Cycloplatination of thiosemicarbazones derived from furane. Crystal and molecular structure of [{Pt[(OC4H2)C(Me)=NN=C(S)NHEt]} 2{μ-Ph2P(CH2)2PPh2}]

Article abstract of DOI:10.1002/zaac.200700244

Treatment of thiosemicarbazones (OC₄H₃)C(Me)= NN(H)C(=S)NHR (R: Me, a; Et, b) with [cis-PtMe₂(cod)] afforded the tetranuclear compounds [Pt{(OC₄H₂)C(Me)=NN=C(S)NHR}] ₄ (R: Me, 1a; Et, 1b). The reaction of la and lb with triphenylphosphine in 1:4 molar ratio gave rise to the mononuclear compounds [Pt{(OC₄H₂)C(Me)=NN=C(S)NHR)(PPh₃)] (2a, 2b). Treatment of la and lb with large-bite diphosphines Ph₂P(CH ₂)_nPPh₂ (n = 2, dppe; n = 3, dppp; n = 4, dppb) afforded the dinuclear compounds [{Pt[(OC₄H₂)C(Me) = NN=C(S)NHR]}₂{μ-Ph₂P(CH₂) _nPPh₂}], (3a-5a, 3b-5b), with the diphosphine in a bridging mode. Similar reactions with the short-bite diphosphines Ph ₂PCH₂PPh₂ (dppm) and Ph₂PC(=CH ₂)PPh₂ (vdpp) yielded the mononuclear compounds [Pt {(OC₄H₂)C(Me)=NN=C(S)NHR}-(Ph₂PCH ₂PPh₂-P)] (6a, 6b) and [Pt{(OC₄H ₂)C(Me)=NN=C(S)NHR}(Ph₂P-C(= CH₂)PPh ₂-P)] (7a, 7b) with the diphosphine in a monodentate coordination. Treatment of la and lb with [W(CO)₅(Ph₂CH ₂PPh₂)] gave the novel heterodinuclear species [{Pt[(OC₄H₂)C(Me)=NN= C(S)NHR]}[W(CO)₅(Ph ₂CH₂PPh₂-P)}] (8a, 8b), which could also be synthesized by reaction of 6a and 6b with [W(CO)₅(THF)], ¹H, ³¹P-{¹H} and ¹³C-{¹H} NMR and IR data are given. The crystal structure of compound 3b has been determined by X-ray crystallography.

Full text of DOI:10.1002/zaac.200700244

DOI: 10.1002/zaac.200700244
Cycloplatination of Thiosemicarbazones Derived from Furane. Crystal and
Molecular Structure of [{Pt[(OC4H2)C(Me)؍NN؍C(S)NHEt]}2{µ-
Ph2P(CH2)2PPh2}]
a
a
a
a
a
a
´
´
´
Luis Adrio , Jose M. Antelo , Juan M. Ortigueira , Darıo Lata , M Teresa Pereira , Margarita Lopez-
b
a,
´
Torres , Jose M. Vila *
a
´
´
Santiago de Compostela, Spain, Universidad de Santiago de Compostela Departamento de Quımica Inorganica,
b
´
A Corun˜a / Spain, Universidad de A Corun˜a, Departamento de Quımica Fundamental
Received May 10th, 2007.
˜
Dedicated to Professor Alfonso Castineiras on the Occasion of his 65th Birthday
Abstract. Treatment of thiosemicarbazones (OC4H3)C(Me)ϭ
NN(H)C(ϭS)NHR (R: Me, a; Et, b) with [cis-PtMe2(cod)] afforded
the tetranuclear compounds [Pt{(OC4H2)C(Me)ϭNNϭC(S)NHR}]4
(R: Me, 1a; Et, 1b). The reaction of 1a and 1b with triphenylphos-
phine in 1:4 molar ratio gave rise to the mononuclear compounds
[Pt{(OC4H2)C(Me)ϭNNϭC(S)NHR}(PPh3)] (2a, 2b). Treatment
of 1a and 1b with large-bite diphosphines Ph2P(CH2)nPPh2 (n ϭ 2,
dppe; n ϭ 3, dppp; n ϭ 4, dppb) afforded the dinuclear compounds
[{Pt[(OC4H2)C(Me)ϭNNϭC(S)NHR]}2{µ-Ph2P(CH2)nPPh2}],
(3a؊5a, 3b؊5b), with the diphosphine in a bridging mode. Similar
reactions with the short-bite diphosphines Ph2PCH2PPh2 (dppm)
and Ph2PC(ϭCH2)PPh2 (vdpp) yielded the mononuclear com-
pounds [Pt{(OC4H2)C(Me)ϭNNϭC(S)NHR}-(Ph2PCH2PPh2-P)]
(6a, 6b) and [Pt{(OC4H2)C(Me)ϭNNϭC(S)NHR}(Ph2P-C(ϭ
CH2)PPh2-P)] (7a, 7b) with the diphosphine in a monodentate co-
ordination. Treatment of 1a and 1b with [W(CO)5(Ph2CH2PPh2)]
gave the novel heterodinuclear species [{Pt[(OC4H2)C(Me)ϭNNϭ
C(S)NHR]}{W(CO)5(Ph2CH2PPh2-P)}] (8a, 8b), which could also
be synthesized by reaction of 6a and 6b with [W(CO)5(THF)].
1H, 31P-{1H} and 13C-{1H} NMR and IR data are given. The crys-
tal structure of compound 3b has been determined by X-ray crys-
tallography.
Keywords: Platinum; Metallation; Thiosemicarbazone; Furane;
Phosphorus ligands; Crystal structures
1 Introduction
[11], or as highly tunable photooxidants or photoreductants
[12]. Recently, platinum species have represented an import-
ant class of complexes particularly from the point of view
of their luminescent properties, and the usage of the phos-
phorescent complexes as emitters in light-emitting diodes
(LEDS) [13].
The cyclometallation reaction, i.e. the intramolecular acti-
vation of aromatic C-H bonds by transition metals in coor-
dinated ligands, has been widely investigated, especially in
the case of phenyl rings. The ease of metallation is depen-
dent on the directing influence of the ring substituents, as
well as on steric factors [1]. The main interest in this type
of compounds stems from their salient applications, such as
for instance, to serve as intermediates in organic and or-
ganometallic synthesis [2], as active catalysts [3], liquid crys-
tals [4], analytical tools [5], to allow the resolution of ra-
cemic mixtures [6], and for the design of metal complexes
with promising anticancer [7] or photochemical properties
[8]. In particular, nitrogen, phosphorus or sulfur containing
platinacycles [9] also offer attractive applications as cata-
lysts in the assymmetric aldol-type condensation of isocyan-
Cyclometallation reactions of heterocyclic derivatives
have been less extensively studied, in spite that heterocycles
are expected to possess unique properties in applied fields
of chemistry and pharmacy [14], not encountered in phenyl
derivatives. Work related to cyclometallated complexes
derived from simple five-membered heterocycles such as fu-
rane, thiophene and pyrrole [15], or benzo fused five-mem-
bered heterocycles [16], have been reported. Thus, treatment
of the appropriate ligands with Li2[PdCl4] or K2[PtCl4] gave
chloro-bridged dinuclear complexes; whilst reaction with
palladium(II) acetate (the most commonly used pal-
ladium(II) salt in metallation processes) did not afford the
well known acetato-bridged dimer complexes [17]; instead,
unexpected mononuclear nitro complexes were formed via
oxidation of the acetonitrile used as solvent.
i
ides and aldehydes in the presence of Pr2NEt [10], in
Michael and Diels-Alder reactions for C-C bond formation
´
* Prof. Dr. Jose M. Vila
Furthermore, thiosemicarbazones and semicarbazones
have been known to form stable complexes with many tran-
sition metal ions [18]. Our interest in cyclometallated com-
pounds has been, in part, focused on the study of complexes
derived from [C,N,S] terdentate ligands such as thiosemicar-
Universidad de Santiago de Compostela
´
´
Departamento de Quımica Inorganica
E-15782 Santiago de Compostela / Spain
Fax: ϩ34/981-595012
E-mail: qideport@usc.es
Z. Anorg. Allg. Chem. 2007, 633, 1875Ϫ1882
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1875

´
L. Adrio, J. M. Antelo, J. M. Ortigueira, D. Lata, M. T. Pereira, M. Lopez-Torres, J. M. Vila
added. The resulting mixture was heated under reflux for 6 h. After
cooling to room temperature the white solid formed was filtered
off, washed with water, dried in vacuo and recrystallized in etanol.
Yield 749 mg, 80 %. Anal. Found: C, 49.1; H, 5.5; N, 21.1; S, 16,0;
C8H11N3OS (197.26 g/mol) requires C, 48.7; H, 5.6; N, 21.3; S,
16.3 %.
IR /cmϪ1: ν(CϭN) 1631w, ν(CϭS) 824w. 1H NMR (CDCl3, δ, J Hz): 8.59
(s, NH); 7.64 (b, NHMe); 7.48 (d, H5, 3J(H4H5) 1.9); 6.72 (d, H3, 3J(H4H3)
3.5); 6.46 (dd, H4, 3J(H4H3) 3.5, 3J(H4H5) 1.9); 3.25 (d, NHMe, 3J(MeH) ϭ
4.7); 2.18 (s, CMe). 13C NMR (CDCl3, δ, J Hz): 178,99 (s, CCϭS); 149,50
(s, C2); 144,87 (s, CCϭN); 144,54 (s, C5); 112,33 (s, C3); 111,56 (s, C4); 31,64
(s, CMe); 21,20 (s, NMe).
bazones or Schiff base ligands with additional sulfur donor
atoms, which react readily with M2[PdCl4] (M ϭ Li, K),
Pd(OAc)2 or K2[PtCl4] to give mono- or tetranuclear com-
pounds (see Figure 1) [19], depending on the nature of the
starting ligand. All complexes showed a metallated carbon
atom belonging to a phenyl ring as depicted in Figure 1,
Ligand b was prepared similarly.
(OC4H3)C(Me)؍NN(H)C(؍S)NHEt (b). ؊ Yield: 739 mg, 83 %.
Anal. Found: C, 51.4; H, 6.0; N, 20.0; S, 15.3; C9H13N3OS
(211.28 g/mol) requires C, 51.2; H, 6.2; N, 19.9; S, 15.2 %.
IR (cmϪ1): ν(CϭN) 1611w, ν(CϭS) 814w. 1H NMR (CDCl3, δ, J Hz): 8,51
(s, NH); 7.58 (b, NHEt); 7.49 (d, H5, 3J(H4H5) ϭ 1.6); 6,73 (d, H3,
3J(H3H4) ϭ 3.5); 6.47 (dd, H4, 3J(H3H4) ϭ 3.5; 3J(H4H5) ϭ 1.6); 3.76 (qd,
NCH2Me, 3J(HH) ϭ 5.5, 3J(HH) ϭ 8.1); 2.19 (s, CMe); 1.31 (t, NCH2Me,
3J(HH) ϭ 8.1). 13C NMR (CDCl3, δ, J Hz): 177,79 (s, CCϭS); 149,52 (s, C2);
144,86 (s, CCϭN); 144,52 (s, C5); 112,34 (s, C3); 111,42 (s, C4); 39,89
(s, NCH2); 21,21 (s, CMe); 14,84 (s, NCH2Me).
Preparation of [Pt{(OC4H2)C(Me)؍NN؍C(S)NHMe}]4 (1a). ؊ Li-
Figure 1
gand
a (65 mg, 0.330 mmol) and [cis-PtMe2(cod)] (100 mg,
0.300 mmol) were refluxed in 25 cm3 of anhydrous n-octane for 2 h
under nitrogen. After cooling to room temperature, the orange
solid formed was filtered and dried in vacuo. Yield: 67 mg, 57 %.
Anal. Found: C, 24.8; H, 2.4; N, 10.6; S, 8.4; C32H36N12O4Pt4S4
(1561.28 g/mol) requires C, 24.6; H, 2.3; N, 10.8; S, 8.2 %.
IR /cmϪ1: ν(CϭN) 1618sh. 1H NMR (CDCl3, δ, J Hz): 7.29 (s, H5); 6.41
(s, H4); 5.02 (q, NHMe, 3J(MeH) ϭ 4.9); 3.01 (d, NHMe, 3J(MeH) ϭ 4.9);
1.97 (s, CMe). ESI-MS: m/z ϭ 1561 [M]ϩ; 390 [M/4]ϩ.
However, work concerning the heteroaromatic thio- and
semicarbazone derivatives are scarce, mainly due to the
large number of potential coordination sites they present,
which usually gives rise to a complex chelation chemistry.
In the present paper we report the synthesis of new cyclo-
platinated compounds derived from thiosemicarbazones in
which the metallated carbon atom belongs to a furane ring,
as well as the preliminary results concerning novel heterodi-
nuclear platinum-tungsten compounds.
Compound 1b was prepared analogously.
[Pt{(OC4H2)C(Me)؍NN؍C(S)NHEt}]4 (1b).
؊ Yield: 69 mg,
57 %. Anal. Found: C, 27.0; H, 2.9; N, 10.3; S, 7.8;
C36H44N12O4Pt4S4 (1617.38 g/mol) requires C, 26.7; H, 2.7; N,
10.4; S, 7.9 %.
IR /cmϪ1: ν(CϭN) 1590sh. 1H NMR (CDCl3, δ, J Hz): 7.28 (d, H5,
3J(H4H5) ϭ 1.6); 6.40 (d, H4, 3J(H4H5) ϭ 1.6); 5.04 (t, NHEt, 3J(HH) ϭ
5.9); 3.43 (qd, NCH2Me, 3J(HH) ϭ 5.9, 3J(HH) ϭ 9.3); 1.96 (s, CMe); 1.22
(t, NCH2Me, 3J(HH) ϭ 9.3). ESI-MS: m/z ϭ 1617 [M]ϩ; 404 [M/4]ϩ.
2 Experimental Section
General procedures
All solvents were distilled prior to use from appropriate drying
agents [20]. Chemicals were used as supplied from commercial
´
sources. Microanalyses were carried out at the Servicio de Analisis
Preparation of [Pt{(OC4H2)C(Me)؍NN؍C(S)NHMe}(PPh3)] (2a).
؊ To 1a (20 mg, 0.013 mmol) in chloroform (10 cm3), PPh3 (14 mg,
0.053 mmol) was added in a complex/phosphine 1:4 molar ratio.
The resulting mixture was heated under nitrogen for 10 min. The
solvent was removed under reduced pressure and the residue recrys-
tallized from chloroform/n-hexane. Yield: 19 mg, 56 %. Anal.
Found: C, 48.1; H, 3.9; N, 6.3; S, 5.1. C26H24N3OPPtS (652.61 g/mol)
requires C, 47.9; H, 3.7; N, 6.4; S, 4.9 %.
Elemental at the University of Santiago, with a Carlo-Erba El-
emental Analyser 1108. IR spectra were recorded as KBr pellets or
Nujol mulls with a Perkin-Elmer 1330 and with a Mattson spectro-
photometers. NMR spectra were obtained as CDCl3 solutions and
referenced to SiMe4 (1H, 13C-{1H}) or 85 % H3PO4 (31P-{1H}); and
were recorded on a Bruker WM250 and AMX 300 spectrometers
(200.0 MHz for 1H, 50.3 MHz for 13C-{1H}, 81.0 MHz for
31P-{1H}). Electrospray mass spectra were recorded on a Finnigan
Navigator spectrometer with acetonitrile as the solvent.
IR /cmϪ1: ν(CϭN) 1610sh. 1H NMR (CDCl3, δ, J Hz): 6.97 (s, H5); 4.99
(s, H4); 4.65 (q, NHMe, 3J(MeH) ϭ 4.7); 2.96 (d, NHMe); 2.34 (s, CMe).
31P-{1H} NMR (CDCl3, δ, J Hz): 16.60 (s, 1J(PtP) ϭ 3743.4).
Synthesis
Compound 2b was prepared in a similar manner.
Preparation of (OC4H3)C(Me)؍NN(H)C(؍S)NHMe (a). ؊ To a
solution obtained by heating methyl-thiosemicarbazide (0.500 g,
4.755 mmol) and 1 cm3 of acetic acid in 25 cm3 of water a solution
of 2-acetylfurane (0.524 g, 4.759 mmol) in 25 cm3 of ethanol was
[Pt{(OC4H2)C(Me)؍NN؍C(S)NHEt}(PPh3)] (2b).
؊
Yield:
16 mg, 49 %. Anal. Found: C, 48.4; H, 4.1; N, 6.2; S, 4.6;
C27H26N3OPPtS (666.63 g/mol) requires C, 48.7; H, 3.9; N, 6.3;
S, 4.8 %.
1876
www.zaac.wiley-vch.de
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 1875Ϫ1882

Cycloplatination of Thiosemicarbazones Derived from Furane
IR /cmϪ1: ν(CϭN) 1595sh. 1H NMR (CDCl3, δ, J Hz): 6.98 (d, H5,
3J(H4H5) ϭ 1.6); 5.01 (d, H4, 3J(H4H5) ϭ 1.6); 4.66 (b, NHEt); 3.37 (qd,
NCH2Me, 3J(HH) ϭ 5.2, 3J(HH) ϭ 8.5); 2.34 (s, CMe); 1.12 (t, NCH2Me,
3J(HH) ϭ 8.5). 31P-{1H} NMR (CDCl3, δ, J Hz): 16.65 (s, 1J(PtP) ϭ 3743.4).
Preparation
(Ph2PCH2PPh2-P)] (6a). To
of
[Pt{(OC4H2)C(Me)؍NN؍C(S)NHMe}-
´
suspension of 1a (20 mg,
a
0.013 mmol) in chloroform (10 cm3) 1,1-bis(diphenylphosphino)-
methane (dppm, 20 mg, 0.052 mmol) was added and the resulting
mixture was heated under nitrogen for 10 min. The solvent was
removed under reduced pressure and the residue recrystallized in
chloroform/n-hexane. Yield: 16 mg, 41 %. Anal. Found: C, 50.9; H,
4.2; N, 5.5; S, 4.3. C33H31N3OP2PtS (774.71 g/mol) requires C,
51.2; H, 4.0; N, 5.4; S, 4.1 %.
Preparation
Ph2P(CH2)2PPh2}] (3a).
of
[{Pt[(OC4H2)C(Me)؍NN؍C(S)NHMe]}2{µ-
To suspension of 1a (20 mg,
؊
a
0.013 mmol) in chloroform (10 cm3) 1,2-bis(diphenylphosphino)-
ethane (10 mg, 0.025 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. Yield: 16 mg, 53 %. Anal. Found: C, 42.5; H, 3.7; N, 7.0;
S, 5.46. C42H42N6O2P2Pt2S2 (1178.16 g/mol) requires C, 42.8; H,
3.6; N, 7.1; S, 5.44 %.
IR /cmϪ1: ν(CϭN) 1616sh. 1H NMR (CDCl3, δ, J Hz): 6.94 (s, H5); 5.08 (s,
H4); 4.72 (d, NHMe, 3J(MeH) ϭ 5.2); 3.37 (d, PCH2); 3.00 (d, NHMe,
3J(MeH) ϭ 5.2); 2.28 (s, CMe). 31P-{1H} NMR (CDCl3, δ, J Hz): 6.15d,
2J(PP) ϭ 71.2; 1J(PtP) ϭ 3723.2; Ϫ27.90d, 1J(PP) ϭ 71.2.
IR /cmϪ1: ν(CϭN) 1615sh. 1H NMR (CDCl3, δ, J Hz): 6.95 (b, H5); 5.05 (b,
H4); 4.65 (q, NHMe, 3J(MeH) ϭ 4.7), 3.01 (d, NHMe, 3J(MeH) ϭ 4.7); 2.34
(s, CMe). 31P-{1H} NMR (CDCl3, δ, J Hz): 12.56 (s, 1J(PtP) ϭ 3692.6).
Compounds 7a, 6b and 7b were synthesized following a similar pro-
cedure.
[Pt{(OC4H2)C(Me)؍NN؍C(S)NHMe}{Ph2PC(؍CH2)PPh2-P}]
(7a). ؊ Yield: 23 mg, 56 %. Anal. Found: C, 51.6; H, 4.2; N, 5.1;
S, 4.0. C34H31N3OP2PtS (786.72 g/mol) requires C, 51.9; H, 4.0; N,
5.3; S, 4.1 %.
IR /cmϪ1: ν(CϭN) 1615sh. 1H NMR (CDCl3, δ, J Hz): 6.97 (s, H5); 5.07 (s,
H4); 6.81, 5.79 (dd, CϭCH2, trans-3J(PH) ϭ 27, cis-3J(PH) ϭ 16); 4.70 (d,
NHMe, 3J(MeH) ϭ 4.7); 2.99 (d, NHMe, 3J(MeH) ϭ 4.7); 2.31 (s, CMe).
31P-{1H} NMR (CDCl3, δ, J Hz): 23.00d, 2J(PP) ϭ 76.3, 1J(PtP) ϭ 3784.2;
Ϫ12.55d, 2J(PP) ϭ 76.3.
Compounds 4a, 5a, and 3b؊5b were synthesized following a simi-
lar procedure.
[{Pt[(OC4H2)C(Me)؍NN؍C(S)NHMe]}2{µ-Ph2P(CH2)3PPh2}]
(4a). ؊ Yield: 18 mg, 60 %. Anal. Found: C, 43.5; H, 3.9; N, 6.9;
S, 5.3. C43H44N6O2P2Pt2S2 (1193.08 g/mol) requires C, 43.3; H, 3.7;
N, 7.0; S, 5.4 %.
IR /cmϪ1: ν(CϭN) 1610sh. 1H NMR (CDCl3, δ, J Hz): 6.98 (s, H5); 5.13 (s,
H4); 3.24 (d, NHMe, 3J(MeH) ϭ 4.7); 2.74 (s, CMe); 2.74 (b, PCH2); 2.40
(b, PCH2CH2). 31P-{1H} NMR (CDCl3, δ, J Hz): 8.11 (s, 1J(PtP) ϭ 3672.2).
[Pt{(OC4H2)C(Me)؍NN؍C(S)NHEt}(Ph2PCH2PPh2-P)] (6b). ؊
Yield: 19 mg, 45 %. Anal. Found: C, 51.5; H, 4.4; N, 5.2; S, 4.1.
C34H33N3OP2PtS (788.74 g/mol) requires C, 51.8; H, 4.2; N, 5.3;
S, 4.1 %.
IR /cmϪ1: ν(CϭN) 1596sh. 1H NMR (CDCl3, δ, J Hz) 6.94 (d, H5,
3J(H4H5) ϭ 1.6, 4J(PtH5) ϭ 10.6); 5.07 (d, H4, 3J(PtH4) ϭ 10.6); 4.73 (t,
NHEt, 3J(HH) ϭ 5.6); 3.41 (qd, NCH2Me, 3J(HH) ϭ 5.6, 3J(HH) ϭ 8.7);
2.27 (s, CMe); 1.79 (d, PCH2); 1.15 (t, NCH2Me, 3J(HH) ϭ 8.7). 31P-{1H}
NMR (CDCl3, δ, J Hz): 3.70d, 2J(PP) ϭ 73.2, 1J(PtP) ϭ 3717.0; Ϫ30.40d,
2J(PP) ϭ 73.2.
[{Pt[(OC4H2)C(Me)؍NN؍C(S)NHMe]}2{µ-Ph2P(CH2)4PPh2}]
(5a). ؊ Yield: 23 mg, 73 %. Anal. Found: C, 43.7; H, 4.0; N, 7.2;
S, 5.5. C44H46N6O2P2Pt2S2 (1207.11 g/mol) requires C, 43.8; H, 3.8;
N, 7.0; S, 5.3 %.
IR /cmϪ1: ν(CϭN) 1610sh. 1H NMR (CDCl3, δ, J Hz): 6.99 (s, H5); 5.14 (s,
H4); 4.71 (q, NHMe, 3J(MeH) ϭ 4.9); 2.98 (d, NHMe); 2.46 (b, PCH2CH2);
2.31 (s, CMe); 1.99 (b, PCH2CH2). 31P-{1H} NMR (CDCl3, δ, J Hz): 7.33 (s,
1J(PtP) ϭ 3692.6).
[Pt{(OC4H2)C(Me)؍NN؍C(S)NHEt}{Ph2PC(؍CH2)PPh2-P}]
(7b). ؊ Yield: 18 mg, 46 %. Anal. Found: C, 52.2; H, 4.3; N, 5.4;
S, 3.9. C35H33N3OP2PtS (800.75 g/mol) requires C, 52.5; H, 4.2; N,
5.3; S, 4.0 %.
[{Pt[(OC4H2)C(Me)؍NN؍C(S)NHEt]}2{µ-Ph2P(CH2)2PPh2}]
(3b). ؊ Yield: 23 mg, 77 %. Anal. Found: C, 43.6; H, 3.9; N, 7.2;
S, 5.1; C44H46N6O2P2Pt2S2 (1206.19 g/mol) requires C, 43.8; H, 3.8;
N, 7.0; S, 5.3 %.
IR /cmϪ1: ν(CϭN) 1590sh. 1H NMR (CDCl3, δ, J Hz): 6.97 (s, H5); 6.84,
5.81dd (dd, CϭCH2, trans-3J(PH) ϭ 29, cis-3J(PH) ϭ 17); 5.09 (s, H4); 4.71
(b, NHEt); 3.41 (qd, NCH2Me, 3J(HH) ϭ 5.3, 3J(HH) ϭ 8.4); 2.30 (s, CMe);
1.16 (t, NCH2Me, 3J(HH) ϭ 8.4). 31P-{1H} NMR (CDCl3, δ, J Hz): 23.10d,
2J(PP) ϭ 76.2, 1J(PtP) ϭ 3684.2; Ϫ12.50d, 2J(PP) ϭ 76.2.
IR /cmϪ1: ν(CϭN) 1591sh. 1H NMR (CDCl3, δ, J Hz): 6.95 (b, H5); 5.07 (b,
H4); 4.71(b, NHEt); 3.41 (qd, NCH2Me, 3J(HH) ϭ 5.1, 3J(HH) ϭ 7.8); 2.86
(b, PCH2); 2.33 (s, CMe); 1.17 (t, NCH2Me, 3J(HH) ϭ 7.8). 31P-{1H} NMR
(CDCl3, δ, J Hz): 12.56 (s, 1J(PtP) ϭ 3743.4).
[{Pt[(OC4H2)C(Me)؍NN؍C(S)NHEt]}2{µ-Ph2P(CH2)3PPh2}]
(4b). ؊ Yield: 24 mg, 79 %. Anal. Found: C, 44.5; H, 3.9; N, 7.1;
S, 5.4.; C45H48N6O2P2Pt2S2 (1221.14 g/mol) requires C, 44.3; H,
4.0; N, 6.9; S, 5.3 %.
IR /cmϪ1: ν(CϭN) 1590sh. 1H NMR (CDCl3, δ, J Hz): 6.98 (s, H5); 5.15 (s,
H4); 4.68 (b, NHEt); 3.42 (qd, NCH2Me, 3J(HH) ϭ 5.2, 3J(HH) ϭ 8.4); 2.75
(b, PCH2CH2); 2.47 (b, PCH2CH2); 2.31 (s, CMe); 2.09 (b, PCH2CH2); 1.16
(t, NCH2Me, 3J(HH) ϭ 8.4). 31P-{1H} NMR (CDCl3, δ, J Hz): 8.14 (s,
1J(PtP) ϭ 3662.2).
Preparation of [Pt{(OC4H2)C(Me)؍NN؍C(S)NHMe}{(WCO)5-
(Ph2CH2PPh2-P)}] (8a).
؊ To a suspension of 1a (20 mg,
0.012 mmol) in chloroform (10 cm3) [W(CO)5(Ph2CH2PPh2)]
(35 mg, 0.049 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: 40 mg, 71 %. Anal. Found: C, 41.9; H, 2.7; N, 3.6;
S, 3.1. C38H31N3O6P2PtSW (1098.60 g/mol) requires C, 41.5; H,
2.8; N, 3.8; S, 2.9 %.
[{Pt[(OC4H2)C(Me)؍NN؍C(S)NHEt]}2{µ-Ph2P(CH2)4PPh2}]
(5b). ؊ Yield: 19 mg, 61 %. Anal. Found: C, 44.9; H, 4.2; N, 7.0;
S, 5.0. C46H50N6O2P2Pt2S2 (1235.16 g/mol) requires C, 44.7; H, 4.1;
N, 6.8; S, 5.2 %.
IR /cmϪ1: ν(CϭN) 1611m. 1H NMR (CDCl3, δ, J Hz): 7.02 (s, H5); 5.23 (s,
H4); 4.68 (b, NHMe); 3.00 (d, NHMe, 3J(MeH) ϭ 4.7); 2.28 (s, CMe); 2.01
(b, PCH2). 31P-{1H} NMR (CDCl3, δ, J Hz): 8.75d, 2J(PP) ϭ 25.4, 1J(WP) ϭ
245.7; 2.87d, 1J(PP) ϭ 25.4, 1J(PtP) ϭ 3784.2.
IR /cmϪ1: ν(CϭN) 1586sh. 1H NMR (CDCl3, δ, J Hz): 6.97 (d, H5,
3J(H4H5) ϭ 1.6, 4J(PtH5) ϭ 10.6); 5.15 (d, H4, 3J(H4H5) ϭ 1.6, 3J(PtH4) ϭ
11.3); 4.70 (t, NHEt); 3.38 (qd, NCH2Me, 3J(HH) ϭ 5.9, 3J(HH) ϭ 9.1);
2.46 (b, PCH2CH2); 2.30 (s, CMe); 1.76 (b, PCH2CH2); 1.14 (t, NCH2Me,
3J(HH) ϭ 9.1). 31P-{1H} NMR (CDCl3, δ, J Hz): 7.28 (s, 1J(PtP) ϭ 3680.4).
Compound 8b was prepared analogously.
[Pt{(OC4H2)C(Me)؍NN؍C(S)NHEt}{(WCO)5(Ph2CH2PPh2-P)}]
(8b). ؊ Yield: 42 mg, 77 %. Anal. Found: C, 42.2; H, 3.1; N, 3.6;
Z. Anorg. Allg. Chem. 2007, 1875Ϫ1882
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1877

´
L. Adrio, J. M. Antelo, J. M. Ortigueira, D. Lata, M. T. Pereira, M. Lopez-Torres, J. M. Vila
S, 2.8. C39H33N3O6P2PtSW (1112.63 g/mol) requires C, 42.1; H,
3.0; N, 3.8; S, 2.9 %.
IR /cmϪ1: ν(CϭN) 1607m. 1H NMR (CDCl3, δ, J Hz): 7.01 (d, H5,
3J(H4H5) ϭ 1.6); 5.22 (d, H4, 3J(H4H5) ϭ 1.6); 4.75 (b, NHEt); 3.42 (qd,
NCH2Me, 3J(HH) ϭ 5.7, 3J(HH) ϭ 8.9); 2.28 (s, CMe); 2.05 (b, PCH2). 1.19
(t, NCH2Me, 3J(HH) ϭ 8.9). 31P-{1H} NMR (CDCl3, δ, J Hz): 6.27d,
2J(PP) ϭ 24.9, 1J(WP) ϭ 246.3; 0.40d, 2J(PP) ϭ 24.9, 1J(PtP) ϭ 3772.0.
formulations, but the FAB mass spectra only showed peaks
at low values of m/z probably due to a fast fragmentation of
the compounds. Nevertheless, the electrospray mass spectra
registered the corresponding peaks at m/z 1561 (1a) and
1617 (1b) whose isotopic composition suggests a structure
comprising four cyclometallated units [24]. A similar trend
has been observed for other cyclometallated compounds of
PdII and PtII derived from thiosemicarbazones by us [19a,
19b] and others [7a, 25]. The IR data were in agreement
with deprotonation of the ligand at the hydrazynic nitrogen
on complex formation [25, 26], and also showed the ν(Cϭ
N) band shifted to lower wavenumbers [26a, 27], contrary
to the trend observed for other thiosemicarbazone com-
plexes, with shift to higher wavenumbers [23]; likewise, the
ν(CϭS) band disappeared in agreement with loss of the
double bond character upon deprotonation of the NH
Crystal structure
Three-dimensional, room temperature X-ray data were collected on
a Siemens SMART CCD diffractometer by the omega scan
method. Reflections were measured from a hemisphere of data col-
lected of frames each covering 0.3 degrees in omega. Of the 42816
reflections measured, all of which were corrected from Lorentz and
polarisation effects and for absorption by semi-empirical methods
based on symmetry-equivalent and repeated reflections (max./min.
transmissions; 0.389, 0.076), 12823 independent reflections ex-
ceeded the significance level IFI/σIFI > 4.0. The structure was
solved by direct methods and refined by full matrix least squares
on F2. Hydrogen atoms were included in calculated positions and
refined in riding mode. Refinement converged at a final R ϭ 0.0434
(wR2 ϭ 0.0924, for all 12823 unique data; 626 parameters), with
allowance for the thermal anisotropy of all non-hydrogen atoms.
Minimum and maximum final density Ϫ0.838 and 0.767 eAϪ3. The
structure solution and refinement were carried out using the pro-
gram package SHELX-97 [21].
1
group. The H NMR spectra showed absence of the NH
group resonance, in agreement as well, with deprotonation
as observed in other coordination and organometallic com-
pounds of similar ligands [26]. The absence of the H3 reson-
ance put forward metallation of the ligands and two singlets
or two doublets, as appropriate, ca. 7.25 and ca. 6.40 ppm
were assigned to the H5 and H4 proton resonances, respec-
tively. The CMe resonance was upfield shifted ca. 0.2 ppm
indicating a shielding effect which has not been observed in
any other derivative of these ligands. These results were in
agreement with a tetranuclear structure in which the coordi-
nation sphere at platinum is occupied by a carbon atom, a
nitrogen atom and a sulfur atom of the thiosemicarbazone
ligand, with the fourth coordination site being occupied by
a sulfur atom of an adjacent cycloplatinated moiety. No
coupling of the CMe group, nor of the H4 and H5 protons
with the 195Pt nucleus was observed, following the trend
shown in related as with other cycloplatinated complexes
[28].
Treatment of 1a and 1b with tertiary phosphines gave
mono- or dinuclear species, as appropriate, where only the
bond at palladium atom to the Sbridging atom was cleaved.
The Pd-Schelating bond of the tridentate thiosemicarbazone
ligands remains, even when a large excess of monophos-
phine or diphosphine was used; in the latter case stabiliz-
ation caused by the chelate effect of the bidentate phos-
phine did not promote Schelating bond cleavage. This is remi-
niscent of the trend observed in related cyclometallated
thiosemicarbazone Pd4 cluster complexes, and further sup-
ports the greater strength of the Pd-Schelating bond as com-
pared to the Pd-Sbridging bond [19a]. Thus, the reaction
of 1a and 1b with tertiary phosphines in 1:4 or in 1:2 molar
Crystallographic data (excluding structure factors) for the structure
reported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no.
645840. Copies of the data can be obtained free of charge on appli-
cation to The Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK.
3 Results and Discussion
For the convenience of the reader the compounds and reac-
tions are shown in Scheme 1. The compounds described in
this paper were characterized by elemental analysis (C, H,
N), and by IR and 1H, 31P-{1H} and (for the ligands)
13C-{1H} NMR spectroscopy.
The thiosemicarbazones a and b were obtained as air-
stable solids by the reaction of 2-acetylfurane with methyl-
thiosemicarbazide and ethyl-thiosemicarbazide, respec-
tively, and were fully characterized. In the 1H NMR spectra
a singlet ca. 8.50 and a broad signal ca. 7.60 ppm, were
assigned to the NH and NHMe resonances, respectively.
Two doublets and a doublet of doublets ca. 7.5Ϫ6.5 ppm
were assigned to the furane ring protons. The IR spectra
showed the ν(CϭN) stretches at 1631 (a) and 1611 cmϪ1
(b) [22], and the ν(N-H) bands due to the NH groups ca.
3200Ϫ3150 cmϪ1 [23]. Characteristic bands at 824 (a) and
814 cmϪ1 (b) were ascribed to the ν(CϭS) stretching mode.
The reaction of a and b with [cis-PtMe2(cod)] in refluxing
ratio,
as
appropriate,
gave
the
mononuclear
[{Pt[(OC4H2)C(Me)ϭNNϭC(S)NHR]}(PPh3)] (2a, R ϭ
Me; 2b, R ϭ Et) or dinuclear [{Pt[(OC4H2)C(Me)ϭNNϭ
C(S)NHR]}2{µ-Ph2P(CH2)nPPh2}] (R ϭ Me: n ϭ 2, 3a;
n ϭ 3, 4a; n ϭ 4, 5a; R ϭ Et: ϭ 2, 3b; n ϭ 3, 4b; n ϭ 4,
5b) compounds as pure air-stable solids, which were charac-
terized by elemental analysis and spectroscopic methods
n-octane
gave
the
cyclometallated
complexes,
[Pt{(OC4H2)C(Me)ϭNNϭC(S)NHR}]4, (1a, R ϭ Me; 1b,
R ϭ Et), respectively, as air-stable solids with the ligand in
the E,Z configuration. The elemental analysis were consist-
ent with a C32H36N12O4Pt4S4, 1a, C36H44N12O4Pt4S4, 1b,
1
(Scheme 1). In the H NMR spectra the H4 resonance was
upfield shifted ca. 1.5 ppm due to the shielding effect of
1878
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Z. Anorg. Allg. Chem. 2007, 1875Ϫ1882

Cycloplatination of Thiosemicarbazones Derived from Furane
Scheme 1
i) cis-[PtMe2(cod)], n-octane; ii) PPh3 (1:4), CHCl3; iii) Ph2(CH2)nPPh2, n ϭ 2, 3, 4, (1:2), chloroform; iv) Ph2PCH2PPh2; Ph2PC(ϭ
CH2)PPh2 (1:4), CHCl3; v) [W(CO)5(Ph2CH2PPh2)], CHCl3; vi) [W(CO)5(THF)]; CHCl3.
the adjacent phosphine phenyl rings. The 31P-{1H} NMR
spectra showed a singlet ca. 16 ppm, 2a, 2b, and ca.
12Ϫ7 ppm, 3a؊5a, 3b؊5b, (downfield shifted from its posi-
tion in the free ligand), in accordance with P-coordination
to the platinum atom in a phosphorus trans to nitrogen dis-
4J(PtH5) and 3J(PtH4) coupling constants, 10.6 and
11.3 Hz, respectively, could be unambiguously assigned. Re-
action of 1a and 1b with the diphosphines in Ն 1:4 molar
ratio gave a mixture of the dinuclear compounds and free
diphosphine; the strength of the Pt-Schelating bond impedes
the formation of a chelate ring for the diphoshine ligand.
This behaviour is in contrast with that shown by the related
cyclometallated complexes derived from [C,N,S] terdentate
Schiff base ligands [19c] and semicarbazones [31], where the
M-Schelating and M-Ochelating bonds were easily cleaved,
respectively. The resolution of the molecular structure of
compound 3b (see below) confirmed these findings.
1
position [29] with J(Pt-P) ca. 3700 Hz, and in the line of
the “transphobic effect” [30]. For the dinuclear compounds
3a؊5a and 3b؊5b the presence of only a set of signals in
the 1H NMR spectra and of a singlet in the 31P-{1H} NMR
spectra put forward the equivalence of the cycloplatinated
moieties, on the one hand, and of the phosphorus nuclei,
on the other. In the 1H NMR of compound 5b, the
Z. Anorg. Allg. Chem. 2007, 1875Ϫ1882
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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1879

´
L. Adrio, J. M. Antelo, J. M. Ortigueira, D. Lata, M. T. Pereira, M. Lopez-Torres, J. M. Vila
Reactions of 1a and 1b with short-bite diphosphines
Molecular structure of [{Pt[(OC4H2)C(Me)؍NN؍
C(S)NH(CH2Me)]}2{µ-Ph2P-(CH2)2PPh2}] (3b)
Ph2PCH2PPh2 (dppm) and Ph2PC(ϭCH2)PPh2 (vdpp)
yielded the mononuclear compounds [Pt{(OC4H2)C(Me)ϭ
NNϭC(S)NHR}(Ph2PCH2PPh2-P)] (6a, R ϭ Me; 6b, R ϭ
Et) and [Pt{(OC4H2)C(Me)ϭNNϭC(S)NHR}(Ph2PC(ϭ
CH2)PPh2-P)] (7a, R ϭ Me; 7b, R ϭ Et) as air-stable solids.
Notwithstanding, these short bite bidentate diphosphines
were uncapable of splitting the Pd-Schelating bond, even
when a large excess of the diphosphine was used, and the
products obtained here were the mononuclear compounds
with the thiosemicarbazone as terdentate [C,N,S] and with
the diphosphine ligand acting as monocoordinate. The 31P-
{1H} NMR spectra showed two doublets assigned to the
two inequivalent phosphorus nuclei, the resonance of the
coordinated phosphorus nucleus appeared at higher fre-
quency, and showed coupling to the platinum nucleus, with
1J(Pt-P) ca. 3700 Hz. The 1H NMR spectra showed an
apparent doublet for the PCH2P resonance (ABXY spin
system); whereas a doublet of doublets ca. 5.8 ppm was as-
signed to the vinylidene protons.
Treatment of 1a and 1b with [W(CO)5(Ph2CH2PPh2)] gave
the new heterodinuclear compounds [Pt{(OC4H2)C(Me)ϭ
NNϭC(S)NHR}{W(CO)5(Ph2CH2PPh2-P)}] (8a, R ϭ Me;
8b, R ϭ Et) as air-stable solids which were characterized
by elemental analysis and spectroscopic methods. The most
salient feature was the shift of the resonance of the non-
coordinated phosphorus nucleus, in the 31P NMR spectra,
as compared to its position in the spectrum of the starting
material, towards higher frequency upon coordination to
the tungsten nucleus by ca. 30 ppm, with 1J(W-P) ca.
245 Hz. Alternatively, compounds 8a and 8b could be syn-
thesized by stirring equimolecular amounts of 6a or 6b with
[W(CO)5(THF)] in chloroform for 1 h. A new and vast
range of bimetallic species, whether homo- or heteronu-
clear, may be obtained by this method employing com-
pounds of type 6 and 7, of which the results depicted herein
are but the initial step, and ensuing preparations are cur-
rently in progress.
Suitable crystals of the title compound were grown by
slowly evaporating a chloroform solution. The labeling
scheme for the compound is shown in Figure 2. Crystallo-
graphic data and selected interatomic distances and angles
are listed in Tables 1 and 2.
The crystal structure comprises a molecule of 3b, and
three molecules of CHCl3 per asymmetric unit. The four-
Table 1 Crystal data and structure refinement data for com-
pound 3b.
Empirical formula
C44H46N6O2P2Pt2S2 ·3CHCl3
Formula weight
Temperature
Wavelength
1565.21
293(2) K
0.71073 A
˚
Crystal system
Space group
Unit cell dimensions
triclinic
P1
a ϭ 11.634(2) A
b ϭ 15.890(3) A
¯
˚
˚
˚
Ͱ ϭ 90.090(3)°
β ϭ 100.443(3)°
γ ϭ 92.456(3)°
c ϭ 17.350(3) A
3
˚
Volume
Z
Density (calculated)
Absorption coefficient
F(000)
3151.2(10) A
2
1.650 Mg/m3
4.972 mmϪ1
1520
Crystal size
θ range for data collection
Index ranges
0.63 x 0.47 x 0.19 mm
1.28 to 26.40°
Ϫ14< h< 14, Ϫ19< k< 19, 0< l< 21
42816
Reflections collected
Independent reflections
Completeness to θ ϭ 26.40°
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2σ(I)]
R indices (all data)
Largest diff. peak and hole
12823 [R(int) ϭ 0.0255]
99.1 %
0.389 and 0.076
Full-matrix least-squares on F2
12823 / 0 / 626
1.018
R1 ϭ 0.0323, wR2 ϭ 0.0880
R1 ϭ 0.0434, wR2 ϭ 0.0924
Ϫ3
˚
0.767 and Ϫ0.838 e.A
˚
Table 2 Selected bond distances /A and angles /° for compound
3b.
Pt(1)-C(3)
Pt(1)-N(1)
Pt(1)-S(1)
Pt(1)-P(1)
C(3)-C(4)
C(4)-C(5)
C(5)-N(1)
N(1)-N(2)
N(2)-C(7)
C(7)-S(1)
2.022(5)
2.050(4)
2.317(2)
2.220(1)
1.345(7)
1.442(8)
1.303(6)
1.395(5)
1.298(6)
1.773(5)
Pt(2)-C(38)
Pt(2)-N(4)
Pt(2)-S(2)
Pt(2)-P(2)
C(38)-C(39)
C(39)-C(40)
C(40)-N(4)
N(4)-N(5)
N(5)-C(42)
C(42)-S(2)
2.033(4)
2.052(4)
2.319(1)
2.229(1)
1.357(6)
1.433(7)
1.298(6)
1.387(6)
1.322(7)
1.759(5)
C(3)-Pt(1)-N(1)
N(1)-Pt(1)-S(1)
S(1)-Pt(1)-P(1)
P(1)-Pt(1)-C(3)
Pt(1)-C(3)-C(4)
C(3)-C(4)-C(5)
C(4)-C(5)-N(1)
C(5)-N(1)-Pt(1)
Pt(1)-N(1)-N(2)
N(1)-N(2)-C(7)
N(2)-C(7)-S(1)
C(7)-S(1)-Pt(1)
Pt(1)-P(1)-C(22)
80.42(2)
82.00(12)
103.00(4)
94.60(15)
108.6(4)
124.1(5)
109.3(4)
117.4(3)
123.7(3)
112.7(4)
126.2(4)
95.99(16)
112.37(14)
C(38)-Pt(2)-N(4)
N(4)-Pt(2)-S(2)
S(2)-Pt(2)-P(2)
80.17(18)
82.08(12)
103.93(4)
93.66(14)
108.8(3)
123.2(4)
110.5(4)
117.3(3)
124.0(3)
111.3(4)
126.6(4)
95.96(18)
108.92(14)
P(2)-Pt(2)-C(38)
Pt(2)-C(38)-C(39)
C(38)-C(39)-C(40)
C(39)-C(40)-N(4)
C(40)-N(4)-Pt(2)
Pt(2)-N(4)-N(5)
N(4)-N(5)-C(42)
N(5)-C(42)-S(2)
C(42)-S(2)-Pt(2)
Pt(2)-P(2)-C(23)
Figure
2 Molecular structure of [{Pt[(OC4H2)C(Me)ϭNNϭ
C(S)NHEt]}2{µ-Ph2P(CH2)2PPh2}] (3b), with labelling scheme.
Hydrogen atoms have been omitted for clarity.
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Z. Anorg. Allg. Chem. 2007, 1875Ϫ1882

Cycloplatination of Thiosemicarbazones Derived from Furane
Figure 3 Hydrogen bond interactions in complex 3b. The atoms involved have been labeled.
coordinated platinum(II) is bonded to an α-carbon atom of
the furane ring, a nitrogen atom of the imine group and a
thioamide sulfur atom (trans to C3) of the deprotonated
thiosemicarbazone ligand. A phosphorus atom from the di-
phosphine ligand, which bridges the two metal atoms, com-
pletes the metal coordination sphere. The sum of angles
about platinum is 360.04°, with the distortion most notice-
able in the somewhat reduced “bite” angle of the metallated
moiety consequent upon double C,N and N,S chelation.
The requirements of the five-membered rings force the
bond angles C(3)ϪPt(1)ϪN(1) and N(1)ϪPt(1)ϪS(1) to
80.42(2)° and 82.00(12)°, respectively. The configuration
around the palladium atom is slightly distorted square-
planar, the mean deviation from the least squares plane is
with angle between planes of 5.01°. The N,S- chelate ring
(Pt1, N1, N2, C7, S1) is also planar, r.m.s. 0.0136, and the
angle between the two fused five-membered chelate rings
is 1.38°.
The molecular units are stacked in dimers held together
by intermolecular hydrogen bonding between the NHEt hy-
drogen atom and the sulfur atom with N(3)ϪH(3)···S(1)#1
˚
3.499 A, with an angle of 126.70° (see Figure 3).
´
Acknowledgments. We thank the Ministerio de Educacion y Ciencia
(Project CTQ2006-15621-C02-01/BQU) for financial support. L. A.
Adrio and J. M. Antelo acknowledge fellowships from the Xunta
de Galicia.
˚
˚
0.0044 A, Pt(1) and 0.0622 A, Pt(2).
The platinum-nitrogen bond lengths in the metallacycle,
˚
˚
Pt(1)ϪN(1) 2.050(4) A, Pt(2)ϪN(4) 2.052(4) A, are longer
˚
References
than the predicted single bond value of 1.981 A, based on
the sum of covalent radii for nitrogen(sp2) and platinum,
˚
[1] (a) E. C. Constable, Polyhedron 1984, 3, 1037; (b) G. R.
Newkome, W. E. Puckett, V. K. Gupta, G. E. Kiefer, Chem.
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137.
[2] (a) L. Main, B. K. Nicholson, Adv. Met. Org. Chem. 1994,
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[3] (a) J. Dupont, M. Pfeffer, J. Spencer, Eur. J. Inorg. Chem. 2001,
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0.701 and 1.28 A, respectively [32] and reflect the trans in-
fluence of the phosphorus atom [28]. The PtϪC and PtϪP
˚
bond lengths, Pt(1)ϪC(3) 2.022(5) A, Pt(2)ϪC(38)
˚
˚
2.033(4) A, and Pt(1)ϪP(1) 2.220(1) A, Pt(2)ϪP(2)
2.229(1), respectively, are shorter than the expected values
˚
˚
of 2.051 A and 2.34 A, also respectively, (based on the sum
2
˚
of the covalent radii for platinum, 1.28 A, carbon(sp ),
0.771 A, and phosphorus, 1.06 A) [33] suggesting a partial
multiple-bond character [34]. The platinum-sulfur bond
lengths, Pt(1)ϪS(1) 2.317(2) A, Pt(2)ϪS(2) 2.319(1) A, are
within the expected ranges and reflect the strong trans influ-
ence of the furane carbon atoms. The C(7)ϪS(1) 1.773(5) A
˚
˚
˚
˚
˚
˚
and C(42)ϪS(2) 1.759(5) A bond distances are consistent
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with increased single-bond character, and the N(2)ϪC(7)
˚
˚
1.298(6) A and N(5)ϪC(42) 1.322 A, with increased
double-bond character in the deprotonated form of the
thiosemicarbazone ligand. The cyclometallated moieties are
nearly co-planar at an angle of 15.16°. The mean deviations
from the least squares planes determined for the metallacy-
cle (Pt1, C3, C4, C5, N1) and the metallated furane ring
˚
(O1, C1, C2, C3, C4) are 0.0211 and 0.0090 A, respectively,
Z. Anorg. Allg. Chem. 2007, 1875Ϫ1882
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www.zaac.wiley-vch.de
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 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 1875Ϫ1882