1)
2.2260(1)
1.417(7)
1.454(7)
1.288(6)
1.380(5)
1.302(7)
1.760(5)
1.839(5)
80.8(2)
2.047(6)
2.040(4)
2.331(2)
2.235(1)
1.425(8)
1.431(8)
1.300(7)
1.370(6)
1.291(7)
1.773(6)
1.839(5)
81.4(2)
N(2)–C(9)
S(1)–C(9)
P(1)–C(12)
N(1)–Pt(1)–C(1)
N(1)–Pt(1)–S(1)
P(1)–Pt(1)–S(1)
C(1)–Pt(1)–P(1)
N(1)–Pt(1)–P(1)
C(1)–Pt(1)–S(1)
C(7)–C(1)–Pt(1)
C(1)–C(7)–C(8)
N(1)–C(8)–C(7)
C(8)–N(1)–Pt(1)
N(2)–N(1)–Pt(1)
C(9)–N(2)–N(1)
N(2)–C(9)–S(1)
C(9)–S(1)–Pt(1)
82.3(1)
98.74(5)
98.1(2)
81.8(1)
100.90(5)
95.9(2)
177.3(1)
163.08(2)
111.0(4)
115.4(4)
116.4(4)
116.32(3)
124.1(3)
111.7(4)
126.8(4)
95.05(17)
175.6(1)
163.2(2)
109.9(4)
116.8(5)
117.0(5)
114.8(4)
124.5(3)
112.0(5)
126.7(5)
95.0(2)
The cyclometallated moieties are almost co-planar. The mean
deviations from the least squares planes determined for the metal-
lated phenyl ring (plane 1) the cyclometallated ring (plane 2) and
the N,S coordination ring (plane 3) are 0.0039, 0.0096 and
0.0013, respectively, for complex 3e; and 0.0056, 0.0166 and
0.0053, also respectively, for complex 5c. The angles between

34
D. Lata et al. / Polyhedron 41 (2012) 30–39
ppm, J Hz): 9.81 (s, NH); 7.84 (s, HC@N); 7.52 (m, H2, H6,
3. Conclusions
N = 7.6), 7.42 (b, NHEt); 7.19 (m, H3, H5 N = 7.6); 3.76 (m,
NCH2Me); 2.38 (s, 4-Me); 1.32 (t, NCH2Me, 3J(HH) 9.0). 13C NMR
(CDCl3, d ppm, J Hz): 177.34 (s, CC@S); 143.12 (s, CC@N); 141.26 (s,
C1); 130.96 (s, C4); 129.96 (s, C3,C5); 127.69 (s, C2,C6); 39.75 (s,
NCH2Me); 21.95 (s, 4-Me); 14.97 (s, NCH2Me).
In summary, we have shown thiosemicarbazones can be metal-
lated yielding tetranuclear complexes, which readily react with
tertiary phosphines to give mono- and di-nuclear platinacycles.
The compounds with monodentate diphosphine are metalloligand
precursors for preparing heterodinuclear species where the second
metal binds solely through the phosphorus atom, as opposed to
analogous [P,S] bonded complexes. Further studies are in progress
to deal with the potential applications of the reported complexes
and shall be reported in future articles.
4.5. 2-MeC6H4C(H)@NN(H)C(@S)NH2 (d)
Yield: 94%. Anal. Calc. for C9H11N3S (193.3 g/mol): C, 55.9; H,
5.7; N, 21.7; S, 16.6. Found: C, 55.5; H, 5.8; N, 21.5; S, 16.7%. IR
m
max/cmꢀ1 (C@S) 826w. 1H NMR (CDCl3, d ppm,
: m (C@N) 1593s, m
J Hz): 9.86 (b, NH); 8.22 (s, HC@N); 7.78 (dd, H6, 4J(H4H6) 1.6;
3J(H5H6) 7.8); 7.31 (m, H3, H4, H5); 7.10, 6.45 (b, NH2); 2.51 (s,
2-Me). 13C NMR (CDCl3, d ppm, J Hz): 178.77 (s, CC@S); 143.39 (s,
4. Experimental
4.1. Materials and instrumentation
CC@N); 137.98 (s, C1); 131.36 (s, C4); 130.94 (s, C3, C5); 127.31
(s, C2, C6); 20.26 (s, 2-Me).
All solvents were distilled prior to use from appropriate drying
agents [28]. Chemicals were used as supplied from commercial
sources. Microanalyses were carried out at the Servicio de Análisis
Elemental at the University of Santiago, with a Carlo-Erba Elemen-
tal Analyser 1108. IR spectra were recorded as KBr pellets or Nujol
mulls with a Perkin-Elmer 1330 and with a Mattson spectropho-
tometers. NMR spectra were obtained as CDCl3 solutions and refer-
4.6. 2-MeC6H4C(H)@NN(H)C(@S)NHMe (e)
Yield: 93%. Anal. Calc. for C10H13N3S (207.3 g/mol): C, 57.9; H,
6.3; N, 20.3; S, 15.5. Found: C, 58.1; H, 6.4; N, 20.0; S, 15.3%. IR
m
max/cmꢀ1
: m (C@N) 1608w, m (C@S) 801w.
1H NMR (CDCl3, d ppm, J Hz): 9.76 (s, NH); 8.15 (s, HC@N); 7.76
enced to SiMe4 (1H, 13C–{1H}) or 85% H3PO4
(
31P–{1H}); and were
Bruker WM250 and AMX 300 spectrometers
(d, H6, 4J(H4H6) 1.5; 3J(H5H6) 7,4); 7.42 (b NHMe); 7.24 (m, H3,
recorded on
a
H4, H5); 2.46 (s, 2-Me). 13C NMR (CDCl3, d ppm, J Hz): 178.60 (s,
(200.0 MHz for 1H, 50.3 MHz for 13C–{1H}, 81.0 MHz for 31P–
{1H}). All chemical shifts are reported downfield from standards.
The FAB mass spectra were recorded with a Fisons Quatro mass
spectrometer with a Cs ion gun; 3-nitrobenzyl alcohol was used
as the matrix.
CC@S); 141.89 (s, CC@N); 137.75 (s, C1); 131.77 (s, C4); 131.49 (s,
C3, C5); 126.87 (s, C2, C6); 31.59 (s, NMe); 20.14 (s, 2-Me).
4.7. 2-MeC6H4C(H)@NN(H)C(@S)NHEt (f)
Yield: 95%. Anal. Calc. for C11H15N3S (221.3 g/mol): C, 59.7; H,
4.2. Preparation of 4-MeC6H4C(H)@NN(H)C(@S)NH2 (a)
6.8; N, 19.0; S, 14.5. Found: C, 59.4; H, 6.8; N, 18.9; S, 14.2%. IR
m
max/cmꢀ1 (C@S) 802b. 1H NMR (CDCl3, d
: m (C@N) 1592w, m
To a solution of thiosemicarbazide (0.500 g, 5.486 mmol) in
water (25 cm3) and 0.65 cm3 of hydrochloric acid, 4-methylbenzal-
dehyde (0.626 g, 5.211 mmol) was added. The resulting mixture
was stirred for 15 m at room temperature. The white solid formed
was filtered off, washed with water, dried in vacuo and recrystal-
lized from ethanol.
ppm, J Hz): 9.61 (s, NH); 8.13 (s, HC@N); 7.75 (d, H6, 3J(H5H6)
7,4); 7.40 (b, NHEt); 7.27 (m, H3, H4, H5); 2.50 (s, 2-Me). 13C
NMR (CDCl3, d ppm, J Hz): 177.45 (s, CC@S); 141.86 (s, CC@N);
137.72 (s, C1); 131.80 (s, C4); 131.50 (s, C3, C5); 126.97 (s, C2,
C6); 39.77 (s, NCH2Me); 20.19 (s, 2-Me); 14.93 (s, NCH2Me).
Yield: 92%. Anal. Calc. for C9H11N3S (193.30 g/mol): C, 55.9; H,
5.7; N, 21.7; S, 16.6. Found: C, 55.6; H, 5.8; N, 21.5; S, 16.6%. IR
m
J Hz): 9.89 (s, NH); 7.88 (s, HC@N); 6.45 (b, NH2); 7.53 (m, H2,
H6, N = 7.8), 7.30 (b, NH2); 7.20 (m, H3, H5, N = 7.7); 2.38 (s, 4-
Me). 13C NMR (CDCl3, d ppm, J Hz): 178.55 (s, C@S); 144.86 (s,
C@N); 141.72 (s, C1); 130.02 (s, C3, C5); 130.59 (s, C4); 127.26 (s,
C2, C6); 21.98 (s, 4-Me).
4.8. Preparation of [Pt{4-MeC6H3C(H)@NN@C(S)NH2}]4 (1a)
max/cmꢀ1: (C@N) 1600s, (C@S) 829w. 1H NMR (CDCl3, d ppm,
Ligand a (128 mg, 0.660 mmol) and [cis-PtMe2(cod)] (200 mg,
0.600 mmol) were refluxed in anhydrous n-octane (25 cm3) for
2 h under nitrogen. After cooling to room temperature, the orange
solid formed was filtered and dried in vacuo.
Yield: 70%. Anal.Calc. for C36H36N12S4Pt4C8H18 (1659.60 g/mol):
C, 31.8; H, 3.3; N, 10.2; S, 7.8. Found: C, 31.5; H, 3.6; N, 10.5; S, 8.0%.
Ligands b–f were prepared similarly.
IR m : m (C@N) 1584s, m
max/cmꢀ1 (C@S) 809b. 1H NMR (CDCl3, d ppm,
J Hz): 7.92 (s, HC@N); 7.50 (d, H2, 3J(H2H3) 8.2); 7.14 (d, H3); 6.55
(s, H5); 5.07 (s, NH2); 2.32 (s, 4-Me). ESI-MS: m/z = 1545 [M]+.
Compounds 1b–1f were prepared analogously.
4.3. 4-MeC6H4C(H)@NN(H)C(@S)NHMe (b)
Yield: 95%. Anal. Calc. for C10H13N3S (207.3 g/mol): C, 57.9; H,
6.3; N, 20.3; S, 15.5. Found: C, 57.9; H, 6.4; N, 20.1; S, 15.3%. IR
m
4.9. [Pt{4-MeC6H3C(H)@NN@C(S)NHMe}]4 (1b)
max/cmꢀ1 (C@S) 811 m. 1H NMR (CDCl3, d
: m(C@N) 1608w, m
ppm, J Hz): 9.72 (s, NH); 7.85 (s, HC@N); 7.51 (b, NHMe); 7.57
(m, H2, H6, N = 7.5), 7.23 (m, H3, H5, N = 7.6); 3.29 (b, NHMe);
2.32 (s, 4-Me). 13C NMR (CDCl3, d ppm, J Hz): 178.54 (s, CC@S);
143.07 (s, CC@N); 141.31 (s, C1); 130.89 (s, C4); 129.98 (s, C3,
C5); 127.68 (s, C2, C6); 31.57 (s, NHMe); 21.95 (s, 4-Me).
Yield: 80%. Anal. Calc. for C40H44N12S4Pt4 (1601.40 g/mol): C,
30.0; H, 2.8; N, 10.5; S, 8.1. Found: C, 30.3; H, 3.0; N, 10.7; S,
7.9%. IR m : m (C@N) 1585s, m
max/cmꢀ1 (C@S) 797w. 1H NMR (CDCl3,
d ppm, J Hz): 8.00 (s, HC@N); 7.64 (d, H2, 3J(H2H3) 7.5); 7.09 (d,
H3); 6.73 (s, H5); 4.81 (s, NHMe); 2.78 (s, NHMe); 2.19 (s, 2-Me).
ESI-MS: m/z = 1600 [M]+.
4.4. 4-MeC6H4C(H)@NN(H)C(@S)NHEt (c)
4.10. [Pt{4-MeC6H3C(H)@NN@C(S)NHEt}]4 (1c)
Yield:>95%. Anal. Calc. for C11H15N3S (221.3 g/mol) C, 59.7; H,
6.8; N, 18.9; S, 14.5. Found: C, 59.5; H, 6.8; N, 18.7; S, 14.7%. IR
Yield: 72%. Anal. Calc. for C44H52N12S4Pt4 (1657.50 g/mol): C,
31.9; H, 3.2; N, 10.1; S, 7.7. Found: C, 31.9; H, 3.3; N, 10.1; S,
m
max/cmꢀ1
:
m
(C@N) 1606w,
m
(C@S) 809 m. 1H NMR (CDCl3, d

D. Lata et al. / Polyhedron 41 (2012) 30–39
35
7.9%. IR
m
max/cmꢀ1
:
m
(C@N) 1584s,
m
(C@S) 798w. 1H NMR (CDCl3, d
3J(H2H3) 7.4); 6.61 (d, H3); 6.09 (s, H5, 3J(PtH5) 47.4); 4.69 (b,
NHEt); 3.36 (m, NCH2Me); 1.75 (s, 4-Me)ß 1.10 (t, NCH2Me,
ppm, J Hz): 7.28 (s, HC@N, 3J(PtH) 49.6); 6.72 (d, H2, 3J(H2H3) 7.5);
6,66 (d, H3); 6.59 (s, H5, 3J(PtH5) 98.9); 5.09 (t, NHEt, 3J(NHCH2)
5.5); 3.42 (m, NCH2Me); 2.28 (s, 4-Me)ß 1.18 (t, NCH2Me, 3J(HH)
9.3). 13C NMR (CDCl3, d ppm, J Hz): 164.3 (s, CC@S); 162.09 (s, CC@N);
145.48 (s, C1); 139.64 (s, C6); 132.21 (s, C4); 127.92 (s, C2); 124.02,
121.51 (s, C3, C5); 41.71 (s, NCH2Me); 22.31 (s, 4-Me); 15.22 (s,
NCH2Me). ESI-MS: m/z = 1657 [M]+.
3J(HH) 9.1).31P–{1H} NMR (CDCl3,
1J(PtP) = 3859.0).
d ppm, J Hz): 20.02 (s,
4.17. [Pt{2-MeC6H3C(H)@NN@C(S)NH2}(PPh3)] (2d)
Yield: 58%. Anal.Calc. for C27H24N3PSPt (648.6 g/mol): C, 50.0; H,
3.7; N, 6.5; S, 4.9. Found: C, 50.3; H, 3.9; N, 6.6; S, 4.5%. IR mmax
/
4.11. Preparation of [Pt{2-MeC6H3C(H)@NN@C(S)NH2}]4 (1d)
cmꢀ1 (C@S) 784w. 1H NMR (CDCl3, d ppm,
: m (C@N) 1584 m, m
J Hz): 8.00 (d, HC@N, 4J(PH) 7.9, 4J(PtH) 74.8); 6.56 (d, H3,
3J(H3H4) 7.4); 6.40 (t, H4, 3J(H4H5) 7.4); 6.15 (s, H5, 3J(PtH5)
48.4); 5.02 (s, NH2); 2.35 (s, 2-Me). 31P–{1H} NMR (CDCl3, d ppm,
J Hz): 20.77 (s, 1J(PtP) = 3875.8).
Yield: 68%. Anal.Calc. for C36H36N12S4Pt4C8H18 (1660.00 g/mol):
C, 31.8; H, 3.3; N, 10.1; S, 7.7. Found: C, 31.9; H, 3.5; N, 10.0; S, 7.8%.
IR m : m
max/cmꢀ1 (C@N) 1565sh. 1H NMR (CDCl3, d ppm, J Hz): 8.17
(s, HC@N); 7.67 (d, H3, 3J(H3H4) 7.5); 6.84 (t, H4, 3J(H4H5) 7.5);
6.61 (d, H5); 5.06 (s, NH2); 2.41 (s, 2-Me). ESI-MS: m/z = 1544 [M]+.
4.18. [Pt{2-MeC6H3C(H)@NN@C(S)NHMe}(PPh3)] (2e)
4.12. [Pt{2-MeC6H3C(H)@NN@C(S)NHMe}]4 (1e)
Yield: 27%. Anal. Calc. for C28H26N3PSPt (662.6 g/mol): C, 51.5;
Yield: 84%. Anal. Calc. for C40H44N12S4Pt4 (1601.40 g/mol): C,
H, 4.2; N, 6.2; S, 4.7. Found: C, 51.4; H, 4.1; N, 6.3; S, 4.6%. IR
30.0; H, 2.8; N, 10.5; S, 8.1. Found: C, 30.1; H, 2.7; N, 10.7; S,
m
max/cmꢀ1 (C@N) 1585w. 1H NMR (CDCl3, d ppm, J Hz): 8.13
: m
10.7%. IR
m : m
max/cmꢀ1 (C@N) 1584 m. 1H NMR (CDCl3, d ppm,
(d, HC@N, 4J(PH) 8.4, 3J(PtH) 67.4); 6.57 (d, H3, 3J(H3H4) 7.4);
6.41 (t, H4, 3J(H4H5) 7.4); 6.17 (s, H5, 3J(PtH5) 46.4); 4.76 (s,
NHMe); 2.95 (b, NMe); 2.37 (s, 2-Me). 31P–{1H} NMR (CDCl3, d
ppm, J Hz): 20.30 (s, 1J(PtP) = 3865.6).
J Hz): 8.10 (s, HC@N); 7.70 (d, H3, 3J(H3H4) 8.0); 6.90 (t, H4,
3J(H4H5) 7.5); 6.70 (d, H5); 4.65 (s, NHMe); 2.85 (s, NHMe); 2.10
(s, 2-Me). ESI-MS: m/z = 1600 [M]+.
4.13. [Pt{2-MeC6H3C(H)@NN@C(S)NHEt}]4 (1f)
4.19. [Pt{2-MeC6H3C(H)@NN@C(S)NHEt}(PPh3)] (2f)
Yield: 77%. Anal. Calc. for C44H52N12S4Pt4 (1657.50 g/mol): C,
31.9; H, 3.2; N, 10.1; S, 7.7. Found: C, 32.0; H, 3.5; N, 10.3; S,
7.8%. 1H NMR (CDCl3, d ppm, J Hz): 8.17 (s, HC@N); 7.82 (d, H3,
3J(H3H4) 7.7); 6.97 (t, H4, 3J(H4H5) 7.7); 6.61 (d, H5); 4.65 (s,
NHMe); 3.40 (m, NCH2Me); 1.21 (b, NCH2Me). ESI-MS: m/z = 1657
[M]+.
Yield: 31%. Anal. Calc. for C29H28N3PSPt (676.7 g/mol): C, 51.5;
H, 4.2; N, 5.6; S, 5.7. Found: C, 51.4; H, 4.4; N, 5.9; S, 5.5%. IR
m
max/cmꢀ1 (C@S) 804b. 1H NMR (CDCl3, d
: m (C@N) 1586w, m
ppm, J Hz): 8.11 (d, HC@N, 4J(PH) 8.4, 3J(PtH) 73.6,); 6.56 (d, H3,
3J(H3H4) 7.4); 6.40 (t, H4, 3J(H4H5) 7.4); 6.17 (d, H5, 3J(PtH5)
52.4); 4.71(b, NHEt); 3.36 (m, NCH2Me); 2.38 (s, 2-Me)ß 1.12 (t,
NCH2Me, 3J(HH) 9.0). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 20.19
(s, 1J(PtP) = 3865.6).
4.14. Preparation of [Pt{4-MeC6H3C(H)@NN@C(S)NH2}(PPh3)] (2a)
Compound 1a (20 mg, 0.013 mmol) and PPh3 (14 mg,
0.053 mmol) were added in chloroform (10 cm3) in a complex/
phosphine 1:4 M ratio. The resulting mixture was heated under
nitrogen for 10 min. The solvent was removed under reduced pres-
sure and the residue recrystallized from chloroform/n-hexane.
Yield: 75%. Anal. Calc. for C27H24N3PSPt (648.6 g/mol): C, 47.9; H,
4.20. Preparation of [{Pt[4-MeC6H3C(H)@NN@C(S)NH2]}2
{l
-Ph2P(CH2)2PPh2}] (3a)
To a suspension of 1a (20 mg, 0.017 mmol) in chloroform
(10 cm3) 1,2-bis(diphenylphosphino)ethane (13 mg, 0.033 mmol)
was added and the resulting mixture was heated under nitrogen
for 10 min. The solvent was removed at reduced pressure and
the residue recrystallized from chloroform/n-hexane.
3.7; N, 6.4; S, 4.9. Found: C, 48.1; H, 3.9; N, 6.3; S, 5.1%. IR mmax
/
cmꢀ1 (C@S) 806w. 1H NMR (CDCl3, d ppm,
: m (C@N) 1583s, m
J Hz): 7.54 (d, HC@N, 4J(PH) 8.1), 6.92 (d, H2, 3J(H2H3) 7,4); 6.61
(d, H3); 6.08 (s, H5, 3J(PtH5) 46.4); 5.02 (s, NH2); 1.75 (s, 4-Me).
31P–{1H} NMR (CDCl3, d ppm, J Hz): 19.91 (s, 1J(PtP) = 3870.0).
Compounds 2b–2f were prepared in a similar manner.
Yield: 55%. Anal. Calc. for C44H42N6P2S2Pt2 (1157.1 g/mol): C,
44.6; H, 3.6; N, 7.3; S, 5.5. Found: C, 44.8; H, 4.0; N, 7.5; S, 5.7%.
IR m : m (C@N) 1585 m, m
max/cmꢀ1 (C@S) 820w. 1H NMR (CDCl3, d
ppm, J Hz): 6.92 (d, H2, 3J(H2H3) 7,4); 6.63 (d, H3); 6.09 (b, H5);
5.09 (b, NH2); 2.33 (s, 4-Me). 31P–{1H} NMR (CDCl3, d ppm, J Hz):
44.06 (s, 1J(PtP) = 3000.9).
4.15. [Pt{4-MeC6H3C(H)@NN@C(S)NHMe}(PPh3)] (2b)
Yield: 49%. Anal.Calc. for C28H26N3PSPt (662.6 g/mol): C, 50.0; H,
Compounds 3b–3f, 4b–4f and 5b–5f were prepared in a similar
manner, using the appropriate diphosphine.
3.7; N, 6.5; S, 4.9. Found: C, 50.1; H, 4.0; N, 6.8; S, 5.1%. IR mmax
/
cmꢀ1 (C@S) 801w. 1H NMR (CDCl3, d ppm,
: m (C@N) 1580s, m
J Hz): 7.77 (d, HC@N, 4J(PH) 8.4, 4J(PtHi) 66.6); 6.93 (d, H2,
3J(H2H3) 7,4); 6.62 (d, H3); 6.09 (s, H5, 4J(PtH5) 45.8); 4.72 (b,
NHMe); 2.93 (b, NMe); 1.75 (s, 4-Me). 31P–{1H} NMR (CDCl3, d
ppm, J Hz): 19.91 (s, 1J(PtP) = 3865.6).
4.21. [{Pt[4-MeC6H3C(H)@NN@C(S)NHMe]}2
{l
-Ph2P(CH2)2PPh2}] (3b)
Yield: 82%. Anal. Calc. for C46H46N6P2S2Pt2 (1199.1 g/mol): C,
4.16. [Pt{4-MeC6H3C(H)@NN@C(S)NHEt}(PPh3)] (2c)
46.0; H, 3.8; N, 7.0; S, 5.3. Found: C, 45.7; H, 3.7; N, 6.7; S, 4.9%.
IR m : m (C@N) 1581m, m
max/cmꢀ1 (C@S) 812b. 1H NMR (CDCl3, d
Yield: 88%. Anal. Calc. for C29H28N3PSPt (676.7 g/mol): C, 51.5;
ppm, J Hz): 7.78 (d, HC@N, 4J(PH) 7.4); 6.93 (d, H2, 3J(H2H3) 7.4);
6.62 (d, H3); 6.03 (s, H5, 3J(PtH5) 46.3); 4.80 (b, NHMe); 3.00 (b,
NMe); 2.17 (b, PCH2); 1.74 (s, 4-Me). 31P–{1H} NMR (CDCl3, d
ppm, J Hz): 15.24 (s, 1J(PtP) = 3819.8).
H, 4.2; N, 6.2; S, 4.7. Found: C, 51.9; H, 4.4; N, 6.4; S, 4.5%. IR
m
max/cmꢀ1
:
m
(C@N) 1582 m,
m
(C@S) 806b. 1H NMR (CDCl3, d
ppm, J Hz): 7.76 (d, HC@N, 4J(PH) 7.9, 3J(PtH) 69.4); 6.93 (d, H2,

36
D. Lata et al. / Polyhedron 41 (2012) 30–39
4.22. [{Pt[4-MeC6H3C(H)@NN@C(S)NHEt]}2{
l
-Ph2P(CH2)2PPh2}] (3c)
ppm, J Hz): 7.78 (d, HC@N, 4J(PH) 7.9); 6.91 (d, H2, 3J(H2H3) 7.4);
6.62 (d, H3); 6.10 (s, H5, 3J(PtH5) 45.4); 4.77 (b, NHEt); 1.81 (s,
4-Me)ß 2.80 (m, NCH2Me); 2.70, 2.28 (b, PCH2CH2CH2P); 1.17 (t,
NCH2Me, 3J(HH) 9.2). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 10.35
(s, 1J(PtP) = 3779.0).
Yield: 90%. Anal. Calc for C48H50N6P2S2Pt2 (1227.2 g/mol): C,
47.0; H, 4.1; N, 6.8; S, 5.2. Found: C, 47.1; H, 4.3; N, 6.7; S, 5.5%.
IR m : m (C@N) 1582m, m
max/cmꢀ1 (C@S) 806b. 1H NMR (CDCl3, d
ppm, J Hz): 7.78 (d, HC@N, 4J(PH) 7.9, 3J(PtH) 45.4,); 6.91 (d, H2,
3J(H2H3) 7.4); 6.62 (d, H3); 6.10 (s, H5, 3J(PtH) 45.4); 4.77 (b,
NHEt); 3.80 (m, NCH2Me); 3.04 (b, PCH2); 1.81 (s, 4-Me); 1.17 (t,
NCH2Me, 3J(HH) 9.3). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 15.17
(s, 1J(PtP) = 3820.0).
4.29. [{Pt[2-MeC6H3C(H)@NN@C(S)NH2]}2{l-Ph2P(CH2)3PPh2}] (4d)
Yield: 84%. Anal. Calc. for C45H44N6P2S2Pt2 (1185.1 g/mol): C,
45.6; H, 3.7; N, 7.1; S, 5.4. Found: C, 45.7; H, 3.4; N, 7.4; S, 5.4%.
IR
m : m
max/cmꢀ1 (C@N) 1585 m. 1H NMR (CDCl3, d ppm, J Hz):
4.23. [{Pt[2-MeC6H3C(H)@NN@C(S)NH2]}2{
l
-Ph2P(CH2)2PPh2}] (3d)
7.96 (d, HC@N, 4J(PH) 7.9, 3J(PtH) 71.6); 6.56 (d, H3, 3J(H3H4)
7.4); 6.46 (t, H4, 3J(H4H5) 7.4); 6.20 (b, H5, 3J(PtH5) 37.0); 5.11
(s, NH2); 2.74, 2.20 (b, PCH2CH2CH2P); 2.33 (s, 2-Me). 31P–{1H}
NMR (CDCl3, d ppm, J Hz): 11.02 (s, 1J(PtP) = 3784.2).
Yield: 60%. Anal. Calc for C44H42N6P2S2Pt2 (1157.1 g/mol): C,
44.6; H, 3.5; N, 7.3; S, 5.5. Found: C, 44.9; H, 3.8; N, 7.1; S, 5.2%.
IR
m : m
max/cmꢀ1 (C@N) 1584 m. 1H NMR (CDCl3, d ppm, J Hz):
8.02 (s, HC@N, 3J(PtH) 65.0); 6.58 (d, H3, 3J(H3H4) 7.4); 5.10 (s,
NH2); 6,45 (b, H4); 6.20 (b, H5); 2.45 (b, PCH2); 2.34 (s, 2-Me).
31P–{1H} NMR (CDCl3, d ppm, J Hz): 15.29 (s, 1J(PtP) = 3840.0).
4.30. [Pt{2-MeC6H3C(H)@NN@C(S)NHMe]}2{l-Ph2P(CH2)3PPh2}] (4e)
Yield: 42%. Anal. Calc for C47H48N6P2S2Pt2 (1213.2 g/mol): C,
46.5; H, 4.0; N, 6.9; S, 5.3. Found: C, 46.7; H, 4.1; N, 6.6; S, 5.1%.
4.24. [Pt{2-MeC6H3C(H)@NN@C(S)NHMe]}2{
l
-Ph2P(CH2)2PPh2}] (3e)
IR m : m
max/cmꢀ1 (C@N) 1585w. 1H NMR (CDCl3, d ppm, J Hz): 8.10
(s, HC@N, 3J(PtH) 73.6); 6.57 (d, H3, 3J(H3H4) 7.4); 6.47 (t, H4,
3J(H4H5) 7.4); 6.24 (d, H5); 3.01 (s, NMe); 2.74, 2.45 (b,
PCH2CH2CH2P); 2.35 (s, 2-Me). 31P–{1H} NMR (CDCl3, d ppm,
J Hz): 10.97 (s, 1J(PtP) = 3784.2).
Yield: 56%. Anal. Calc. for C46H46N6P2S2Pt2 (1440.0 g/mol): C,
40.0; H, 3.5; N, 5.8; S, 4.5. Found: C, 40.4; H, 3.9; N, 5.6; S, 4.3%.
IR
m : m
max/cmꢀ1 (C@N) 1580 m. 1H NMR (CDCl3, d ppm, J Hz):
8.13 (s, HC@N, 3J(PtH) 73.6); 6.58 (d, H3, 3J(H3H4) 7.4); 6.43 (b,
H4); 6.20 (b, H5); 3.02 (s, NCH3); 2.44 (b, PCH2); 2.36 (s, 2-Me).
31P–{1H} NMR (CDCl3, d ppm, J Hz): 15.42 (s, 1J(PtP) = 3865.6).
4.31. [Pt{2-MeC6H3C(H)@NN@C(S)NHEt}(PPh3)]}2
{l-Ph2P(CH2)3PPh2}] (4f)
4.25. [Pt{2-MeC6H3C(H)@NN@C(S)NHEt}(PPh3)]}2
Yield: 47%. Anal. Calc for C49H52N6P2S2Pt2 (1241.2 g/mol): C,
{
l
-Ph2P(CH2)2PPh2}] (3f)
47.4; H, 4.2; N, 6.8; S, 5.2. Found: C, 47.5; H, 4.4; N, 6.5; S, 5.1%.
IR m : m (C@N) 1584sh, m
max/cmꢀ1 (C@S) 800w. 1H NMR (CDCl3, d
Yield: 36%. Anal. Calc. for C48H50N6P2S2Pt2 (1347.6 g/mol): C,
ppm, J Hz): 8.08 (s, HC@N, 3J(PtH) 66.2); 6.57 (d, H3, 3J(H3H4)
7.4); 6,47 (t, H4, 3J(H4H5) 7.4); 6.24 (dd, H5, 4J(PtH5) 5.6,
3J(PtH5) 43.2); 3.42 (m, NCH2Me); 2.74, 2.45 (b, PCH2CH2CH2P),
2.33 (s, 2-Me); 1.17 (t, NCH2Me, 3J(HH) 9.2). no asignada(NHEt).
31P–{1H} NMR (CDCl3, d ppm, J Hz): 11.00 (s, 1J(PtP) = 3784.2).
43.7; H, 3.9; N, 6.2; S, 4.8. Found: C, 43.4; H, 3.8; N, 6.0; S, 4.6%.
IR m : m (C@N) 1587w, m
max/cmꢀ1 (C@S) 798w. 1H NMR (CDCl3, d
ppm, J Hz): 8.11 (s, HC@N, 3J(PtH) 67.2); 6.58 (d, H3, 3J(H3H4)
7.4); 6.44 (b, H4); 6.20 (b, H5); 3.42 (m, NCH2Me); 2.45 (b,
PCH2); 2.28 (s, 2-Me); 1.18 (t, NCH2Me, 3J(HH) 9.2) 31P–{1H} NMR
(CDCl3, d ppm, J Hz): 15.27 (s, 1J(PtP) = 3794.4).
4.32. Preparation of [{Pt[4-MeC6H3C(H)@NN@C(S)NH2]}2
{l-Ph2P(CH2)4PPh2}] (5a)
4.26. Preparation of [{Pt[4-MeC6H3C(H)@NN@C(S)NH2]}2
{l
-Ph2P(CH2)3PPh2}] (4a)
Yield: 71%. Anal. Calc. for C46H46N6P2S2Pt2 (1199.1 g/mol): C,
46.1; H, 3.9; N, 7.0; S, 5.3. Found: C, 46.3; H, 4.0; N, 7.2; S, 5.6%.
Yield: 60%. Anal. Calc. for C45H44N6P2S2Pt2 (1185.1 g/mol): C,
IR m : m (C@N) 1582m, m
max/cmꢀ1 (C@S) 801sh. 1H NMR (CDCl3, d
45.6; H, 3.7; N, 7.1; S, 5.4. Found: C, 45.9; H, 3.8; N, 7.4; S, 5.5%.
ppm, J Hz): 7.70 (d, HC@N, 4J(PH) 7.7); 6.90 (d, H2, 3J(H2H3) 7,4);
6.60 (d, H3); 6.12 (s, H5, 3J(PtH5) 44.2); 5.08 (b, NH2); 2.32 (s, 4-
Me). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 12.35 (s, 1J(PtP) = 3804.0).
IR m : m (C@N) 1582s, m
max/cmꢀ1 (C@S) 810w. 1H NMR (CDCl3, d
ppm, J Hz): 7.83 (s, HC@N); 6.90 (d, H2, 3J(H2H3) 7.9); 6.62 (d,
H3); 6.09 (b, H5); 5.09 (b, NH2); 2.38 (s, 4-Me). 31P–{1H} NMR
(CDCl3, d ppm, J Hz): 10.36 (s, 1J(PtP) = 3784.2).
4.33. [{Pt[4-MeC6H3C(H)@NN@C(S)NHMe]}2{l-Ph2P(CH2)4PPh2}]
(5b)
4.27. [{Pt[4-MeC6H3C(H)@NN@C(S)NHMe]}2
{l
-Ph2P(CH2)3PPh2}] (4b)
Yield: 80%. Anal. Calc. for C48H50N6P2S2Pt2 (1227.2 g/mol): C,
47.0; H, 4.1; N, 6.8; S, 5.2. Found: C, 47.5; H, 4.4; N, 6.9; S, 5.0%.
Yield: 85%. Anal. Calc. for C47H48N6P2S2Pt2 (1213.2 g/mol): C,
IR m : m (C@N) 1582 m, m
max/cmꢀ1 (C@S) 808b. 1H NMR (CDCl3, d
46.5; H, 4.0; N, 6.9; S, 5.3. Found: C, 46.6; H, 4.2; N, 7.1; S, 5.1%.
ppm, J Hz): 7.73 (d, HC@N, 4J(PH) 8.9); 6.91 (d, H2, 3J(H2H3) 7.4);
6.61 (d, H3); 6.12 (s, H5, 3J(PtH5) 44.7); 4.82 (b, NHMe); 2.98 (s,
NMe); 2.49, 1.68 (b, PCH2CH2CH2CH2P); 1.80 (s, 4-Me). 31P–{1H}
NMR (CDCl3, d ppm, J Hz): 12.35 (s, 1J(PtP) = 3810.0).
IR m : m (C@N) 1582m, m
max/cmꢀ1 (C@S) 808b. 1H NMR (CDCl3, d
ppm, J Hz): 7.74 (d, HC@N, 3J(PH) 7.4); 6.91 (d, H2, 3J(H2H3) 7.4);
6.62 (d, H3); 6.09 (s, H5, 3J(PtH5) 46.2); 4.82 (b, NHMe); 3.00 (s,
NMe); 2.78, 2.30 (b, PCH2CH2CH2P); 1.81 (s, 4-Me). 31P–{1H} NMR
(CDCl3, d ppm, J Hz): 10.31 (s, 1J(PtP) = 3780.0).
4.34. [{Pt[4-MeC6H3C(H)@NN@C(S)NHEt]}2{l-Ph2P(CH2)4PPh2}] (5c)
4.28. [{Pt[4-MeC6H3C(H)@NN@C(S)NHEt]}2{
l
-Ph2P(CH2)3PPh2}] (4c)
Yield: 84%. Anal. Calc. for C50H54N6P2S2Pt2ꢁ2CHCl3 (1495.0 g/
mol): C, 41.7; H, 3.9; N, 5.6; S, 4.3. Found: C, 42.0; H, 4.0; N, 5.3;
Yield: 91%. Anal. Calc. for C49H52N6P2S2Pt2 (1241.2 g/mol): C,
S, 4.1%. IR m : m (C@N) 1585 m, m
max/cmꢀ1 (C@S) 811b. 1H NMR
47.4; H, 4.2; N, 6.8; S, 5.1. Found: C, 47.3; H, 4.0; N, 6.9; S, 5.2%.
(CDCl3, d ppm, J Hz): 7.90 (d, HC@N, 4J(PH) 8.0); 6,90 (d, H2,
3J(H2H3) 7.4); 6.61 (d, H3); 6.13 (s, H5, 3J(PtH5) 49.6); 4.77 (b,
IR m : m (C@N) 1582m, m
max/cmꢀ1 (C@S) 804b. 1H NMR (CDCl3, d

D. Lata et al. / Polyhedron 41 (2012) 30–39
37
NHEt); 3.41 (m, NCH2Me); 2.49 (b, PCH2CH2CH2CH2P); 1.80 (s, 4-
4.40. [Pt{4-MeC6H3C(H)@NN@C(S)NHEt}(Ph2PCH2PPh2-P)] (6c)
Me); 1.16 (t, NCH2Me, 3J(HH) 9.0). 31P–{1H} NMR (CDCl3, d ppm,
J Hz): 12.33 (s, 1J(PtP) = 3804.6).
Yield: 91%. Anal.Calc. for C36H35N3P2SPtꢁCHCl3 (919.2 g/mol): C,
48.3; H, 4.1; N, 4.6; S, 3.5. Found: C, 48.5; H, 4.0; N, 4.5; S, 3.5%. IR
m
max/cmꢀ1 (C@S) 813w. 1H NMR (CDCl3, d ppm,
: m (C@N) 1580m, m
J Hz): 7.67 (d, HC@N, 4J(PH) 8.4, 3J(PtH) 45.8); 6.84 (d, H2, 3J(H2H3)
7.4); 6.57 (d, H3); 6.06 (s, H5, 3J(PtH5) 45.8); 4.79 (b, NHEt); 3.44
(d, PCH2P); 3.41 (m, NCH2Me); 1.80 (s, 4-Me); 1.15(t, NCH2Me,
3J(HH) 9.2). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 8.90 (d, 2J(PP)
71.2, 1J(PtP) = 3835.0); ꢀ27.05 (d).
4.35. [{Pt[2-MeC6H3C(H)@NN@C(S)NH2]}2{l-Ph2P(CH2)4PPh2}] (5d)
Yield: 43%. Anal. Calc. for C46H46N6P2S2Pt2 (1199.1 g/mol): C,
46.1; H, 3.9; N, 7.0; S, 5.3. Found: C, 46.3; H, 4.0; N, 6.8; S, 5.1%.
IR m : m
max/cmꢀ1 (C@N) 1577sh. 1H NMR (CDCl3, d ppm, J Hz): 8.00
(d, HC@N, 3J(PtH) 66.0); 6.55 (d, H3, 3J(H3H4) 7.9); 6,46 (t, H4,
3J(H4H5) 7.4); 6.22 (b, H5, 3J(PtH5) 66.0); 5.10 (s, NH2); 2.45,
2.01 (b, PCH2CH2CH2CH2P); 2.32 (s, 2-Me). 31P–{1H} NMR (CDCl3,
d ppm, J Hz): 12.88 (s, 1J(PtP) = 3804.6).
4.41. [Pt{2-MeC6H3C(H)@NN@C(S)NH2}(Ph2PCH2PPh2-P)] (6d)
Yield: 35%. Anal. Calc. for C34H31N3P2SPt (770.7 g/mol): C, 53.0;
H, 4.1; N, 5.5; S, 4.2. Found: C, 52.8; H, 4.0; N, 5.3 S, 4.1%. IR mmax
/
cmꢀ1 (C@N) 1572sh. 1H NMR (CDCl3, d ppm, J Hz): 7.89 (d,
: m
4.36. [Pt{2-MeC6H3C(H)@NN@C(S)NHMe]}2{l-Ph2P(CH2)4PPh2}] (5e)
HC@N, 4J(PH) 7.9); 6.50 (d, H3, 3J(H3H4) 7.4); 6,39 (t, H4,
3J(H4H5) 7.4); 6.10 (d, H5, 3J(PtH5) 44.2); 5.10 (s, NH2); 3.44 (d,
PCH2P); 2.29 (s, 2-Me). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 8.90
(d, 2J(PP) 71.2, 1J(PtP) = 3845.2); ꢀ27.20 (d).
Yield: 58%. Anal. Calc. for C48H50N6P2S2Pt2 (1227.2 g/mol): C,
47.0; H, 4.1; N, 6.8; S, 5.2. Found: C, 47.1; H, 4.2; N, 6.6; S, 4.8%.
IR m : m
max/cmꢀ1 (C@N) 1586w. 1H NMR (CDCl3, d ppm, J Hz): 8.11
(b, HC@N, 3J(PtH) 69.4); 6.56 (d, H3, 3J(H3H4) 7.4); 6.45 (t, H4,
3J(H4H5) 7.4); 6.23 (d, H5, 4J(PtH5) 52.6); 4.83 (b, NHMe); 3.00
(d, NMe); 2.45, 1.55 (b, PCH2CH2CH2P); 2.34 (s, 2-Me). 31P–{1H}
NMR (CDCl3, d ppm, J Hz): 12.86 (s, 1J(PtP) = 3804.6).
4.42. [Pt{2-MeC6H3C(H)@NN@C(S) NHMe}(Ph2PCH2PPh2-P)] (6e)
Yield: 26%. Anal. Calc. for C35H33N3P2SPt (784.7 g/mol): C, 53.6;
H, 4.2; N, 5.4; S, 4.1. Found: C, 53.3; H, 4.4; N, 5.2; S, 4.0%. IR mmax
/
cmꢀ1 (C@N) 1586w. 1H NMR (CDCl3, d ppm, J Hz): 8.02 (d, HC@N,
: m
4J(PH) 7.9, 3J(PtH) 74.8); 6.51 (d, H3, 3J(H3H4) 7.4); 6.40 (t, H4,
3J(H4H5) 7.4); 6.12 (d, H5, 3J(PtH5) 47.4); 4.87 (b, NHMe); 3.43
(d, PCH2P); 3.00 (b, NMe); 2.34 (s, 2-Me). 31P–{1H} NMR (CDCl3, d
ppm, J Hz): 9.30 (d, 2J(PP) 71.2; 1J(PtP) = 3845.2); ꢀ27.20 (d).
4.37. [Pt{2-MeC6H3C(H)@NN@C(S)NHEt}(PPh3)]}2
{
l-Ph2P(CH2)4PPh2}] (5f)
Yield: 68%. Anal. Calc. for C50H54N6P2S2Pt2 (1255.2 g/mol): C,
47.8; H, 4.3; N, 6.7; S, 5.1. Found: C, 47.9; H, 4.5; N, 6.8; S, 4.8%.
4.43. [Pt{2-MeC6H3C(H)@NN@C(S)NHEt}(Ph2PCH2PPh2-P)] (6f)
Yield: 20%. Anal. Calc. for C36H35N3P2SPt (798.8 g/mol): C, 54.1;
IR m : m (C@N) 1585w, m
max/cmꢀ1 (C@S) 798sh. 1H NMR (CDCl3, d
ppm, J Hz): 8.08 (b, HC@N, 3J(PtH) 64.2); 6.56 (d, H3, 3J(H3H4)
7.9); 6.45 (t, H4, 3J(H4H5) 7.4); 6.24 (d, H5, 3J(PtH5) 52.6); 4.79
(b, NHEt); 3.42 (m, NCH2Me); 2.46, 1.77 (b, PCH2CH2CH2P); 2.32
(s, 2-Me); 1.17 (t, NCH2Me, 3J(HH) 9.3). 31P–{1H} NMR (CDCl3, d
ppm, J Hz): 18.81 (s, 1J(PtP) = 3790.6).
H, 4.4; N, 5.3; S, 4.0. Found: C, 54.4; H, 4.6; N, 5.0; S, 3.8%. IR mmax
/
cmꢀ1 (C@N) 1585w. 1H NMR (CDCl3, d ppm, J Hz): 8.02 (d, HC@N,
:
m
4J(PH) 7.4, 3J(PtH) 65.2); 6.51 (d, H3, 3J(H3H4) 7.9); 6.39 (t, H4,
3J(H4H5) 6.8); 6.12 (d, H5, 3J(PtH5) 52.6); 4.82 (b, NHEt); 3.62 (d,
PCH2P); 3.42 (m, NCH2Me); 2.31 (s, 2-Me)ß 1.17 (t, NCH2Me,
3J(HH) 8.9); 31P–{1H} NMR (CDCl3, d ppm, J Hz): 9.30 (d, 2J(PP)
71.2; 1J(PtP) = 3830.5); ꢀ27.15 d.
4.38. Preparation of [Pt{4-MeC6H3C(H)@NN@C(S)NH2}
(Ph2PCH2PPh2-P)] (6a)
4.44. Preparation of [Pt{4-MeC6H3C(H)@NN@C(S)NH2}
{Ph2PC(@CH2)PPh2-P}] (7a)
To a suspensión of 1a (15 mg, 0.097 mmol) in chloroform (10
cm3)
1,1-bis(diphenylphosphino)methane
(dppm,
8 mg,
0.194 mmol) was added and the resulting mixture was heated un-
der nitrogen for 10 min. The solvent was removed under reduced
pressure and the residue recrystallized in chloroform/n-hexane.
Yield: 32%. Anal. Calc. for C34H31N3P2SPt (770.7 g/mol): C, 53.0;
To a suspensión of 1a (15 mg, 0.097 mmol) in chloroform
(10 cm3)
1,1-bis(diphenylphosphino)ethene
(vdpp,
15 mg,
0.387 mmol) was added and the resulting mixture was heated un-
der nitrogen for 10 min. The solvent was removed under reduced
pressure and the residue recrystallized in chloroform/n-hexane.
Yield: 35%. Anal. Calc. for C35H31N3P2SPt (782.7 g/mol): C, 53.7;
H, 4.1; N, 5.5; S, 4.2. Found: C, 53.2; H, 4.2; N, 5.3; S, 4.1%. IR mmax
/
cmꢀ1 (C@S) 809w. 1H NMR (CDCl3, d ppm, J Hz):
: m (C@N) 1582s, m
6.83 (d, H2, 3J(H2H3) 7.4); 6.57 (d, H3); 6.04 (s, H5, 3J(PtH5) 46.3);
5.09 (s, NH2); 3.44 (d, PCH2); 1.80 (s, 4-Me). 31P–{1H} NMR (CDCl3, d
ppm, J Hz): 8.45 (d, 2J(PP) 71.2, 1J(PtP) = 3845,2); -27.05 (d).
Compounds 6b-6f were prepared in a similar manner.
H, 4.0; N, 5.4; S, 4.1. Found: C, 54.0; H, 4.3; N, 5.2; S, 4.0%. IR mmax
/
cmꢀ1 (C@S) 810b. 1H NMR (CDCl3, d ppm, J Hz):
:
m
(C@N) 1582m,
m
7.62 (d, HC@N, 4J(PH) 8.4,); 6.98, 5.80 (dd, C@CH2,
trans-3J(PH) = 29.5, cis-3J(PH) = 19.4); 6.92 (d, H2, 3J(H2H3) 7.4);
6.65 (d, H3); 6,30 (s, H5, 3J(PtH5) 45.2); 5.01 (s, NH2); 1.91 (s, 4-
Me). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 27.90 (d, 2J(PP) 71.2;
1J(PtP) = 3930.0); ꢀ13.90 d.
4.39. [Pt{4-MeC6H3C(H)@NN@C(S)NHMe}(Ph2PCH2PPh2-P)] (6b)
Yield: 45%. Anal. Found: C, 53.3; H, 4.1; N, 4.8; S, 3.9;
Compounds 7b–7f were prepared in a similar manner.
C35H33N3P2SPt (784.8 g/mol) requires C, 53.6; H, 4.2; N, 5.3; S,
4.1. IR
m
max/cmꢀ1
:
m
(C@N) 1582 m,
m
(C@S) 808b. 1H NMR (CDCl3,
4.45. [Pt{4-MeC6H3C(H)@NN@C(S)NHMe}{Ph2PC(@CH2)PPh2-P}] (7b)
Yield: 37%. Anal. Calc. for C36H33N3P2SPt (796.8 g/mol): C, 54.3;
d ppm, J Hz): 7.69 (d, HC@N, 4J(PH) 8.4, 3J(PtH) 66.3); 6.85 (d, H2,
3J(H2H3) 7.8); 6.57 (d, H3); 6.05 (s, H5, 3J(PtH5) 46.1); 4.82 (b,
NHMe); 3.43 (d, PCH2P); 2.98 (b, NMe); 1.79 (s, 4-Me). 31P–{1H}
NMR (CDCl3, d ppm, J Hz): 8.85 (d, 2J(PP) 71.2, 1J(PtP) 3840.0);
ꢀ27.10 (d).
H, 4.2; N, 5.3; S, 4.0. Found: C, 54.6; H, 4.4; N, 5.3; S, 3.8%. IR mmax
cmꢀ1 (C@S) 806b. 1H NMR (CDCl3, d ppm, J Hz):
(C@N) 1582m,
7.74 (d, HC@N, 4J(PH) 8.4); 6.96, 5.70 (dd, C@CH2,
/
:
m
m

38
D. Lata et al. / Polyhedron 41 (2012) 30–39
trans-3J(PH) = 28.1, cis-3J(PH) = 19.7); 6.92 (d, H2, 3J(H2H3) 7.4);
6.64 (d, H3); 6.30 (s, H5, 3J(PtH5) 45.6); 4.78 (b, NHMe); 2.98 (b,
NMe); 1.79 (s, 4-Me). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 28.00
(d, 2J(PP) 71.2; 1J(PtP) = 3920.0); ꢀ14.05 (d).
Compounds 8b–8f were prepared analogously.
4.51. [Pt{4-MeC6H3C(H)@NN@C(S)NHMe}{Ph2PCH2PPh2W(CO)5}]
(8b)
4.46. [Pt{4-MeC6H3C(H)@NN@C(S)NHEt}{Ph2PC(@CH2)PPh2-P}] (7c)
Yield: 55%. Anal. Calc. for C40H33N3O5P2PtSW (1108.7 g/mol): C,
43.3; H, 3.0; N, 3.8; S, 2.9. Found: C, 43.6; H, 3.2; N, 3.6; S, 2.7%. IR
Yield: 80%. Anal.Calc. for C37H35N3P2SPtꢁCHCl3 (931.2 g/mol): C,
m : m (C@N) 1585m, m
max/cmꢀ1 (C@S) 815a. 1H NMR (CDCl3, d ppm,
49.0; H, 4.0; N, 4.5; S, 3.4. Found: C, 49.2; H, 4.0; N, 4.6; S, 3.7%. IR
m
J Hz): 7.86 (d, HC@N, 4J(PH) 7.0, 3J(PtH) 54.2);6.94 (d, H2, 3J(H2H3)
7.3); 6.69 (d, H3); 6.20 (s, H5, 3J(PtH5) 42.4); 4.82 (b, NHMe); 4.11
(m, PCH2P); 2.81 (b, NMe);1.85 (s, 4-Me). 31P–{1H} NMR (CDCl3, d
ppm, J Hz): 10.05 (d, 2J(PP) 25.0, 1J(WP) 250.1); 5.85 (d, 1J(PP)
25.0, 1J(PtP) = 3908.7).
max/cmꢀ1 (C@S) 804w. 1H NMR (CDCl3, d ppm,
: m (C@N) 1582m, m
J Hz): 7.72 (d, HC@N, 4J(PH) 8.4); 7.00, 5.90, (dd, C@CH2,
trans-3J(PH) = 27.3, cis-3J(PH) = 19.3); 6.92 (d, H2, 3J(H2H3) 7.4);
6.64 (d, H3); 6.32 (s, H5, 3J(PtH5) 45.6); 4.75(b, NHEt); 3.38 (m,
NCH2Me); 1.91 (s, 4-Me); 1.14 (t, NCH2Me, 3J(HH) 9.3). 31P–{1H}
NMR (CDCl3, d ppm, J Hz): 8.90 (d, 2J(PP) 76.3, 1J(PtP) = 3918.0);
ꢀ27.05 (d).
4.52. [Pt{4-MeC6H3C(H)@NN@C(S)NHEt}{Ph2PCH2PPh2W(CO)5}] (8c)
Yield: 61%. Anal. Calc. for C41H35N3O5P2PtSW (1122.7 g/mol): C,
4.47. [Pt{2-MeC6H3C(H)@NN@C(S)NH2}{Ph2PC(@CH2)PPh2-P}] (7d)
43.9; H, 3.1; N, 3.7; S, 2.9. Found: C, 44.2; H, 3.4; N, 3.9; S, 3.0%. IR
m
max/cmꢀ1 (C@S) 780d. 1H NMR (CDCl3, d ppm,
: m (C@N) 1584d, m
Yield: 50%. Anal. Calc. for C35H31N3P2SPt (782.7 g/mol): C, 53.7;
J Hz): 7.95 (d, HC@N, 4J(PH) 7.3, 3J(PtH) 56.0); 7.01 (d, H2,
3J(H2H3) 7.6); 6.76 (d, H3); 6.42 (s, H5, 3J(PtH5) 44.1); 4.00 (m,
PCH2P); 3.67 (m, NCH2Me); 1.85 (s, 4-Me); 1.45 (t, NCH2Me). 31P–
{1H} NMR (CDCl3, d ppm, J Hz): 9.85 (d, 2J(PP) 23.4, 1J(WP)
246.2); 4.86 (d, 1J(PP) 23.4, 1J(PtP) = 3943.6).
H, 4.0; N, 5.4; S, 4.1. Found: C, 54.1; H, 4.1; N, 5.6; S, 4.1%. IR mmax
/
cmꢀ1 (C@N) 1583m. 1H NMR (CDCl3, d ppm, J Hz): 7.95 (d, HC@N,
: m
4J(PHi) 8.4, 4J(PtHi) 73.8); 6.87, 5.92 (dd, C@CH2, trans-3J(PH) = 29.6,
cis-3J(PH) = 20.3); 6.57 (d, H3, 3J(H3H4) 7.4); 6.47 (t, H4, 3J(H4H5)
7.4); 6.23 (d, H5, 4J(PtH5) 39.8); 5.06 (s, NH2); 2.34 (s, 2-Me).
31P–{1H} NMR (CDCl3,
d
ppm, J Hz): 27.95 (d, 2J(PP) 76.3,
4.53. [Pt{2-MeC6H3C(H)@NN@C(S)NH2}{Ph2PCH2PPh2W(CO)5}] (8d)
1J(PtP) = 3926.6); ꢀ13.80 (d).
Yield: 41%. Anal. Calc. for C39H31N3O5P2PtSW (1094.6 g/mol): C,
4.48. [Pt{2-MeC6H3C(H)@NN@C(S) NHMe}{Ph2PC(@CH2)PPh2-P}]
(7e)
42.8; H, 2.9; N, 3.8; S, 2.9. Found: C, 43.0; H, 3.0; N, 3.5; S, 2.8%. IR
m
max/cmꢀ1 (C@N) 1580 m. 1H NMR (CDCl3, d ppm, J Hz): 7.82 (d,
: m
HC@N, 4J(PH) 8.9, 3J(PtH) 59.0); 6.59 (d, H3, 3J(H3H4) 7.9); 6.54 (t,
H4, 3J(H4H5) 7.9); 6.14 (d, H5, 3J(PtH5) 44.6); 5.01 (s, NH2); 3.99
(m, PCH2P); 2.34 (s, 2-Me). 31P–{1H} NMR (CDCl3, d ppm, J Hz):
9.10 (d, 2J(PP) 20.3, 1J(WP) 245.4); 7.15 (d, 1J(PP) 20.3,
1J(PtP) = 3916.4).
Yield: 20%. Anal. Calc. for C36H33N3P2SPt (796.8 g/mol): C, 54.3;
H, 4.2; N, 5.3; S, 4.0. Found: C, 54.5; H, 4.2; N, 5.2; S, 3.9%. IR mmax
/
cmꢀ1 (C@N) 1584 m. 1H NMR (CDCl3, d ppm, J Hz): 8.08 (d,
:
m
HC@N, 4J(PH) 8.4); 6.85dd, 5.91d (C@CH2, trans-3J(PH) = 29.5,
cis-3J(PH) = 19.3); 6.58 (d, H3, 3J(H3H4) 7.4); 6.47(t, H4, 3J(H4H5)
7.4); 6.24 (d, H5, 3J(PtH5) 40.0); 4.87 (b, NHMe); 2.99 (d, NCH3);
2.36 (s, 2-Me). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 28.05 (d,
2J(PP) 76.3, 1J(PtP) = 3926.6); ꢀ13.90 (d).
4.54. [Pt{2-MeC6H3C(H)@NN@C(S)NHMe}{Ph2PCH2PPh2W(CO)5}]
(8e)
Yield: 64%. Anal. Calc. for C40H33N3O5P2PtSW (1108.7 g/mol): C,
4.49. [Pt{2-MeC6H3C(H)@NN@C(S)NHEt}{Ph2PC(@CH2)PPh2-P}] (7f)
43.3; H, 3.0; N, 3.8; S, 2.9. Found: C, 43.7; H, 3.1; N, 3.9; S, 2.8%. IR
m
max/cmꢀ1 (C@S) 780b. 1H NMR (CDCl3, d ppm,
: m (C@N) 1568w, m
Yield: 18%. Anal. Calc. for C37H35N3P2SPt (798.8 g/mol): C, 54.8;
J Hz): 7.89 (d, HC@N, 4J(PH) 8.4, 3J(PtH) 55.8); 6.67 (d, H3, 3J(H3H4)
8.0); 6.45 (m, H4); 6.14 (t, H5, 3J(H4H5) 7.0, 3J(PtH5) 43.1); 4.71 (b,
NHMe); 3.87 (m, PCH2P); 2.70 (b, NMe); 2.23 (s, 2-Me). 31P–{1H}
NMR (CDCl3, d ppm, J Hz): 9.92 (d, 2J(PP) 21.1, 1J(WP) 249.4);
6.85 (d, 1J(PP) 21.1, 1J(PtP) = 3901.1).
H, 4.4; N, 5.2; S, 3.9. Found: C, 55.0; H, 4.6; N, 5.0; S, 3.7%. IR mmax
/
cmꢀ1: C@N) 1585w,
m
(C@S) 801b.
1H NMR (CDCl3, d ppm, J Hz): 8.06 (d, HC@N, 4J(PHi) 8.4); 6.88,
5.92 (dd, C@CH2, trans-3J(PH) = 28.6, cis-3J(PH) = 20.7); 6.58 (d,
H3, 3J(H3H4) 7.4); 6.47 (t, H4, 3J(H4H5) 7.4); 6.25 (d, H5, 3J(PtH5)
41.7); 4.79 (b, NHEt); 3.41 (m, NCH2Me); 2.36 (s, 2-Me); 1.16 (t,
NCH2Me, 3J(HH) 9.1). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 9.30 (d,
2J(PP) 71.2, 1J(PtP) = 3920.0); ꢀ27.15 (d).
4.55. [Pt{2-MeC6H3C(H)@NN@C(S)NHEt}{Ph2PCH2PPh2W(CO)5}] (8f)
Yield: 69%. Anal. Calc. for C41H35N3O5P2PtSW (1122.7 g/mol): C,
43.9; H, 3.1; N, 3.7; S, 2.9. Found: C, 43.8; H, 3.1; N, 3.9; S, 3.1%. IR
4.50. Preparation of [Pt{4-MeC6H3C(H)@NN@C(S)NH2}
{Ph2PCH2PPh2W(CO)5}] (8a)
m : m (C@N) 1583d, m
max/cmꢀ1 (C@S) 791b. 1H NMR (CDCl3, d ppm,
J Hz): 7.81 (d, HC@N, 4J(PH) 7.8, 3J(PtH) 53.5); 6.86 (d, H3,
3J(H3H4) 8.4); 6.46 (m, H4); 6.09 (t, H5, 3J(H4H5) 7.8, 4J(PtH5)
41.1); 3.90 (m, PCH2P); 3.52 (m, NCH2Me); 2.31 (s, 2-Me); 1.29 (t,
NCH2Me). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 8.85 (d, 2J(PP) 20.2,
1J(WP) 241.3); 5.10 (d, 1J(PP) 20.9, 1J(PtP) = 3930.0).
To a suspension of 1a (15 mg, 0.097 mmol) in chloroform
(10 cm3) [W(CO)5(Ph2CH2PPh2)] (27 mg, 0.381 mmol) was added
and the resulting mixture was stirred under nitrogen for 15 min.
The solvent was removed under reduced pressure and the residue
recrystallized in chloroform/n-hexane. Yield: 45%. Anal. Calc. for
4.56. Crystal structures for 3e and 5c
C
39H31N3O5P2PtSW (1094.6 g/mol): C, 42.8; H, 2.9; N, 3.8; S, 2.9.
Found: C, 43.0; H, 3.0; N, 3.7; S, 2.7%. IR (C@N)
m
max/cmꢀ1
:
m
Crystals of 3e and 5c were mounted on a glass fiber and trans-
ferred to the diffractometer. Three-dimensional, room temperature
X-ray data were collected on a Siemens SMART CCD diffractometer
1583s,
m
(C@S) 810b. 1H NMR (CDCl3, d ppm, J Hz): 6.90 (d, H2,
3J(H2H3) 7.4); 6.61 (d, H3); 6.08 (s, H5, 3J(PtH5) 43.1); 4.02 (m,
PCH2P); 1.91 (s, 4-Me). 31P–{1H} NMR (CDCl3, d ppm, J Hz): 9.11
(d, 2J(PP) 26.9, 1J(WP) 244.2); 6.45 (d, 1J(PP) 26.9, 1J(PtP) = 3916.4).
by the omega scan method, using monochromated Mo K
a radia-
tion. All the measured reflections were corrected for Lorentz and

D. Lata et al. / Polyhedron 41 (2012) 30–39
39
21 (2002) 4604;
polarization effects and for absorption by semiempirical methods
based on symmetry-equivalent and repeated reflections
[Tmax/Tmin = 0.2324/0.4611 (3e) and 0.2461/0.4680 (5c)]. The struc-
turs were solved by direct methods and refined by full matrix least
squares on F2. Hydrogen atoms were included in calculated posi-
tions and refined in riding mode. Refinement converged at a final
R = 0.0292 (3e), 0.0367 (5c) (observed data, F), and wR2 = 0.0814
(3e), 0.0530 (5c) (all unique data, F2), and with allowance for the
thermal anisotropy of all non-hydrogen atoms. Minimum and
maximum final density 0.2324 and 0.4611 (3e) and 0.2461 and
0.4680 (5c) eAꢀ3. The structure solution and refinement were
carried out using the program package SHELX-97 [29].
(c) P.V. Bernhardt, C. Gallego, M. Martínez, T. Parella, Inorg. Chem. 41 (2002)
1747.
[8] J.S. Fossey, C.J. Richards, Organometallics 21 (2002) 5259.
[9] (a) M. Akaiwa, T. Kanbara, H. Fukumoto, T. Yamamoto, J. Organomet Chem.
690 (2005) 4192;
(b) A.F. Rausch, L. Murphy, J.A.G. Williams, H. Yersin, Inorg. Chem. 48 (2010)
11407;
(c) S.U. Pandya, K.C. Moss, M.R. Bryce, A.S. Batsanov, M.A. Fox, V. Jankus, H.A.
Al Attar, A.P. Monkman, Eur. J. Inorg. Chem. 2010 (1963).
[10] S. Padhye, Coord. Chem. Rev. 63 (1985) 127.
[11] (a) F. Niedermair, K. Waich, S. Kappaun, T. Mayr, G. Trimmel, K. Mereiter, C.
Slugovc, Inorg. Chim. Acta 360 (2007) 2767;
(b) C.P. Newman, K. Casey-Green, G.J. Clarkson, G.W.V. Cave, W. Errington, J.P.
Rourke, Dalton Trans. (2007) 3170;
(c) N. Godbert, T. Pugliese, I. Aiello, A. Bellusci, A. Crispini, M. Ghedini, Eur. J.
Inorg. Chem. (2007) 5105.
[12] (a) A. Amoedo, M. Graña, J. Martínez, T. Pereira, M. López-Torres, A. Fernández,
J.J. Fernández, J.M. Vila, Eur. J. Inorg. Chem. (2002) 613;
Acknowledgments
(b) A. Fernández, D. Vázquez-García, J.J. Fernández, M. López-Torres, A. Suárez,
S. Castro-Juiz, J.M. Ortigueira, J.M. Vila, New J. Chem. 26 (2002) 105;
(c) D. Vázquez-García, A. Fernández, J.J. Fernández, M. López-Torres, A. Suárez,
J.M. Ortigueira, J.M. Vila, H. Adams, J. Organomet. Chem. 595 (2000) 199.
[13] J.M. Vila, M.T. Pereira, A. Fernández, M. López-Torres, H. Adams, J. Chem. Soc.,
Dalton Trans. (1999) 4193.
[14] J. Martínez, M.T. Pereira, I. Buceta, G. Alberdi, A. Amoedo, J.J. Fernández, M.
López-Torres, J.M. Vila, Organometallics 22 (2003) 5581.
[15] A. Amoedo, L.A.J.M. Antelo, J. Martínez, M.T. Pereira, A. Fernández, J.M. Vila,
Eur. J. Inorg. Chem. (2006) 3016.
[16] T.S. Lobana, A. Sánchez, J.S. Casas, A. Castiñeiras, J. Sordo, M.S. García-Tasende,
E. Vázquez-López, J. Chem. Soc., Dalton Trans. (1997) 4289.
[17] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination
Compounds, 5th ed., Wiley & Sons, New York, 1997.
[18] K. Kawamoto, Y. Nagasawa, H. Kuma, Y. Kushi, Inorg. Chem. 35 (1996) 2427.
[19] (a) D. Kovala-Demertzi, A. Domopoulou, M.A. Demertzis, C.P. Raptopoulou, A.
Terzis, Polyhedron 1994 (1917) 13;
(b) F. Hueso-Ureña, N.A. Illán-Cabeza, M. Moreno-Carretero, A.M. Peñas-
Chamorro, R. Faure, Inorg. Chem. Commun. 2 (1999) 323.
[20] D.X. West, J.S. Ives, G.A. Bain, A. Liberta, J. Valdés-Martínez, K.H. Ebert, S.
Hernández-Ortega, Polyhedron 1997 (1995) 16.
[21] (a) J.M. Vila, M.T. Pereira, J.M. Ortigueira, D. Lata, M. López-Torres, J.J.
Fernández, A. Fernández, H. Adams, J. Organomet. Chem. 566 (1998) 93;
(b) E. Ceci, R. Cini, J. Konopa, L. Maresca, G. Natile, Inorg. Chem. 35 (1996) 876.
[22] A. Fernández, M. López-Torres, A. Suárez, J.M. Ortigueira, T. Pereira, J.J.
Fernández, J.M. Vila, H. Adams, J. Organomet. Chem. 598 (2000) 1.
[23] (a) P.S. Pregosin, R.W. Kuntz, 31P and 13C NMR of Transition Metal Phosphine
Complexes, in: P. Diehl, E. Fluck, R. Kosfeld (Eds.), NMR Basic Principles and
Progress, vol. 16, Springer-Verlag, Berlín, 1979;
We thank the Xunta de Galicia (Projects 10DPI209017PR and
10PXIB209226PR) for financial support.
Appendix A. Supplementary data
CCDC 839102 and 839103 contains the supplementary crystal-
lographic data for 3e and 5c. 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.
References
[1] (a) E.C. Constable, Polyhedron 1037 (1984) 3;
(b) G.R. Newkome, W.E. Puckett, V.K. Gupta, G.E. Kiefer, Chem. Rev. 86 (1986)
451;
(c) O.A. Dunina, V.M. Zalewskaya, V.M. Potapov, Russ. Chem. Rev. 57 (1988)
250;
(d) I. Omae, Organometallic Intramolecular-Coordination Compounds, in
Journal of Organometallic Chemistry Library, Elsevier, Amterdam, 1986;
(e) I. Omae, Coord. Chem. Rev. 83 (1988) 137;
(f) J. Dupont, M. Pfeffer (Eds.), Palladacycles, Wiley-VCH, Weinheim, 2008.
[2] (a) L. Main, B.K. Nicholson, Adv. Met. Org. Chem. 3 (1994) 1;
(b) J. Spencer, M. Pfeffer, Adv. Met. Org. Chem. 6 (1998) 103.
[3] (a) J. Dupont, M. Pfeffer, J. Spencer, Eur. J. Inorg. Chem. 2001 (1917);
(b) L. Botella, C. Najera, Angew. Chem. Int. Ed. 41 (2002) 179.
[4] (a) M. Marcos, in: J.L. Serrano (Ed.), Metallomesogens. Synthesis, Properties
and Applications, VCH, Weinheim, 1996;
(b) D. Pucci, G. Barneiro, A. Bellusci, A. Crispini, M. Ghedini, J. Organomet.
Chem. 691 (2006) 1138.
[5] (a) A.G. Quiroga, J.M. Perez, I. Lopez-Solera, J.R. Masaguer, A. Luque, P. Roman,
A. Edwards, C. Alonso, C. Navarro-Ranninger, J. Med. Chem. 41 (1998) 1399;
(b) A. Gomez-Quiroga, C. Navarro-Ranninger, Coord. Chem. Rev. 248 (2004)
119.
(b) P.E. Garrou, Chem. Rev. 81 (1981) 229;
(c) O. Kuhl, Phosphorus-31 NMR Spectroscopy, Springer, Berlin, 2008.
[24] (a) J.M. Antelo, L. Adrio, M.T. Pereira, J.M. Ortigueira, J.J. Fernandez, J.M. Vila,
Crystal Growth Des. 10 (2010) 701;
(b) J.M. Antelo, L. Adrio, M.T. Pereira, J.M. Ortigueira, A. Fernandez, J.M. Vila,
Eur. J. Inorg. Chem. (2011) 368.
[25] L. Pauling, The Nature of the Chemical Bond, 3rd Ed., Cornell University Press,
New York, 1960.
[26] F.H. Allen, O. Kennard, D.G. Watson, R. Taylor, J. Chem. Soc., Dalton Trans.
(1989) S1.
[27] J. Selbin, K. Abboud, S.F. Watkins, M.A. Gutierrez, F.R. Fronczek, J. Organomet.
Chem. 241 (1983) 259;
(a) C. Navarro-Ranninger, I. López-Solera, A. Álvarez-Valdés, J.H. Rodríguez-
Ramos, J.R. Masaguer, J.L. García-Ruano, Organometallics 12 (1993) 4104.
[28] W.L.F. Armarego, C.L.L. Chai, Purification of Laboratory Chemicals, 5th Ed.,
Butterworth-Heinemann, Bodmin, 2003.
[6] (a) A. von Zelewski, P. Belser, P. Hayos, R. Dux, X. Hua, A. Suckling, H. Stoeckli-
Evans, Coord. Chem. Rev. 132 (1994) 75;
(b) D. Song, Q. Wu, A. Hook, I. Kozin, S. Wang, Organometallics 20 (2000) 4683;
(c) M. Ghedini, I. Aiello, A. Crispini, A. Golemme, M. La Deda, D. Pucci, Coord.
Chem. Rev. 250 (2006) 1373.
[29] G.M. Sheldrick, SHELX-97. An Integrated System for Solving and Refining
Crystal Structures from Diffraction Data, University of Göttingen, Germany,
1997.
[7] (a) M.D. Meijer, A.W. Kleij, B.S. Williams, D. Ellis, M. Lutz, A.L. Spek, G.P.M. van
Klink, G. van Koten, Organometallics 21 (2002) 264;
(b) L.R. Falvello, J. Forniés, A. Martín, V. Sicilia, P. Villarroya, Organometallics