Cyclometallated thiosemicarbazone palladium(II) compounds: The first crystal and molecular structures of mononuclear complexes with a η1-diphosphine ligand

Article abstract of DOI:10.1016/j.jorganchem.2006.02.014

Treatment of the thiosemicarbazones 2-XC₆H₄C(Me){double bond, long}NN(H)C({double bond, long}S)NHR (R = Me, X = F, a; R = Et, X = F, b; R = Me, X = Cl, c; R = Et, X = Br, d) with potassium tetrachloropalladate(II) in ethanol, lithium

Full text of DOI:10.1016/j.jorganchem.2006.02.014

Journal of Organometallic Chemistry 691 (2006) 2721–2733
www.elsevier.com/locate/jorganchem
Cyclometallated thiosemicarbazone palladium(II) compounds:
The first crystal and molecular structures of mononuclear
complexes with a g1-diphosphine ligand
a
a
a
Javier Martınez , Luis A. Adrio , Jose M. Antelo a,b, Juan M. Ortigueira ,
´
´
a
a
b
b
a,
*
´
´
´
M Teresa Pereira , Jesu´s J. Fernandez , Alberto Fernandez , Jose M. Vila
a
Departamento de Quı´mica Inorga´nica, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain
b
Departamento de Quı´mica Fundamental, Universidad de A Corun˜a, 15071 A Corun˜a, Spain
Received 28 December 2005; accepted 3 February 2006
Available online 6 March 2006
Abstract
Treatment of the thiosemicarbazones 2-XC6H4C(Me)@NN(H)C(@S)NHR (R = Me, X = F, a; R = Et, X = F, b; R = Me, X = Cl, c;
R = Et, X = Br, d) with potassium tetrachloropalladate(II) in ethanol, lithium tetrachloropalladate(II) in methanol or palladium(II) ace-
tate in acetic acid, as appropriate, gave the tetranuclear cyclometallated complexes [Pd{2-XC6H3C(Me)@NN@C(S)NHR}]4 (1a–1d).
Reaction of 1a–1d with the diphosphines Ph2PCH2PPh2 (dppm), Ph2P(CH2)2PPh2 (dppe), Ph2P(CH2)3PPh2 (dppp) or trans-
Ph2PCH@CHPPh2 (trans-dpe) in 1:2 molar ratio gave the dinuclear cyclometallated complexes [{Pd[2-XC6H3C(Me)@NN@C(S)-
NHR]}2(l-diphosphine-P,P)] (2a–5a, 3b, 3d, 4c, 5c). Reaction of 1a, 1b with the short-bite or long-bite diphosphines, dppm or
cis-dpe, in a 1:4 molar ratio gave the mononuclear cyclometallated complexes [Pd{2-XC6H3C(Me)@NN@C(S)NHR}(diphosphine-P)]
(6a, 6b, 7a). The molecular structure of ligand a and of complexes 1a, 3d, 5a, 5c, 6a, 6b and 7a have been determined by X-ray diffraction
analysis. The structure of complex 7a shows that the long-bite cis-bis(diphenylphosphino)ethene phosphine appears as monodentate with
an uncoordinated phosphorus donor atom.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Thiosemicarbazones; Cyclometallation; Palladium; Diphosphines; Crystal structure
1. Introduction
We have studied thiosemicarbazone CNS donors which
yield tetranuclear cyclometallated complexes [21]; for the
related compounds with terdentate ligands possessing
CNN [22a] or CNO [22b] donor atoms, only mononuclear
species were isolated. In the case of the thiosemicarbaz-
ones, these produce tetranuclear compounds with two dis-
tinct palladium-sulfur bonds, i.e., Pd–Schelating and Pd–
Cyclometallated complexes are known for a wide range
of ligands and extended coverage regarding the aspects of
their chemistry is described in various general reviews [1–
5]. Cyclometallated compounds are involved in diverse
branches of chemistry such as regiospecific organic and
organometallic synthesis [6–8], insertion reactions [9,10],
asymmetric synthesis with optically active cyclometallated
compounds [11,12], catalytic materials [13–15], liquid crys-
tals [16], and species with specific antitumoral activity [17–
20].
Sbridging, binding tightly to the metal as terdentate [C, N,
S], and when treated with tertiary diphosphines, in the
resulting compounds each metal atom is bonded to only
one phosphorus atom, the strength of the Pd–Schelating
bond preventing the chelating bidentate mode of the
diphosphine ligand [21a,21c]. Hence, in the resulting com-
plexes, the corresponding diphosphine ligand either bridges
two metal centres, yielding dinuclear compounds, or
*
Corresponding author. Fax: +34 981595012.
E-mail address: qideport@usc.es (J.M. Vila).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.02.014

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J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
1
behaves as a g1-ligand, producing mononuclear species.
Whether the diphosphine coordinates through one or the
two phosphorus donors is a function of the nature of the
ligand and of the reaction conditions, both of which may
be modulated appropriately, as we report herein. There-
fore, described in the present paper is the account concern-
ing the synthesis and characterization of a new series of
mono-, di- and tetranuclear cyclopalladated complexes
derived from halogenated thiosemicarbazone ligands,
inclusive of the first crystal and molecular structures of
the corresponding mononuclear compounds with the perti-
nent g1-diphosphine.
lytical, mass spectra, IR and H and 31P–{1H} NMR data
are in Section 4). The mass spectrum (FAB) showed peaks
at m/z 1318 (1a), 1375 (1b), 1384 (1c) and 1620 (1d) for
the molecular ion whose isotopic composition suggests a
tetranuclear complex of formula C40H40F4N12Pd4S4 (1a),
C44H48F4N12Pd4S4 (1b), C40H40Cl4N12Pd4S4 (1c) and
C44H48Br4N12Pd4S4 (1d) (see Section 4). This has been con-
firmed by the crystal structure resolution of complex 1a (vide
infra). The m(C@N) band was shifted to lower wavenumbers
upon complex formation by ca. 30 cmꢀ1 [24] in agreement
with coordination of the palladium atom to the C@N moiety
through the nitrogen lone pair [25,26]. Deprotonation of the
–NH– group was clear from the absence ofthe NH resonance
1
2. Results and discussion
in the H NMR spectra [27,28], which induces loss of the
C@S double bond character as confirmed by the non-exis-
tence of the m(C@S) band. Further proof could be ascer-
tained by comparison of the C–S lengths in the crystal
structures of a, and of 1a and 5a–7a, which showed lengthen-
ing of this bond in the latter cases.
The ligands a–d were prepared by reaction of 4-methyl or
4-ethyl-3-thiosemicarbazide with 20-fluoro-, 20-chloro or 20-
bromo acetophenone as appropriate, which were fully char-
acterized (see Section 4). Characteristic m(N–H) bands for
the NHR and NH groups appeared ca. 3300 and 3200
cmꢀ1, respectively, in the IR spectra, the latter disappears
in the spectra of the complexes [23]; the typical m(C@N)
2.1. Reactivity of the complexes
and m(C@S) stretches were situated ca. 1600 and 830 cmꢀ1
,
Prior to describing the reactivity of the aforementioned
compounds a brief regarding this issue is mandatory. We
have shown that tetranuclear cyclometallated thiosemicar-
bazone compounds, such as those described above, when
reacted with tertiary phosphines only experience cleavage
of the Pd–Sbridging bond, whereas the Pd–Schelating bond pre-
vails in all cases, even when strong chelating diphosphines
are employed, making these ligands excellent terdentate
[C,N,S] pincer species. Hence, although one might consider
that, under the appropriate conditions, derivatives with the
diphosphine bonded to the metal as monodentate leaving
respectively. The 1H NMR spectra showed signals ca. d 8.6
and d 7.5 for the NHR and NH protons, respectively. From
them the cyclometallated complexes shown in Scheme 1
could be prepared by any one of the three alternative meth-
ods described, i.e., (a) potassium tetrachloropalladate in eth-
anol; (b) lithium tetrachloropalladate in methanol; or (c)
palladium(II) acetate in glacial acetic acid, leading in all
cases to the tetranuclear species 1a–1d, as air-stable solids,
with the ligand in the E,Z configuration, which were fully
characterized (preparative details, characterizing microana-
RHN
N
4
3
5
6
R2
S
N
Pd
X
Ph2
P
X
i
ii
X
P
Pd
N
Ph2
Me
X
Pd
N
S
Me
HN
S
N
S
N
R2
NHR
N
NHR
2a,
NHR
3a, 3b, 3d
4a, 4c
4
a: R = Me; X = F
b: R = Et; X = F
c: R = Me; X = Cl
d: R = Et; X = Br
1a, 1b, 1c, 1d
5a, 5c
iii
iv
Ph2
P
PPh2
Ph2
P
Pd
X
Pd
PPh2
N
S
X
R2
N
N
S
R2
NHR
N
NHR
6a, 6b
7a
Scheme 1. Reaction conditions: (i) K2[PdCl4]/EtOH; (ii) PP/acetone, 2: PP = Ph2PCH2PPh2; 3: PP = Ph2P(CH2)2PPh2; 4: PP = Ph2P(CH2)3PPh2; 5:
PP = trans-Ph2PCH@CHPPh2; (iii) Ph2PCH2PPh2/acetone; and (iv) cis-Ph2PCH@CHPPh2/acetone.

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
2723
one uncoordinated phosphorus atom could be obtained,
long-chain diphosphines failed to do so, yielding dinuclear
compounds with the phosphine bridging the two metal cen-
ters; regrettably, only in the case of short bite diphosphines
such as Ph2PCH2PPh2, dppm, and Ph2PC(@CH2)PPh2,
vdpp, could the desired compounds be attained, of which
no crystal structures had yet been reported. However, even
in the latter cases the phosphine may bridge two metals
and mixtures of the mono- and dinuclear compounds have
been found by us [21a]. These compounds may behave as
bidentate [P,S] metalloligands as we have previously shown
[21d]. We then reasoned that although diphosphines bearing
a carbon chain of two or more atoms are not prone to behave
as monodentate, should there be steric hindrance between
the corresponding cyclometallated moieties, phosphine link-
age would be limited to only one phosphorus donor. In order
to prove our assertion, we sought out to develop the chemis-
try related to the case with cis-Ph2PCH@CHPPh2 as is
described below, which typifies the first example where a
long-bite diphosphine coordinates as monodentate in cyclo-
metallated thiosemicarbazones compounds.
Thus, when 1a–1d were treated with the corresponding
diphosphine in 1:2 molar ratio, the compounds 2a, 3a,
3b, 3d, 4a, 4c, 5a and 5c were obtained as pure air-stable
solids, which were fully characterized (see Section 4). The
1H NMR spectra showed the H5 resonance was coupled
to the 31P nucleus and shifted to lower frequency by ca.
1–1.5 ppm, suggesting a P trans to N arrangement [29].
The 31P resonance was a singlet signal in accordance with
two equivalent phosphorus nuclei in each case; the chemi-
Fig. 1. An ORTEP drawing of the molecular structure for a with labeling
scheme (30% probability). Hydrogen atoms have been omitted for clarity.
˚
Selected bond lengths (A) and angles (ꢁ): C(1)–C(7) 1.489(4); N(1)–C(7)
1.279(4); N(1)–N(2) 1.386(3); N(2)–C(8) 1.348(4); S(1)–C(8) 1.694(3);
C(8)–N(3) 1.325(4); C(6)–C(1)–C(7) 121.0(3); N(1)–C(7)–C(1) 115.1(3);
C(7)–N(1)–N(2) 117.1(3); C(8)–N(2)–N(1) 118.9(3); N(3)–C(8)–N(2)
116.9(3); N(3)–C(8)–S(1) 124.1(2); N(2)–C(8)–N(1) 119.0(2).
Fig. 2. An ORTEP drawing of the molecular structure for 1a with labeling scheme (30% probability). Hydrogen atoms have been omitted for clarity.
˚
Selected bond lengths (A) and angles (ꢁ) (at the metal): Pd(1)–C(1) 2.023(11); Pd(1)–N(1) 1.985(10); Pd(1)–S(2) 2.325(4); Pd(1)–S(1) 2.369(3); S(1)–C(8)
1.747(17); N(2)–C(8) 1.338(17); N(1)–N(2) 1.377(13); N(1)–C(7) 1.321(13); C(1)–C(7) 1.440(17); Pd(2)–C(11) 2.000; (12); Pd(2)–N(4) 2-010(10); Pd(2)–
S(1)#1 2.332(4); Pd(2)–S(2) 2.366(3); S(2)–C(18) 1.783(12); N(5)–C(18) 1.298(13); N(4)–N(5) 1.382(13); N(4)–C(17) 1.304(14); C(16)–C(17) 1.448(17);
C(1)–Pd(1)–N(1) 80.6(5); C(1)–Pd(1)–S(2) 96.6(4); S(1)–Pd(1)–S(2) 95.85(14); N(1)–Pd(1)–S(1) 83.9(3); N(1)–Pd(1)–S(2) 177.0(3); C(1)–Pd(1)–S(1)
163.6(4); C(11)–Pd(2)–N(4) 81.8(5); C(11)–Pd(2)–S(1)#1 97.4(4); S(1)#1–Pd(2)–S(2) 98.44(13); N(4)–Pd(2)–S(2) 82.3(3); N(4)–Pd(2)–S(1)#1 179.2(3);
C(11)–Pd(2)–S(2) 163.1(4).

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J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
cal shift values also supported a phosphorus trans to nitro-
gen geometry [30,31,11].
appeared at higher frequency. For 6a and 6b the reso-
nance for the CH2 protons of the phosphine, which are
part of an ABXY spin system, appeared as an apparent
doublet ca. 3.2 ppm; for compound 7a the ethylene phos-
phine protons belong to an AA0XX0 spin system and
appear as an apparent triplet at 5.81 ppm, with an N
value of 28 Hz.
Treatment of 1a–1d with the short-bite and long-bite
diphosphines, dppm or cis-dpe, respectively, in 1:4 molar
ratio produced the compounds 6a, 6b and 7a, as pure
air-stable solids. Characteristic microanalytical and spec-
troscopic data are given in Section 4. The mononuclear
compounds showed cleavage of only the Pd–Sbridging
bonds giving coordination of the phosphine to the metal
atom only through one phosphorus atom. The 31P
NMR spectra showed two doublets assigned to the two
non-equivalent phosphorus nuclei; the 31P resonance of
the phosphorus nucleus bonded to the metal center
2.2. Structural studies: crystal structures of ligand a and
of complexes 1a, 3d, 5a, 5c, 6a, 6b and 7a
Suitable crystals were grown by slowly evaporating a
chloroform/n-hexane solutions. The crystal structures of
Fig. 3. An ORTEP drawing of the molecular structure for 3d with labeling scheme (30% probability). Hydrogen atoms have been omitted for clarity.
˚
Selected bond lengths (A) and angles (ꢁ) (at the metal): Pd(1)–N(1) 2.025(5); Pd(1)–C(1) 2.042(6); Pd(1)–P(1) 2.2544(16); Pd(1)–S(1) 2.3225(19); S(1)–
C(8)1.766(8); N(2)–C(8)1.286(10); N(3)–C(8) 1.356(6);N(1)–N(2) 1.371(7); N(1)–C(7) 1.286(8); C(1)–C(7)1.496(8); P(1)–C(12) 1.829(6); P(1)–C(13)
1.807(7); P(1)–C(19) 1.834(7); N(1)–Pd(1)–C(6) 80.4(2); C(6)–Pd(1)–P(1) 96.47(17); P(1)–Pd(1)–S(1) 99.53(7); N(1)–Pd(1)–S(1) 83.69(16); N(1)–Pd(1)–P(1)
176.03(16); C(1)–Pd(1)–S(1) 163.78(17).
Fig. 4. An ORTEP drawing of the molecular structure for 5a with labeling scheme (30% probability). Hydrogen atoms have been omitted for clarity.
˚
Selected bond lengths (A) and angles (ꢁ) (at the metal): Pd(1)–N(1) 2.022(2); Pd(1)–C(1) 2.036(2); Pd(1)–P(1) 2.2421(7); Pd(1)–S(1) 2.3208(8); S(1)–C(8)
1.759(3); N(2)–C(8) 1.309(3); N(3)–C(8) 1.342(3); N(1)–N(2) 1.381(3); N(1)–C(7) 1.297(3); C(6)–C(7) 1.478(4); P(1)–C(11) 1.818(3); P(1)–C(12) 1.821(3);
P(1)–C(18) 1.824(2); N(1)–Pd(1)–C(1) 81.26(9); C(1)–Pd(1)–P(1) 97.97(8); P(1)–Pd(1)–S(1) 97.51(3); N(1)–Pd(1)–S(1) 83.25(6); N(1)–Pd(1)–P(1) 178.77(6);
C(1)–Pd(1)–S(1) 164.51(8).

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
2725
Fig. 5. An ORTEP drawing of the molecular structure for 5c with labeling scheme (30% probability). Hydrogen atoms have been omitted for clarity.
˚
Selected bond lengths (A) and angles (ꢁ) (at the metal): Pd(1)–N(1) 2.012(9); Pd(1)–C(6) 2.023(12); Pd(1)–P(1) 2.259(3); Pd(1)–S(1) 2.327(4); S(1)–C(8)
1.764(12); N(2)–C(8) 1.323(14); N(3)–C(8) 1.313(13); N(1)–N(2) 1.380(12); N(1)–C(7) 1.314(14); C(1)–C(7) 1.427(15); P(1)–C(11) 1.795(10); P(1)–C(12)
1.799(10); P(1)–C(18) 1.807(11); N(1)–Pd(1)–C(6) 81.0(4); C(6)–Pd(1)–P(1) 99.1(3); P(1)–Pd(1)–S(1) 96.18(12); N(1)–Pd(1)–S(1) 83.6(3); N(1)–Pd(1)–P(1)
178.7(3); C(6)–Pd(1)–S(1) 164.7 (3).
Fig. 6. An ORTEP drawing of the molecular structure for 5a depicting the parallel arrangement of the cyclometallated moieties.
the complexes are shown in Figs. 1–8, respectively. Crystal
data are given in Tables 1 and 2.
planar (rms = 0.0367) and at an angle of 39.4(4)ꢁ with the
fluorinated phenyl ring (rms = 0.0015). The parameters for
the hydrogen bonding interaction in ligand a are as follows:
˚
˚
2.2.1. 2-FC6H4C(Me)@NN(H)C(@S)NHMe (a)
Ligand a crystallizes in the orthorhombic C2cb space
group as the E,Z-isomer with relation to the N(1)–C(7)
and N(8)–C(3) bonds, respectively, Fig. 1.
H(3)ꢁ ꢁ ꢁO(1) 2.55 A, N(3)ꢁ ꢁ ꢁO(1) 3.224(3) A, N(3)–
˚
H(3)ꢁ ꢁ ꢁO(1) 136.4ꢁ, H(3)ꢁ ꢁ ꢁN(1) 2.23 A, N(3)ꢁ ꢁ ꢁN(1)
˚
2.624(4) A, N(3)–H(3)ꢁ ꢁ ꢁN(1) 107.7ꢁ, H(1S)ꢁ ꢁ ꢁS(1)#1
˚
˚
2.57(6) A, O(1)ꢁ ꢁ ꢁS(1)#1 3.364(5) A, O(1)–H(1S)ꢁ ꢁ ꢁS(1)#1
˚
˚
This arrangement is often found in thiosemicarbazones
with at least one hydrogen attached to N(3) due to weak
N(3)–H(3)ꢁ ꢁ ꢁN(1) hydrogen bonding. The C(8)–S(1),
158(5) ꢁ, H(2)ꢁ ꢁ ꢁS(1)#2 2.98 A, N(2)ꢁ ꢁ ꢁS(1)#2 3.736(3) A,
N(2)–H(2)ꢁ ꢁ ꢁS(1)#2 147.9ꢁ, with the symmetry transforma-
tions #1: x ꢀ 1/2, ꢀy + 2, z + 1/2; #2: x, ꢀy + 2, ꢀz.
˚
˚
1.747(17) A, and the N(1)–C(7) bond distances,
1.321(13) A, are consistent with a formal double bond char-
2.2.2. [Pd{2-FC6H3C(Me)@NN@C(S)NHMe}]4 (1a)
The core of the molecule consists of an eight-membered
ring of alternating palladium and sulfur atoms, Fig. 2.
The remaining two coordination sites of each palladium
atom are occupied by the phenyl carbon atom and the
acter. The C(1)–C(7)–N(1) 111.7(12)ꢁ and C(7)–N(1)–N(2)
118.1(12)ꢁ bond angles, are in agreement with sp2 hybridiza-
tion of the carbon and nitrogen atoms of the C@N moiety.
The thioamide chain C(7)–N(1)–N(2)–C(8)–[S(1)]–N(3) is

2726
J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
Fig. 7. An ORTEP drawing of the molecular structure for 6a with labeling scheme (30% probability). Hydrogen atoms have been omitted for clarity.
˚
Selected bond lengths (A) and angles (ꢁ) (at the metal): Pd(1)–N(1) 2.034(3); Pd(1)–C(1) 2.035(3); Pd(1)–P(1) 2.2592(8); Pd(1)–S(1) 2.3204(10); S(1)–C(8)
1.753(4); N(2)–C(8)1.307(5); N(3)–C(8) 1.352(5); N(1)–N(2) 1.387(4); N(1)–C(7) 1.292(4); C(6)–C(7) 1.467(5); P(1)–C(11) 1.839(3); P(2)–C(11) 1.862(3);
N(1)–Pd(1)–C(1) 81.21(12); C(1)–Pd(1)–P(1) 97.44(10); P(1)–Pd(1)–S(1) 98.52(3); N(1)–Pd(1)–S(1) 82.75(8); N(1)–Pd(1)–P(1) 177.75(8); C(1)–Pd(1)–S(1)
163.81(10).
Fig. 8. An ORTEP drawing of the molecular structure for 6b with labeling scheme (30% probability). Hydrogen atoms have been omitted for clarity.
˚
Selected bond lengths (A) and angles (ꢁ) (at the metal): Pd(1)–N(1) 2.031(4); Pd(1)–C(1) 2.038(5); Pd(1)–P(1) 2.2616(13); Pd(1)–S(1) 2.3323(15); S(1)–C(8)
1.758(6); N(2)–C(8) 1.313(7); N(3)–C(8) 1.343(7); N(1)–N(2) 1.379(6); N(1)–C(7) 1.300(6); C(6)–C(7) 1.457(8); P(1)–C(12) 1.858(5); P(2)–C(12) 1.855(5);
N(1)–Pd(1)–C(1) 81.30(19); C(1)–Pd(1)–P(1) 97.74(15); P(1)–Pd(1)–S(1) 98.34(5); N(1)–Pd(1)–S(1) 82.56(12); N(1)–Pd(1)–P(1) 177.45(12); C(1)–Pd(1)–S(1)
163.80(15).
nitrogen atom of the C@N group in a square-planar envi-
ronment. Each of the four palladium atoms belongs to two
fused five-membered chelate rings: the C,N metalacycle and
the N,S-chelate moiety, as a result of bonding to a triden-
tate C,N,S ligand. The C(8)–S(1) and S(2)–C(18) distances,
1.747(17) and 1.783(12) A, respectively, are consistent with
˚

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
2727
Table 1
Crystal data and structure refinement data for a, 1a, 3d and 5a
Compound
a
1a
3d
5a
Empirical formula
Formula weight
Temperature (K)
C10H13FN3O0.50
234.29
293(2)
1.54184
S
C40H40F4N12Pd4S4
1318.68
293(2)
C48H48Br2N6P2Pd2S2
1207.60
293(2)
C48H44Cl6F2N6P2Pd2S2
1294.45
293(2)
˚
Wavelength (A)
0.71073
0.71073
0.71073
Crystal system
Space group
Unit cell dimensions
Orthorhombic
C2cb
Prism
I41/a
Monoclinic
C2/c
Triclinic
ꢀ
P1
˚
a (A)
7.4210(7)
23.1470(17)
13.6180(8)
13.688(5)
13.688(5)
52.59(2)
29.709(5)
18.535(3)
10.0522(17)
10.5849(15)
11.2957(16)
12.4969(17)
86.684(5)
66.445(4)
76.396(5)
1330.2(3)
1
1.616
1.163
648
0.38 · 0.16 · 0.13
1.78–30.62
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
99.005(3)
3
˚
V (A )
2339.2(3)
8
1.331
2.410
984
9854(6)
8
1.778
1.664
5467.1(16)
4
1.467
2.290
2408
0.30 · 0.20 · 0.13
1.30–26.40
ꢀ37/h/36, 0/k/23, 0/l/12
5613
5613 (0.0000)
99.9% (26.40ꢁ)
Semi-empiric
0.7550 and 0.5466
Z
Dcalc (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
)
5184
Crystal size (mm3)
0.40 · 0.28 · 0.08
0.44 · 0.24 · 0.16
2.61–28.02
ꢀ18/h/0, ꢀ18/k/0, 0/l/69
6429
5951 (0.0846)
99.8% (28.02ꢁ)
Semi-empiric
0.7767 and 0.5280
h Range for data collection (ꢁ) 3.82–57.52
Index ranges
ꢀ8/h/8, ꢀ25/k/0, ꢀ14/l/0
ꢀ15/h/15, ꢀ15/k/16, ꢀ16/l/17
Reflections collected
Independent reflections (Rint
Completeness to h
Absorption correction
Maximum and minimum
transmission
1598
20765
)
1598 (0.0000)
99.8% (57.52ꢁ)
Semi-empiric
0.8306 and 0.4457
8021 (0.0380)
97.9% (30.62ꢁ)
Semi-empiric
0.8635 and 0.6662
Refinement method
Full-matrix least-squares
on F2
Full-matrix least-squares
on F2
Full-matrix least-squares
on F2
Full-matrix least-squares
on F2
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
1598/1/148
1.071
5951/13/299
0.902
5613/6/329
1.004
8021/0/322
0.949
R1 = 0.0433, wR2 = 0.1169 R1 = 0.0599, wR2 = 0.1189 R1 = 0.0523, wR2 = 0.1574 R1 = 0.0353, wR2 = 0.0774
R1 = 0.0484, wR2 = 0.1212 R1 = 0.3078, wR2 = 0.1757 R1 = 0.0920, wR2 = 0.1853 R1 = 0.0657, wR2 = 0.0874
Largest difference in peak and 0.255 and ꢀ0.292
1.085 and ꢀ0.793
1.673 and ꢀ1.080
0.662 and ꢀ0.633
ꢀ3
˚
hole (e A
)
increased single-bond character, and the C(8)–N(2) and
N(5)–C(18) distance, 1.338(17) and 1.298(13) A, respec-
sulfur atom, and to a phosphorus atom P(1) of the bridging
diphosphine ligand, in a slightly distorted square-planar
coordination, [Pd(1), N(1), S(1), C(6), P(1), plane 1] (rms =
˚
tively, with increased double-bond character in the depro-
tonated form. The Pd–Schelating distances [Pd(1)–S(2)
2.325(4) and Pd(2)–S(1)#1 2.332(4)] are shorter than the
Pd–Sbridging ones [Pd(1)–S(1) 2.369(3) and Pd(2)–S(2)
2.366(3)] putting forward the greater trans influence of
the phenyl carbon as compared to the imine nitrogen atom.
The Pd(1)–Pd(1)# and Pd(2)–Pd(2)# lengths of 3.3001(10)
˚
0.0495 A) 3d, [Pd(1), N(1), S(1), C(1), P(1), plane 1] (rms =
˚
0.0060 A) 5a, [Pd(1), N(1), S(1), C(6), P(1), plane 1]
˚
(rms = 0.0049 A) 5c (see Figs. 3–5).
The angles between adjacent atoms in the coordination
sphere are close to the expected value of 90ꢁ, in the range
99.1(3)–80.4(2)ꢁ; angles N(1)–Pd(1)–C(6), N(1)–Pd(1)–C(1)
for 5c, and N(1)–Pd(1)–S(1) on the one hand, and angles
C(6)–Pd(1)–P(1), C(1)–Pd(1)–P(1) for 5c, and P(1)–Pd(1)–
S(1), on the other, are diminished and increased by ca. 7–
˚
and 3.3262(12) A, respectively, preclude any Pd–Pd
interactions.
˚
2.2.3. [{Pd[2-BrC6H3C(Me)@NN@C(S)NHEt]}2(l-
Ph2P(CH2)2PPh2–P,P)] (3d), [{Pd[2-FC6H3C(Me)@
NN@C(S)NHMe]}2(l-Ph2PCH@CHPPh2–P,P)] (5a),
[{Pd[2-ClC6H3-C(Me)@NN@C(S)NHMe]}2(l-
Ph2PCH@CHPPh2–P,P)] (5c)
The crystals consist of discrete molecules, separated by
normal van der Waals distances. The palladium(II) atom
in each case is bonded to four different donor atoms, a triden-
tate C,N,S thiosemicarbazone through the aryl C(1) or C(6)
carbon, the imine N(1) nitrogen, and the thioamide S(1)
9 A, respectively, consequent upon formation of the two
five-membered rings. All bond distances are in their typical
ranges, with allowance for Pd–N bond lengthening due to
the trans influence of the phosphine ligand, which is reflected
˚
˚
in the Pd(1)–N(1) distance of 2.025(5) A for 3d, 2.034(3) A
˚
for 5a, 2.012(9) A for 5c (cf. sum of the covalent radii for pal-
ladium and nitrogen, 2.01 A [32]), also, the Pd–C of
2.042(6) A for 3d, 2.035(3) A for 5a, 2.023(12) A for 5c, bond
length is shorter than the expected value of 2.081 A probably
˚
˚
˚
˚
˚
induced by partial multiple-bond character [33,34]. The

2728
J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
Table 2
Crystal data and structure refinement data for 5c, 6a, 6b and 7a
Compound
5c
6a
6b
7a
Empirical formula
Formula weight
Temperature (K)
C23H21ClN3PPdS
544.31
293(2)
C36H33Cl3FN3P2PdS
833.40
293(2)
C37H34Cl3FN3P2PdS
846.42
293(2)
C36H32FN3P2PdS
726.05
293(2)
˚
Wavelength (A)
0.71069
0.71073
0.71073
0.71069
Crystal system
Space group
Unit cell dimensions
Triclinic
Triclinic
Triclinic
Monoclinic
P21/n
ꢀ
ꢀ
ꢀ
P1
P1
P1
˚
a (A)
9.191(5)
11.331(5)
12.229(5)
80.900(5)
69.200(5)
81.631(5)
1170.1(9)
2
10.7745(2)
11.92770(10)
15.6328(2)
86.9720(10)
78.4630(10)
68.6900(10)
1833.44(4)
2
10.84840(10)
11.9862(2)
15.8380(2)
86.7630(10)
78.7630(10)
68.4240(10)
1878.16(4)
2
10.276(5)
15.983(5)
21.088(5) A
˚
b (A)
˚
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
101.354(5)
3
˚
Volume (A )
3396(2)
4
1.420
0.737
1480
0.37 · 0.21 · 0.09
1.61–26.45
ꢀ12/h/12, 0/k/20, 0/l/26
Z
Dcalc (Mg/m3)
1.545
1.080
548
1.510
0.904
844
1.497
0.884
858
Absorption coefficient (mmꢀ1
F(000)
)
Crystal size (mm3)
0.22 · 0.09 · 0.06
0.50 · 0.30 · 0.20
1.33–28.27
ꢀ9/h/14, ꢀ15/k/15,
ꢀ15/l/20
0.30 · 0.25 · 0.20
1.31–28.26
ꢀ12/h/14, ꢀ8/k/15,
ꢀ21/l/20
h Range for data collection (ꢁ) 1.83–24.79
Index ranges
ꢀ9/h/10, ꢀ13/k/13,
0/l/14
Reflections collected
Independent reflections (Rint
Completeness to h
Absorption correction
Maximum and minimum
transmission
3869
11572
12898
6985
)
3869 (0.0000)
96.1% (24.79ꢁ)
Semi-empiric
0.9380 and 0.7971
8553 (0.0193)
94.1% (28.27ꢁ)
Semi-empiric
0.8398 and 0.6605
8910 (0.0238)
95.7% (28.26ꢁ)
Semi-empiric
0.8430 and 0.7773
6985 (0.0000)
99.8% (26.45ꢁ)
Semi-empiric
0.9366 and 0.7722
Refinement method
Full-matrix least-squares
on F2
Full-matrix least-squares
on F2
Full-matrix least-squares
on F2
Full-matrix least-squares
on F2
Data/restraints/parameters
Goodness-of-fit on F2
3869/0/273
1.020
8553/12/491
1.012
8910/70/472
1.028
6985/0/399
0.948
Final R indices [I > 2sigma(I)]
R indices (all data)
R1 = 0.0674, wR2 = 0.1086 R1 = 0.0441, wR2 = 0.1061 R1 = 0.0622, wR2 = 0.1555 R1 = 0.0329, wR2 = 0.0682
R1 = 0.1936, wR2 = 0.1507 R1 = 0.0597, wR2 = 0.1158 R1 = 0.0904, wR2 = 0.1756 R1 = 0.0753, wR2 = 0.0806
Largest difference in peak
1.033 and ꢀ1.165
0.988 and ꢀ0.958
1.214 and ꢀ1.151
0.353 and ꢀ0.505
ꢀ3
˚
and hole (e A
)
˚
˚
S(1)–C(8) bond length, 1.766(8) A for 3d, 1.753(4) A for 5a,
emplacement across the phosphine carbon–carbon bond,
as depicted, e.g., for compound 5a in Fig. 6.
˚
˚
1.764(12) A for 5c, and the N(2)–C(8) length, 1.286(10) A for
˚
˚
3d, 1.307(5) A for 5a, 1.323(14) A for 5c, are consistent with
increased singleanddoublebond character, respectively, asa
result of deprotonation. The planes at palladium: the coordi-
nation plane [Pd(1), N(1), S(1), C(6) or C(1), P(1), plane 1],
the metallacycle [Pd(1), C(1), C(6), C(7), N(1), plane 2], the
coordination ring [Pd(1), N(1), N(2), C(8), S(1), plane 3]
and the metallated phenyl ring [C(1), C(2), C(3), C(4),
C(5), C(6), plane 4], are nearly coplanar (angles between
planes: 1/2 = 3.38(0.12), 1/3 = 2.31(0.10), 1/4 = 8.17(0.15),
2/3 = 2.42(0.13), 2/4 = 4.86(0.20), 3/4 = 6.47(0.14)ꢁ for 3d;
1/2 = 1.45(0.05), 1/3 = 1.35(0.04), 1/4 = 1.87(0.08), 2/3 =
0.53(0.06), 2/4 = 0.88(0.10), 3/4 = 0.54(0.08)ꢁ for 5a;
1/2 = 1.76(0.15), 1/3 = 1.36(0.17), 1/4 = 2.65(0.28), 2/3 =
0.40(0.20), 2/4 = 3.25(0.35), 3/4 = 3.47(0.31)ꢁ for 5c).
Therefore, the two cyclometallated moieties in each of the
three structures are essentially planar with overall rms values
for the deviations from the least-square planes of 3d, 5a, and
5c, and it is also noteworthy to remark the mutually parallel
alignment of the mentioned groups in a totally symmetric
2.2.4. [Pd{2-FC6H3C(Me)@NN@C(S)NHMe}-
(Ph2PCH2 PPh2–P)] (6a), [Pd{2-FC6H3C–(Me)@NN@
C(S)NHEt}(Ph2PCH2PPh2–P)] (6b), [Pd{2-FC6H3C-
(Me)@NN@C(S)–NHMe}(Ph2PCH@CHPPh2–P)] (7a)
As for the crystal structures of 6a, 6b and 7a, these
exemplify the first accounts of crystal structures pertaining
to cyclopalladated thiosemicarbazone compounds with
mono-coordinated g1-diphosphines (see Figs. 7–9).
The asymmetric unit of each crystal structure comprises a
mononuclear palladium(II) complex, which reveals the pal-
ladium atom is in a square-planar environment with the thi-
osemicarbazone ligand behaving as terdentate, and the
phosphine ligand bonded trans to the iminic nitrogen atom.
All bond distances are within the expected values, with the
Pd–N bond displaying marked lengthening due to the trans
influence of the phosphine ligand. The angles in the environ-
ment of the metal atom show deviations from the ideal 90ꢁ
similar to those described above for compounds 3d, 5a,

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
2729
Fig. 9. An ORTEP drawing of the molecular structure for 7a with labeling scheme (30% probability). Hydrogen atoms, as well as one phosphine phenyl
˚
ring, have been omitted for clarity. Selected bond lengths (A) and angles (ꢁ) (at the metal): Pd(1)–N(1) 2.019(2); Pd(1)–C(1) 2.088(2); Pd(1)–P(1)
2.2536(10); Pd(1)–S(1) 2.3430(13); S(1)–C(8) 1.742(3); N(2)–C(8) 1.302(4); N(3)–C(8) 1.355(4); N(1)–N(2) 1.380(3); N(1)–C(7) 1.294(4); C(1)–C(7)
1.463(4); P(1)–C(11) 1.804(3); P(2)–C(12) 1.823(3); C(11)–C(12) 1.310(4); N(1)–Pd(1)–C(6) 80.88(12); C(6)–Pd(1)–P(1) 98.48(9); P(1)–Pd(1)–S(1) 97.84(3);
N(1)–Pd(1)–S(1) 82.78(8); N(1)–Pd(1)–P(1) 179.07(8); C(6)–Pd(1)–S(1) 163.47(9).
and 5c. The palladium coordination plane [Pd(1), C(1), N(1),
S(1)], 6a, 6b, and the P(1)C(11)P(2), 6a, P(1)C(12) P(2), 6b,
planes are at 69.15ꢁ and 69.70ꢁ, respectively; for compound
7a the coordination [Pd(1), C(6), N(1), S(1)] and
[P(1)C(11)C(12)P(2)] planes are at an angle of 71.29ꢁ.
The Pd(1)–P(2) bond distances, 4.1147(0.0001) 6a,
4.1062(0.0001) 6b and 3.1772(0.0013) 7a, preclude any inter-
action between palladium and the non-coordinated phos-
phorus atom.
bonding of a metallated moiety to a second phosphorus
atom of the phosphine ligand, in view of the resulting steric
impediment, rendering a compound with a g1-diphosphine
ligand.
4. Experimental
4.1. General procedures
Solvents were purified by standard methods [35]. Chem-
icals were reagent grade. Lithium tetrachloropalladate was
prepared in situ by treatment of palladium(II) chloride with
lithium chloride in methanol. Palladium(II) acetate, potas-
sium tetrachloropalladate, and palladium(II) chloride were
purchased from Alfa Products. The phosphines
Ph2PCH2PPh2 (dppm), Ph2P(CH2)2PPh2 (dppe), Ph2P-
(CH2)3PPh2 (dppp), trans-Ph2P(CH@CH)PPh2 (trans-dpe)
and cis-Ph2P(CH@CH)PPh2 (cis-dpe) were purchased from
Aldrich-Chemie. Microanalyses were carried out at the Ser-
3. Conclusions
We have shown that thiosemicarbazone ligands readily
undergo the cyclometallation reaction to give tetranuclear
compounds with a central core consisting of an eight-mem-
berd ring of alternating palladium and sulfur atoms, whose
subsequent reaction with tertiary diphosphines may be
modulated to give dinuclear or mononuclear species as a
function of (1) the molar ratio and of (2) the length of
the carbon chain, P–(C)n–P, connecting both phosphorus
atoms. Although, in principle, for n = 1 mono- or dinu-
clear compounds may be obtained as a function of the
molar ratio used, as is the case with bis(diphenylphosph-
ino)methane, whereas for n = 2, dinuclear species with
bridging phosphine are always obtained, as we have
observed earlier, a third issue to be considered is the nature
of the carbon chain, which may likewise modify the final
product in relation to its mono- or dinuclear essence.
Hence, with the diphospine cis-bis(diphenylphosphino)eth-
ene the spatial arrangement of the donor atoms, imposed
by the cis geometry of the C@C double bond, hinders
´
vicio de Analisis Elemental at the Universidad of Santiago
using a Carlo Erba Elemental Analyzer Model EA1108.
IR spectra were recorded as Nujol mulls or KBr discs with
a Perkin–Elmer 1330, with an IR-FT Mattson Model Cyg-
nus-100 and with a Bruker Model IFS-66 V spectropho-
tometers. NMR spectra were obtained as CDCl3 solutions
and referenced to SiMe4 (1H) or H3PO4 (31P–{1H}) and
were recorded with Bruker AMX 300, AMX 500 and
WM250 spectrometers. 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.

2730
J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
3
4.2. Synthesis
3JHH = 7.4, JH–NH = 5.5), 2.26 (s, 3H, MeC@N), 1.25
(t, 3H, NHCH2CH3, 3JHH = 7.4). FAB-MS: m/z 300 [M]+.
4.2.1. Preparation of 2-FC6H4C(Me)@NN(H)C(@S)-
NHMe (a)
4.2.5. Preparation of [Pd{2-FC6H3C(Me)@NN@C(S)-
NHMe}]4 (1a)
20-Fluoroacetophenone (131 mg, 9.51 mmol) and hydro-
chloric acid (35%, 0.65 mL) were added to a suspension of 4-
methyl-3-thiosemicarbazide (100 mg, 9.51 mmol) in water
(25 cm3) to give a clear solution, which was stirred at room
temperature for 4 h. The white solid that precipitated was fil-
tered off, washed with cold water, and dried in air. Yield:
178 mg, 83%. Anal. Found: C, 53.1; H, 5.4; N, 18.5; S,
14.2%; C10H12FN3S (225.3 g/mol) requires: C, 53.3; H, 5.4;
N, 18.6; S, 14.2%. IR (cmꢀ1): m(N–H) 3317m, 3182m;
Method 1: To a stirred solution of potassium tetrachloro-
palladate (200 mg, 0.61 mmol) in water (6 cm3) was added
ethanol (40 cm3). The fine yellow suspension of potassium
tetrachloropalladate obtained was treated with 2-FC6H4C-
(Me)@NN(H)C(@S)NHMe (a) (152 mg, 0.67 mmol, 10%
excess). The mixture was stirred for 48 h at room tempera-
ture under nitrogen. The yellow precipitate was filtered off,
washed with ethanol and dried. Yield: 172 mg, 85%. Anal.
Found: C, 36.5; H, 3.0; N, 12.6; S, 9.7%; C40H40F4N12Pd4S4
(1318.8 g/mol) requires: C, 36.4; H, 3.1; N, 12.7; S, 9.7%. IR
(cmꢀ1): m(N–H) 3437m; m(C@N) 1584s. 1H NMR (d ppm, J
1
m(C@N) 1616w; m(C@S) 839w. H NMR (d ppm, J Hz):
8.68 (s, 1H, NH), 7.61 (br, 1H, NHMe), 7.50 (td, 1H, H6,
4
4
3JH6H5 = 7.9, JH6F = 7.9, JH6H4 = 1.9), 7.38 (dddd,
3
4
3
1H, H4, JH4H3 = 8.3, JH4H6 = 1.9), 7.17 (td, 1H, H5,
Hz): 7.27 (d, 1H, H5, JH5H4 = 6.9), 6.94 (td, 1H, H4,
3
4
3JH5H4 = 7.9, JH5H6 = 7.9, JH5H3 = 0.9), 7.10 (ddd,
3JH4H3 = 8.3, 4JH4F = 5.1), 6.61 (ddd, 1H, H3, 3JH3F =
1H, H3, 3JH3F = 11.1, 3JH3H4 = 8.3, 4JH3H5 = 0.9),
12.5, JH3H4 = 8.3, JH3H5 = 0.9), 5.03 (q, 1H, NHMe,
3JNH–H = 5.1), 2.98 (d, 3H, NHMe, 3JH–NH = 5.1), 2.08
(d, 3H, MeC@N, 5JHF = 3.7). FAB-MS: m/z 1318 [M]+.
Method 2: Ligand a (267 mg, 1.18 mmol, 5% excess) and
sodium acetate (185 mg, 2.26 mmol) were added to a stir-
red solution of palladium(II) chloride (200 mg, 1.13 mmol)
and lithium chloride (96 mg, 2.26 mmol) in methanol
(40 cm3). The mixture was stirred for 48 h at room temper-
ature under nitrogen. The yellow precipitate was filtered
off, washed with methanol, and dried. Yield: 360 mg, 97%.
Method 3: Ligand a (210 mg, 0.94 mmol, 5% excess) and
palladium(II) acetate (200 mg, 0.89 mmol) were added to
glacial acetic acid (45 mL) to give a clear solution, which
was heated to 60 ꢁC under nitrogen for 24 h. After cooling
to room temperature, the yellow precipitate was filtered off,
washed with ethanol, and dried. Yield: 289 mg, 98%.
Compounds 1b–1d were prepared similarly by the
appropriate methods, as described above.
3
4
3
3.24 (d, 3H, NHMe, JHH = 4.6), 2.28 (d, 3H, MeC@N,
5JHF = 2.3). FAB-MS: m/z 226 [MH]+.
Ligands b and c were prepared analogously.
4.2.2. 2-FC6H4C(Me)@NN(H)C(@S)NHEt (b)
Yield: 188 mg, 93%. Anal. Found: C, 55.0; H, 5.8; N, 17.6;
S, 13.6%; C11H14FN3S (239.3 g/mol) requires: C, 55.2; H,
5.9; N, 17.6; S, 13.4%. IR (cmꢀ1): m(N–H) 3358m, 3235w;
1
m(C@N) 1614w; m(C@S) 837w. H NMR (d ppm, J Hz):
8.63 (s, 1H, NH), 7.56 (br, 1H, NHEt), 7.49 (td, 1H, H6,
3JH6H5 = 7.9 Hz, 4JH6F = 7.9, 4JH6H4 = 1.9), 7.38
3
4
(dddd, 1H, H4, JH4H3 = 8.3, JH4H6 = 1.9), 7.18 (td,
3
3
4
1H, H5, JH5H4 = 7.9 Hz, JH5H6 = 7.9 Hz, JH5H3 =
0.9), 7.10 (ddd, 1H, H3, 3JH3F = 11.1, 3JH3H4 = 8.3,
4JH3H5 = 0.9), 3.75 (dq, 2H, NHCH2CH3, 3JHH = 6.9 Hz,
3JH–NH = 5.6), 2.28 (d, 3H, MeC@N, 5JHF = 2.3), 1.30 (t,
3H, NHCH2CH3, 3JHH = 6.9). FAB-MS: m/z 240 [MH]+.
4.2.3. 2-ClC6H4C(Me)@NN(H)C(@S)NHMe (c)
Yield: 209 mg, 91%. Anal. Found: C, 49.4; H, 5.0; N,
17.4; S, 13.2%; C10H12ClN3S (241.7 g/mol) requires: C,
49.7; H, 5.0; N, 17.4; S, 13.3%. IR (cmꢀ1): m(N–H) 3357s,
4.2.6. [Pd{2-FC6H3C(Me)@NN@C(S)NHEt}]4 (1b)
Method 1: Yield: 335 mg, 86%. Anal. Found: C, 38.4; H,
3.3; N, 12.0; S, 9.3%; C44H48F4N12Pd4S4 (1374.9 g/mol)
requires: C, 38.4; H, 3.5; N, 12.2; S, 9.3%. IR (cmꢀ1): m(N–
1
1
3239m; m(C@N) 1591w; m(C@S) 834m. H NMR (d ppm,
H) 3425m, m(C@N) 1585s. H NMR (d ppm, J Hz): 7.28
3
3
J Hz): 8.62 (s, 1H, NH), 7.53 (br, 1H, NHMe), 7.36 (dd,
1H, H6), 7.26 (m, 3H, H3, H4, H5), 3.15 (d, 3H, NHMe,
3JHH = 4.6), 2.22 (s, 3H, MeC@N). FAB-MS: m/z 242
[M]+.
(d, 1H, H5, JH5H4 = 6.9), 6.94 (td, 1H, H4, JH4H3 =
8.3, 4JH4F = 5.1), 6.62 (ddd, 1H, H3, 3JH3F = 12.5,
3JH3H4 = 8.3, JH3H5 = 0.9), 5.05 (t, 1H, NHEt, JNH–
H = 5.5), 3.40 (m, 2H, NHCH2CH3), 2.03 (d, 3H, MeC@N,
5JHF = 4.2), 1.23 (t, 3H, NHCH2CH3, 3JHH = 6.9). FAB-
MS: m/z 1375 [M]+.
4
3
4.2.4. 2-BrC6H4C(Me)@NN(H)C(@S)NHEt (d)
Yield: 204 mg, 81%. Anal. Found: C, 43.9; H, 4.7; N, 14.2;
S, 10.5%; C11H14BrN3S (300.2 g/mol) requires: C, 44.0; H,
4.7; N, 14.0; S, 10.7%. IR (cmꢀ1): m(N–H) 3367s, 3208m;
4.2.7. [Pd{2-ClC6H3C(Me)@NN@C(S)NHMe}]4 (1c)
Method 2: Yield: 346 mg, 89%. Anal. Found: C, 34.6; H,
2.9; N, 11.9; S, 9.2%; C40H40Cl4N12Pd4S4 (1384.6 g/mol)
requires: C, 34.7; H, 2.9; N, 12.1; S, 9.3%. IR (cmꢀ1): m(N–
1
m(C@N) 1588w; m(C@S) 826m. H NMR (d ppm, J Hz):
3
8.60 (br, 1H, NH), 7.61 (dd, 1H, H6, JH6H5 = 7.9), 7.54
(br, 1H, NHEt), 7.37 (dd, 1H, H3, 3JH3H4 = 7.9,
4JH3H5 = 1.4), 7.31 (td, 1H, H4, 3JH4H3 = 7.9,
3JH4H5 = 7.9, 4JH4H6 = 1.4), 7.25 (ddd, 1H, H5,
3JH5H4 = 7.9, 4JH5H3 = 1.4), 3.72 (dq, 2H, NHCH2CH3,
H) 3425s, m(C@N) 1558s. H NMR (d ppm, J Hz): 7.44
1
(dd, 1H, H5, 3JH5H4 = 7.9, 4J H5H3 = 0.9), 6.96 (dd, 1H,
H3, 3JH3H4 = 7.9, 4JH3H5 = 0.9), 6.84 (t, 1H, H4,
3JH4H3 = 7.9 Hz, 3JH4H5 = 7.9), 5.07 (q, 1H, NHMe,

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
2731
3JNH–H = 4.6), 2.98 (d, 3H, NHMe, 3JH–NH = 4.6), 2.22
4.2.12. [{Pd[2-BrC6H3C(Me)@NN@C(S)NHEt]}2(l-
Ph2P(CH2)2PPh2–P,P)] (3d)
(s, 3H, MeC@N). FAB-MS: m/z 1384 [M]+.
Method 3: Yield: 294 mg, 95%.
Yield: 30.6 mg, 68%. Anal. Found: C, 47.8; H, 4.1; N, 6.9;
S, 5.1%; C48H48Br2N6P2Pd2S2 (1207.7 g/mol) requires: C,
47.7; H, 4.0; N, 7.0; S, 5.3%. IR (cmꢀ1): m(N–H) 3426m;
m(C@N) 1555m. 1H NMR (d ppm, J Hz): 7.07 (dd, 1H, H3,
4.2.8. [Pd{2-BrC6H3C(Me)@NN@C(S)NHEt}]4 (1d)
Method 1: Yield: 353 mg, 77%. Anal. Found: C, 32.5;
H, 2.9; N, 10.3; S, 8.0%; C44H48Br4N12Pd4S4 (1618.5 g/
mol) requires: C, 32.7; H, 3.0; N, 10.4; S, 7.9%. IR
(cmꢀ1): m(N–H) 3425m, m(C@N) 1557s. 1H NMR (d
ppm, J Hz): 7.50 (dd, 1H, H5, 3JH5H4 = 7.9 Hz,
4JH5H3 = 0.9), 7.22 (dd, 1H, H3, 3JH3H4 = 7.9,
4JH3H5 = 0.9), 6.75 (t, 1H, H4, 3JH4H3 = 7.9,
4
3JH3H4 = 7.4, JH3H5 = 1.8), 6.26 (m, 1H, H5), 6.23 (t,
1H, H4, 3JH4H3 = 7.4, 3JH4H5 = 7.4), 4.78 (br, 1H,
NHEt), 3.40 (dq, 2H, NHCH2CH3, 3JHH = 7.4, 3JH–
NH = 5.5), 2.79 (br, 2H, P(CH2)2P), 2.74 (s, 3H, MeC@N),
1.19 (t, 3H, NHCH2CH3, 3JHH = 7.4). 31P–{1H} NMR (d
ppm): 31.8s.
3
3JH4H5 = 7.9), 5.09 (t, 1H, NHEt, JNH–H = 5.5), 3.40
3
3
(dq, 2H, NHCH2CH3, JHH = 7.4, JH–NH = 5.5), 2.21
(s, 3H, MeC@N), 1.24 (t, 3H, NHCH2CH3,
3JHH = 7.4). FAB-MS: m/z 1620 [MH]+.
4.2.13. [{Pd[2-FC6H3C(Me)@NN@C(S)NHMe]}2(l-
Ph2P(CH2)3PPh2–P,P)] (4a)
Yield: 69.5 mg, 85%. Anal. Found: C, 52.8; H, 4.4; N, 7.8;
S, 5.9%; C47H46F2N6P2Pd2S2 (1071.8 g/mol) requires: C,
52.7; H, 4.3; N, 7.8; S, 6.0%. IR (cmꢀ1): m(N–H) 3428m;
m(C@N) 1574m. 1H NMR (d ppm, J Hz): 6.42 (m, 2H, H3,
Method 2: Yield: 302 mg, 84%.
4.2.9. Preparation of [{Pd[2-FC6H3C(Me)@NN@C(S)-
NHMe]}2(l-Ph2PCH2PPh2–P,P)] (2a)
3
H4), 6.05 (m, 1H, H5), 4.76 (q, 1H, NHMe, JNH–H =
3
The diphosphine Ph2PCH2PPh2 (17.8 mg, 0.046 mmol)
was added to a suspension of complex 1a (30 mg, 0.023
mmol) in acetone (15 cm3). The mixture was stirred for 4 h.
and the resulting yellow solid was filtered off and dried.
Yield: 35.5 mg, 75%. Anal. Found: C, 51.6; H, 4.1; N, 8.2;
S, 6.1%; C45H42F2N6P2Pd2S2 (1043.8 g/mol) requires: C,
51.8; H, 4.1; N, 8.1; S, 6.1%. IR (cmꢀ1): m(N–H) 3464m;
m(C@N) 1581m. 1H NMR (d ppm, J Hz): 6.33 (m, 2H, H3,
5.0), 2.90 (d, 3H, NHMe, JH–NH = 5.0), 2.47 (d, 3H,
MeC@N, 5JHF = 4.7), 2.40 (br, 2H, PCH2CH2CH2P),
1.94 (br, 1H, PCH2CH2CH2P). 31P–{1H} NMR (d ppm):
26.9s.
4.2.14. [{Pd[2-ClC6H3C(Me)@NN@C(S)NHMe]}2(l-
Ph2P(CH2)3PPh2–P,P)] (4c)
Yield: 32.8 mg, 69%. Anal. Found: C, 51.2; H, 4.2; N, 7.6;
S, 5.6%; C47H46Cl2N6P2Pd2S2 (1104.7 g/mol) requires: C,
51.1; H, 4.2; N, 7.6; S, 5.8%. IR (cmꢀ1): m(N–H) 3433m;
3
H4), 5.87 (m, 1H, H5), 4.77 (q, 1H, NHMe, JNH–H =
5.1), 3.76 (t, 1H, PCH2P, 2JHP = 10.2), 3.01 (d, 3H, NHMe,
5
1
3JH–NH = 5.1), 2.51 (d, 3H, MeC@N, JHF = 3.7). 31P–
m(C@N) 1558m. H NMR (d ppm, J Hz): 6.82 (d, 1H, H3,
{1H} NMR (d ppm): 23.8s.
3JH3H4 = 7.9), 6.40 (t, 1H, H4, 3JH4H3 = 7.9, 3JH4H5 =
3
4
Compounds 3a–3d, 4a, 4c, 5a and 5c, were synthesized
following a similar procedure.
7.9), 6.27 (dd, 1H, H5, JH5H4 = 7.9, JH5P = 5.1), 4.82
(q, 1H, NHMe, 3JNH–H = 5.1), 2.99 (d, 3H, NHMe, 3JH–
NH = 5.1), 2.72 (s, 3H, MeC@N), 2.51 (m, 2H,
PCH2CH2CH2P), 2.12 (br, 1H, PCH2CH2CH2P). 31P–
{1H} NMR (d ppm): 26.9s.
4.2.10. [{Pd[2-FC6H3C(Me)@NN@C(S)NHMe]}2(l-
Ph2P(CH2)2PPh2–P,P)] (3a)
Yield: 44.2 mg, 92%. Anal. Found: C, 52.4; H, 4.3; N, 7.8;
S, 6.0%; C46H44F2N6P2Pd2S2 (1057.8 g/mol) requires: C,
52.2; H, 4.2; N, 7.9; S, 6.1%. IR (cmꢀ1): m(N–H) 3447m;
m(C@N) 1579m. 1H NMR (d ppm, J Hz): 6.49 (m, 2H, H3,
4.2.15. [{Pd[2-FC6H3C(Me)@NN@C(S)NHMe]}2(l-
Ph2PCH@CHPPh2–P,P)] (5a)
Yield: 69.6 mg, 87%. Anal. Found: C, 52.4; H, 4.0; N, 7.9;
S, 6.0%; C46H42F2N6P2Pd2S2 (1055.8 g/mol) requires: C,
52.3; H, 4.0; N, 8.0; S, 6.1%. IR (cmꢀ1): m(N–H) 3420m;
3
H4), 6.05 (m, 1H, H5), 4.72 (q, 1H, NHMe, JNH–H =
3
5.1), 2.97 (d, 3H, NHMe, JH–NH = 5.1), 2.82 (br, 2H,
5
1
P(CH2)2P), 2.57 (d, 3H, MeC@N, JHF = 4.6 Hz). 31P–
m(C@N) 1577m. H NMR (d ppm, J Hz): 6.48 (ddd, 1H,
{1H} NMR (d ppm): 32.0s.
H3, 3JH3F = 12.5, 3JH3H4 = 8.3, 4JH3H5 = 0.9), 6.34
3
4
(td, 1H, H4, JH4H3 = 8.3, JH4F = 5.1), 6.14 (m, 1H,
3
4.2.11. [{Pd[2-FC6H3C(Me)@NN@C(S)NHEt]}2(l-
Ph2P(CH2)2PPh2–P,P)] (3b)
H5), 4.69 (q, 1H, NHMe, JNH–H = 5.1), 2.92 (d, 3H,
NHMe, JH–NH = 5.1), 2.56 (d, 3H, MeC@N, JHF =
4.2). 31P–{1H} NMR (d ppm): 32.4s.
3
5
Yield: 17.6 mg, 37%. Anal. Found: C, 52.9; H, 4.3; N, 7.5;
S, 5.7%; C48H48F2N6P2Pd2S2 (1085.8 g/mol) requires: C,
53.1; H, 4.5; N, 7.7; S, 5.9%. IR (cmꢀ1): m(N–H) 3432m;
m(C@N) 1578m. 1H NMR (d ppm, J Hz): 6.49 (m, 2H, H3,
H4), 6.07 (m, 1H, H5), 4.72 (t, 1H, NHEt, 3JNH–H = 5.1),
4.2.16. [{Pd[2-ClC6H3C(Me)@NN@C(S)NHMe]}2(l-
Ph2PCH@CHPPh2–P,P)] (5c)
Yield: 24.2 mg, 51%. Anal. Found: C, 50.4; H, 3.7; N, 7.5;
S, 5.8%; C46H42Cl2N6P2Pd2S2 (1088.7 g/mol) requires: C,
50.7; H, 3.9; N, 7.7; S, 5.9%. IR (cmꢀ1): m(N–H) 3446m;
m(C@N) 1559m. 1H NMR (d ppm, J Hz): 6.77 (dd, 1H, H3,
3
3
3.40 (dq, 2H, NHCH2CH3, JHH = 7.4, JH–NH = 5.1),
5
2.83 (br, 2H, P(CH2)2P), 2.56 (d, 3H, MeC@N, JHF =
4.2), 1.19 (t, 3H, NHCH2CH3, 3JHH = 7.4). 31P–{1H}
NMR (d ppm): 31.4s.
4
3JH3H4 = 7.9, JH3H5 = 1.4), 6.29 (m, 1H, H5), 6.20 (t,

2732
J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2721–2733
1H, H4, 3JH4H3 = 7.9, 3JH4H5 = 7.9), 4.73 (br, 1H,
NHMe), 2.92 (d, 3H, NHMe, 3JH–NH = 4.6), 2.72 (s, 3H,
MeC@N). 31P–{1H} NMR (d ppm): 32.4s.
Three dimensional, room temperature X-ray data were
collected with Siemens (6a, 6b) and Bruker (3d, 5a, 5c
and 7a) SMART CCD diffractometers by the omega scan
method, using monochromated Mo Ka radiation.
4.2.17. Preparation of [Pd{2-FC6H3C(Me)@NN@C(S)-
NHMe}(Ph2PCH2PPh2–P)] (6a)
All the measured reflections were corrected for Lorentz
and polarization effects and for absorption by semiempir-
ical methods based on symmetry-equivalent and repeated
reflections [Tmax/Tmin = 0.8306/0.4457 (a), 0.7767/0.528
(1a), 0.755/0.5466 (3d), 0.843/0.7773 (4b), 0.8635/0.6662
(5a), 0.9380/0.7971 (5c), 0.8398/0.6605 (6a) and 0.9366/
0.7722 (7a)]. The structures were solved by direct meth-
ods and refined by full-matrix least-squares on F2. Hydro-
gen atoms were included in calculated positions and
refined in riding mode. Refinement converged at a final
R = 0.0433 (a), 0.0599 (1a), 0.0523 (3d), 0.0353 (5a),
0.0674 (5c), 0.0441 (6a), 0.0622 (6b) and 0.0329 (7a)
(observed data, F), and wR2 = 0.1212 (a), 0.1757 (1a),
0.1853 (3d), 0.0874 (5a), 0.1756 (5b), 0.1507 (5c), 0.1158
(6a), and 0.0806 (7a) (all unique data, F2), with allowance
for thermal anisotropy of all non-hydrogen atoms. Mini-
mum and maximum final electron densities: ꢀ0.292 and
0.255 (a), ꢀ0.793 and 1.085 (1a), ꢀ1.08 and 1.673 (3d),
ꢀ0.633 and 0.662 (5a), ꢀ1.165 and 1.033 (5c), ꢀ0.958
and 0.988 (6a), ꢀ1.151 and 1.214 (6b), ꢀ0.505 and
The diphosphine Ph2PCH2PPh2 (59.5 mg, 0.155 mmol)
was added to a suspension of complex 1a (50 mg, 0.038
mmol) in acetone (15 cm3). The mixture was stirred for 4 h.
The resulting yellow solid was filtered off and dried. Yield:
93.1 mg, 86%. Anal. Found: C, 58.8; H, 4.6; N, 5.8; S,
4.4%; C35H32FN3P2PdS (714.1 g/mol) requires: C, 58.9; H,
4.5; N, 5.9; S, 4.5%. IR (cmꢀ1): m(N–H) 3435m; m(C@N)
1
1577m. H NMR (d ppm, J Hz): 6.44 (m, 2H, H3, H4),
3
6.00 (m, 1H, H5), 4.77 (q, 1H, NHMe, JNH–H = 5.1),
2
3.25 (d, 2H, P CH2P, JHP = 9.2), 2.97 (d, 3H, NHMe,
5
3JH–NH = 5.1), 2.51 (d, 3H, MeC@N, JHF = 4.6). 31P–
2
{1H} NMR (d ppm, J Hz): 24.4 (d, 1P, PA, JPP = 75.1),
ꢀ26.3 (d, 1P, PB, 2JPP = 75.1).
Compounds 6b and 7a were obtained as yellow solids
following a similar procedure.
4.2.18. [Pd{2-FC6H3C(Me)@NN@C(S)NHEt}(Ph2-
PCH2PPh2–P)] (6b)
ꢀ3
˚
Yield: 100 mg, 95%. Anal. Found: C, 59.6; H, 4.7; N, 5.8;
S, 4.3%; C36H34FN3P2PdS (728.1 g/mol) requires: C, 59.4;
H, 4.7; N, 5.8; S, 4.4%. IR (cmꢀ1): m(N–H) 3424m; m(C@N)
0.061e A
(7a). The structure solutions and refine-
ments were carried out with the SHELX-97 [36] program
package.
1
1573m. H NMR (d ppm, J Hz): 6.44 (m, 2H, H3, H4),
6.00 (m, 1H, H5), 4.76 (t, 1H, NHEt, 3JNH–H = 5.1), 3.40
Acknowledgments
3
3
(dq, 2H, NHCH2CH3, JHH = 7.4, JH–NH = 5.1), 3.25
(d, 2H, PCH2P, 2JHP = 9.2), 2.50 (d, 3H, MeC@N,
We thank the DGESIC (Ministerio de Ciencia y Tec-
3
5JHF = 4.6), 1.18 (t, 3H, NHCH2CH3, JHH = 7.4). 31P–
´
nologıa) Proyecto BQU2002-04533-C02-01 and the Xunta
2
{1H} NMR (d ppm, J Hz): 24.4 (d, 1P, PA, JPP = 75.1),
de Galicia, incentive PGIDIT03PXIC20912PN, for finan-
ꢀ26.3 (d, 1P, PB, 2JPP = 75.1).
´
cial support. J. Martınez acknowledges a fellowship from
´
the Ministerio de Ciencia y Tecnologıa (Grant No. PB98-
0638-C02-01/02).
4.2.19. [Pd{2-FC6H3C(Me)@NN@C(S)NHMe}(Ph2-
PCH@CHPPh2–P)] (7a)
Appendix A. Supplementary data
Yield: 66.2 mg, 60%. Anal. Found: C, 59.8; H, 4.5; N, 5.8;
S, 4.5%; C35H32FN3P2PdS (714.1 g/mol) requires: C, 59.6;
H, 4.4; N, 5.8; S, 4.4%. IR (cmꢀ1): m(N–H) 3430m; m(C@N)
Crystallographic data (excluding structure factors) for
the structures reported in this paper have been deposited
with the Cambridge Crystallographic Data Centre as sup-
plementary publication numbers 287850 (a), 287855 (1a),
287857 (3d), 287856 (5a), 287851 (5c), 287853 (6a) and
287852 (7a). Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK. Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2006.02.014.
1
1578m. H NMR (d ppm, J Hz): 6.43 (m, 2H, H3, H4),
6.34 (m, 1H, H5), 5.81 (t, 2H, –HC@CH–, N = 28), 4.69
(q, 1H, NHMe, 3JNH–H = 5.1), 2.94 (d, 3H, NHMe, 3JH–
5
NH = 5.1), 2.50 (d, 3H, MeC@N, JHF = 4.6). 31P–{1H}
2
NMR (d ppm, J Hz): 22.3 (d, 1P, PA, JPP = 75.3), ꢀ25.2
(d, 1P, PB, 2JPP = 75.3).
4.3. Crystal structures
Crystals of ligand a and of complexes (1a, 3d, 5a, 5c, 6a,
6b, 7a) were mounted on a glass fiber and transferred to the
diffractometer.
For a and 1a room temperature X-ray data were col-
lected on a MACH3 Enraf Nonius diffractometer using
graphite monochromated Cu Ka radiation by the x/2h
method (a), and using monochromated Mo Ka radiation
by the omega method (1a).
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