Synthesis, characterization and solid state structures of thiosemicarbazone palladacycles: Influence of hydrogen bonding in the molecular arrangement

Article abstract of DOI:10.1016/j.jorganchem.2006.02.030

Treatment of the thiosemicarbazones 4-FC₆H₄C(Me){double bond, long}NN(H)C({double bond, long}S)NHR, (R = Me, a; Ph, b) and 2-ClC₆H₄C(Me){double bond, long}NN(H)C({double bond, long}S)NHR (R = Ph, c) with lithium

Full text of DOI:10.1016/j.jorganchem.2006.02.030

Journal of Organometallic Chemistry 691 (2006) 2891–2901
www.elsevier.com/locate/jorganchem
Synthesis, characterization and solid state structures
of thiosemicarbazone palladacycles: Influence of hydrogen bonding
in the molecular arrangement
a
a
a
a
´
´
Javier Martınez , Luis A. Adrio , Jose M. Antelo , Juan M. Ortigueira ,
a
a
b
a,
*
´
´
M Teresa Pereira , Margarita Lopez-Torres , 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 11 December 2005; received in revised form 21 February 2006; accepted 22 February 2006
Available online 28 February 2006
Abstract
Treatment of the thiosemicarbazones 4-FC6H4C(Me)@NN(H)C(@S)NHR, (R = Me, a; Ph, b) and 2-ClC6H4C(Me)@
NN(H)C(@S)NHR (R = Ph, c) with lithium tetrachloropalladate(II) in methanol or palladium(II) acetate in acetic acid gave the tetra-
nuclear cyclometallated complex [Pd{4-FC6H3C(Me)@NN@C(S)NHR}]4 (1a, 1b) and [Pd{2-ClC6H3C(Me)@NN@C(S)NHPh}]4 (1c).
Reaction of these tetramers with the diphosphines dppe, t-dppe, dppp or dppb in a 1:2 molar ratio gave the dinuclear cyclometallated
complexes [(Pd{4-FC6H3C(Me)@NN@C(S)NHR})2(l-Ph2P(CH2)nPPh2)], (n = 2, 2a, 2b; 3, 4a, 4b; 4, 5a, 5b), [(Pd{4-FC6H3C(Me)@
NN@C(S)NHPh})2(l-Ph2PCH@CHPPh2)], (3a, 3b) and [(Pd{2-ClC6H3C(Me)@NN@C(S)NHR})2(l-Ph2P(CH2)nPPh2)], (n = 2, 2c,
2d; 3, 4c, 4d; 4, 5c, 5d), [(Pd{2-ClC6H3C(Me)@NN@C(S)NHPh})2(l-PPh2CH@CHPPh2)], (3c, 3d). The X-ray crystal structure of the
ligand b and the complexes 3c, 4a and 4d were determined. The structures of complexes 4a and 4d show that the different disposition
of the chain cyclometallated of the thiosemicarbazones (in the same orientation or in the opposite one) is due to the different H bonds
produced.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Cyclometallated; Thiosemicarbazones; Palladium; C–H activation; H bonds
1. Introduction
pounds containing two non-carbon donor atoms are
known to act as tridentate ligands for palladium(II) or
platinum(II) and can produce cyclometallated complexes
having two fused rings at the metal centre [18–28]; a partic-
ular case being thiosemicarbazone and semicarbazone
ligands [23–25] which may bind to the metal atom as terd-
entate [C, N, S] and [C, N, O], respectively. Two unique
features distinguish thiosemicarbazones form other terden-
tate [C, N, X] (X = N, O, P) ligands: (a) the strength of the
Pd–Schelating bond, which hinders opening of the metallated
and coordination rings at the metal center, thus making the
ligands excellent pincer species which powerfully secure
three of the four coordination positions of the metal, allow-
ing only the fourth coordination site to undergo further
reaction with nucleophiles; (b) metallation of the ligand
Palladium cyclometallated compounds comprise
a
group of chemicals of great interest within organometallic
chemistry, as is inferred from the number of publications
devoted to this subject [1–6]. Particular attention has been
drawn to their applications as catalysts in organic synthe-
sis, in insertion and regio- and stereo-selective reactions
and as catalysts in organic synthesis [7–15], as well as to
the mechanistic aspects [16,17]. Thus, there is a continuing
quest for new cyclometallated species with different types
of ligands bearing N, P, O and/or S donor atoms. Com-
*
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.2006.02.030

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J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
microanalytical, mass spectra, IR and H and 31P–{1H}
NMR determinations (see Section 3). The mass spectrum
(FAB) showed peaks at m/z 1319 (1a), 1568 (1b)
and 1634 (1c) for the molecular ion whose isotopic com-
position suggests a tetranuclear complex of formula
C40H40F4N12Pd4S4 (1a), C60H48F4N12Pd4S4 (1b) and
C60H40Cl4N12Pd4S4 (1c) (see Section 3; Scheme 1).
The t(C@N) band was shifted to lower wavenumbers ca.
30–40 cmꢀ1 [32] indicating palladium coordination to the
C@N moiety at the nitrogen lone pair [33,34]. Absence of
the NH resonance in the 1H NMR spectra indicated depro-
tonation of the –NH– group [35,36], which causes loss of
the C@S double bond character as confirmed by the non-
existence of the t(C@S) band.
1
Ph2
P
Ph2
P
Pd
Pd
S
N
N
S
Me
Me
N
N
RHN
NHR
I
RHN
N
Me
S
N
Pd
Ph2
P
P
Ph2
Pd
N
S
Me
N
NHR
For complexes 1a, 1b metallation of the ligands was
clear from the absence of the AA0XX0 spin system of the
para-substituted phenyl ring; in its place an uncomplicated
first order three-spin system was obtained, where coupling
to the 19F nucleus was observed. For 1d the complex
ABCD spin system in the ligand gave rise to three proton
resonances which were unambiguously assigned (see Sec-
tion 3).
II
Fig. 1. cisoid (I) and transoid (II) geometries for the dinuclear compounds.
yields tetrameric compounds bearing a central Pd4S4 cen-
tral core. Upon reaction of the tetranuclear species with
tertiary diphosphines, compounds with bridging or with
mono-coordinate diphophine are obtained, the strength
of the Pd–Schelating bond preventing the chelating bidentate
mode of the diphosphine ligand [23,24]; with g1-diphos-
phines the corresponding compounds may behave as
bidentate [P,S] metalloligands as we have previously
shown [29]. In the cases with bridging diphosphines the
1H and 31P NMR data suggest symmetrical arrangements
across the phosphine ligand, the transoid geometry being
preferred to the cisoid one, as steric effects are minimized,
as solid structural analysis has shown [24,30] (Fig. 1).
However, the cisoid geometry may appear if intermolec-
ular hydrogen bonding is present as is herein reported.
2.1. Reactivity of the complexes
Treatment of 1a–1c with the corresponding diphosphine
in a 1:2 molar ratio produced compounds [{Pd[4-
FC6H3C(Me)@NN@C(S)NHR]}2(l-Ph2P(CH2)nPPh2)]
(n = 2, R = Me, 2a, R = Ph, 2b; n = 3, R = Me, 4a,
R = Ph, 4b; n = 4, R = Me, 5a, R = Ph, 5b) [{Pd[4-
FC6H3C(Me)@NN@C(S)NHR]}2(l-Ph2PCH@CHPPh2)]
(R = Me, 3a, R = Ph, 3b) [{Pd[2-ClC6H3C(Me)@
NN@C(S)NHPh]}2(l-Ph2P(CH2)nPPh2)] (n = 2, 2c; n = 3,
4c; n = 4, 5c) [{Pd[2-ClC6H3C(Me)@NN@C(S)NHPh]}2-
(l-Ph2PCH@CHPPh2)] (3c) as pure air-stable solids, which
were completely characterised (see Section 3).
2. Results and discussion
1
The H NMR spectra showed the high field shift of the
The ligands a–c were prepared by reaction of 4-methyl
or 4-phenyl-3-thiosemicarbazide with 40-fluoro- or 20-
chloro acetophenone as appropriate, in good yields (see
Section 3). The NHR and NH groups gave rise to charac-
teristic t(N–H) bands in the IR spectra ca. 3300 and
3200 cmꢀ1, respectively, the latter disappears in the spectra
of the complexes [31]; the typical t(C@N) and t(C@S)
stretches appeared in the ranges 1620–1590 and 840–
H5 resonance by ca. 1–1.5 ppm, which was coupled to the
31P nucleus, pointing towards a P trans to N arrangement
[37]. The symmetric nature of the complexes was put for-
1
ward by the H NMR spectra, which showed only one
set of signals; and accordingly, a singlet was observed for
the 31P resonance due to two equivalent phosphorus nuclei;
the chemical shift value for the latter also supported a
phosphorus trans to nitrogen geometry [38–40].
1
800 cmꢀ1, respectively. The H NMR spectra showed sig-
nals ca. d 8.64 (a), d 9.35 (b), d 9.34 (c) and d 7.59 (a), d
7.53 (b), d 7.43 (c) for the NHR and NH protons, respec-
tively. From the ligands synthesis of the compounds was
achieved y anyone of the three alternative methods
described, i.e., (a) potassium tetrachloropalladate in etha-
nol; (b) lithium tetrachloropalladate in methanol; (or) pal-
ladium(II) acetate in glacial acetic acid, resulting in all
cases tetranuclear species, [Pd{4-FC6H3C(Me)@NN@
C(S)NHR}]4 (1a, 1b) and [Pd{2-ClC6H3C(Me)@NN@
C(S)–NHPh}]4 (1c), as air-stable solids, with the ligand in
the E,Z configuration, which were fully characterized by
2.2. Structural studies: crystal structures of ligand b and of
complexes 4a and 4c
Suitable crystals were grown by slowly evaporating
chloroform/n-hexane solutions. The crystal structures are
shown in Figs. 2, 4 and 5. Crystal data are given in Table 1.
2.2.1. 4-FC6H4C(Me)@NN(H)C(@S)NHMe (b)
Ligand b crystallizes in the monoclinic P21/n space
group as the E,Z-isomer relative to the N(1)–C(7) and
N(8)–C(3) bonds, respectively, Fig. 2.

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
2893
RHN
N
Me
S
N
Ph2
P
Pd
X
P
Ph2
X
Pd
RHN
N
S
N
Me
Me
N
S
N
2a, 2b, 2c
ii
NHR
Ph2
P
Pd
X
P
Ph2
X
Pd
N
S
Me
N
NHR
4
3a, 3b, 3c
3
2
5
iii
X
6
i
X
Pd
N
Me
N
S
Me
RHN
HN
S
iv
N
N
Me
NHR
S
N
NHR
Pd
4
Ph2
P
a: R = Me; X = 4-F
b: R = Ph; X = 4-F
c: R = Ph; X = 2-Cl
1a, 1b, 1c
X
P
Ph2
X
Pd
N
S
Me
v
N
NHR
4a, 4b, 4c
RHN
N
Me
S
N
Ph2
P
Pd
X
P
Ph2
X
Pd
N
S
Me
N
5a, 5b, 5c
NHR
Scheme 1. (i) K2[PdCl4]/EtOH; Li2[PdCl4]/MeOH; Pd(AcO)2/AcOH; (ii) Ph2P(CH2)2PPh2/acetone; (iii) trans-Ph2PCH@CHPPh2/acetone; (iv) Ph2P-
(CH2)3PPh2/ acetone; (v) 2: Ph2P(CH2)4PPh2/acetone.
˚
This is typical of thiosemicarbazones where weak N(3)–
H(3). . .N(1) hydrogen bonding is present (Fig. 2). The
C(8)–S(1) and N(1)–C(7) bond distances, 1.6751(18) and
N(3)–H(3). . .N(1)
C(15). . .S(1A) 3.521(4) A, C(15)–H(15). . .S(1A) 137.01ꢁ.
110.37ꢁ,
H(15). . .S(1A)
2.76 A,
˚
˚
1.286(2) A, respectively, are consistent with double bond
2.2.2. [(Pd{4-FC6H3C(Me)@NN@C(S)NHMe})2-
(l-Ph2P(CH2)3PPh2)] (4a), [(Pd{2-ClC6H3C(Me)
@NN@C(S)NHPh})2(l-Ph2P(CH2)3PPh2)] (4c)
character, as are the C(1)–C(7)–N(1) 115.03(16)ꢁ and
C(7)–N(1)–N(2) 119.63(15)ꢁ bond angles in accordance
with sp2 hybridization of the carbon and nitrogen atoms
of the C@N group. The thioamide chain C(1)–C(7)–
N(1)–N(2)–C(8)–N(3)–C(9) is planar (rms = 0.0314) and
at an angle of 39.4(4)ꢁ with the fluorinated phenyl ring
(rms = 0.0015). An intermolecular self-assembly between
the ligands is established through hydrogen bonds by the
MeC@N methyl group, the sulfur atoms and the amido
hydrogen atoms. The parameters for the hydrogen bonding
interaction (Fig. 3) in ligand b are as follows: H(2). . .S(1A)
The crystals consist of discrete molecules, separated by
normal van der Waals distances. The palladium(II) atoms,
which in the case of compound 4a are not symmetry related
(only data for the Pd(1) part will be discussed; those for
Pd(2) are very similar and may be obtained from the sup-
plementary information), are bonded to four different
donor atoms, a terdentate C, N, S thiosemicarbazone
through the aryl C(6) carbon, the imine N(1) nitrogen,
and the thioamide S(1) 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),
˚
˚
2.844 A, N(2). . .S(1A) 3.701 A, N(2)–H(2). . .S(1A)
˚
˚
174.53ꢁ, H(3). . .N(1) 2.144 A, N(3). . .N(1) 2.572(3) A,

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J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
Table 1
Crystal data and structure refinement data for b, 4a and 4c
Compound
b
4a
C50H49Cl9F2N6 P2Pd2S2
1429.86
293(2)
0.71069
4c
C59H52Cl8N6P2Pd2S2
1467.53
293(2)
0.71073
Empirical formula
Formula weight
Temperature (K)
Wavelength (A)
Crystal system
Space group
C15H14FN3S
287.35
293(2)
1.54184
Monoclinic
P21/n
˚
Triclinic
Monoclinic
C2/c
ꢀ
P1
Unit cell dimensions
˚
a (A)
14.7389(11)
5.8895(3)
16.8900(19)
12.612(5)
15.127(5)
15.855(5)
33.954(9)
9.062(2)
20.140(5)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
80.842(5)
84.603(5)
81.827(5)
2948.1(18)
100.534(6)
97.879(5)
3
˚
Volume (A )
1441.4(2)
6138(3)
Z
4
2
4
Density (calculated) (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
1.324
2.038
600
0.64 · 0.08 · 0.08
3.66–73.37
1.611
1.189
1432
0.22 · 0.21 · 0.07
1.30–26.43
1.588
1.098
2952
0.24 · 0.18 · 0.12
1.21–26.43
)
Crystal size (mm3)
h Range for data collection (ꢁ)
Index ranges
Reflections collected
0/h/18, ꢀ7/k/0, ꢀ20/l/20
ꢀ15/h/15, ꢀ18/k/18, 0/l/19
ꢀ42/h/42, 0/k/11, 0/l/25
3026
33653
18508
Independent reflections [R(int)]
Completeness to h
2910 [0.0204]
100.0%
12020 [0.0641]
99.1%
6224 [0.0809]
98.5%
Absorption correction
Maximum and minimum transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
Semi-empiric
0.8539 and 0.3554
Full-matrix least-squares on F2
2910/0/183
Semi-empiric
0.9214 and 0.7798
Full-matrix least-squares on F2
12020/9/664
0.998
R1 = 0.0658, wR2 = 0.1789
R1 = 0.1402, wR2 = 0.1983
1.496 and ꢀ1.337
Semi-empiric
0.8795 and 0.7785
Full-matrix least-squares on F2
6224/0/358
1.084
1.008
R1 = 0.0407, wR2 = 0.1197
R1 = 0.0535, wR2 = 0.1271
0.234 and ꢀ0.228
R1 = 0.0676, wR2 = 0.1640
R1 = 0.1564, wR2 = 0.2127
0.913 and ꢀ1.596
ꢀ3
˚
Largest difference in peak and hole (e A
)
˚
C(6), P(1), plane 1] (rms = 0.0052 A) 4a, (Fig. 4), [Pd(1),
metal, and are decreased by ca. 7–10ꢁ for the C(6)–Pd(1)–
N(1) and C(43)–Pd(2)–N(4) angles, and increased by a sim-
ilar amount for the C(6)–Pd(1)–P(1) and C(43)–Pd(2)–P(2)
angles. All bond distances are within the expected range,
with lengthening of the Pd–N bond due to the trans influ-
ence of the phosphine ligand, which is reflected in the
˚
N(1), S(1), C(1), P(1), plane 1] (rms = 0.0585 A) 4c, (Fig. 5).
The main difference between the structures is the relative
disposition of the cyclometallated moieties, which in com-
pound 4a adopt a cisoid arrangement (Fig. 6), whereas in
compound 4c they appear in a transoid fashion (Fig. 7),
as a consequence of hydrogen bond formation: in 4a an
intermolecular self-assembly between the cyclometallated
groups is established through two hydrogen bonds by the
sulfur atoms and the amido hydrogen atoms; whereas in
4c the hydrogen bonds are between the sulfur atoms and
the central carbon atom of the bridging diphosphine
ligand. In 4a the hydrogen bonding parameters are
H(3). . .S(1A) 2.770 A, N(3). . .S(1A) 3.5838 A, N(3)–
H(3). . .S(1A) 158.50ꢁ, and in 4c the parameters are
H(17). . .S(1A) 2.778 A, C(17). . .S(1A) 3.5278 A, C(17)–
H(17). . .S(1A) 133.65ꢁ, precluding a cisoid geometry in this
case.
As for the bond distances, and for the angles at palla-
dium, the data observed for both structures are similar
and follow essentially analogous alterations from the theo-
retical values. Thus, the angles between adjacent atoms in
the coordination sphere of the palladium centers undergo
distorsions from the theoretical value of 90ꢁ, consequent
upon formation of the two five-membered rings at the
˚
˚
Pd(1)–N(1), 2.039(6) A 4a and 2.020(7) A, 4c, distances
(cf. sum of the covalent radii for palladium and nitrogen,
˚
2.01 A [41]), and shortening of the Pd–C bond with to
˚
the expected value of 2.081 A [41], as has been observed
˚
˚
before [42,43], Pd(1)–C(6) 2.044(8) A 4a and 2.040(10) A
˚
˚
4c. The S(1)–C(8) 1.769(8) A 4a, 1.743(10) A, 4c, bond
˚
˚
lengths, and the N(2)–C(8), 1.303(10) A 4a, 1.319(11) A,
4c, lengths, are consistent with increased single and double
bond character, respectively, as a result of deprotonation.
The planes at palladium: the coordination plane [Pd(1),
N(1), S(1), C(6), 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 =
1.10(0.08), 1/3 = 0.56(0.04), 1/4 = 4.10(0.13), 2/3 = 1.10
(0.09), 2/4 = 3.04(0.14), 3/4 = 4.13(0.13)ꢁ 4a; 1/2 = 4.45
(0.18), 1/3 = 5.06(0.11), 1/4 = 6.57(0.22), 2/3 = 4.72(0.16),
2/4 = 2.27(0.25), 3/4 = 6.58(0.24)ꢁ 4c). As for the overall
˚
˚
˚
˚

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
2895
Fig. 2. An ORTEP drawing of the molecular structure for b with labeling scheme (50% probability). Selected bond lengths and angles: C(1)–C(7) 1.484(2);
N(1)–C(7) 1.286(2); N(1)–N(2) 1.374(2); N(2)–C(8) 1.362(2); S(1)–C(8) 1.6751(18); C(8)–N(3) 1.341(2); C(6)–C(1)–C(7) 120.32(16); N(1)–C(7)–C(1)
115.03(16); C(7)–N(1)–N(2) 119.63(15); C(8)–N(2)–N(1) 118.20(14); N(3)–C(8)–N(2) 114.56(16); N(3)–C(8)–S(1) 125.58(13); N(2)–C(8)–N(1) 119.83(13).
metallated units, in compound 4a they are fixed in a nearly
co-planar parallel mode (angle between planes 3.17(0.03)ꢁ),
and at 4.57(0.03)ꢁ and 4.12(0.03)ꢁ with the P–C–C–C–P
plane, so that the entire molecule may envisaged as planar
with the phosphine phenyl rings jutting out from the
molecular plane (see Fig. 8), whereas in compound 4c the
two metallated moieties are at an angle of 69.10ꢁ.
3. Experimental
3.1. General procedures
Solvents were purified by standard methods [44]. 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,
palladium(II) chloride and potassium tetrachloropalla-
date(II) were purchased from Alfa Products. The phosphines
Ph2P(CH2)2PPh2 (dppe), trans-Ph2P(CH@CH)PPh2(t-dpe),
Ph2P(CH2)3PPh2 (dppp) and Ph2P(CH2)4PPh2- (dppb)
were purchased from Aldrich-Chemie. Microanalyses were
´
carried out at the Servicio de Analisis Elemental at the
Fig. 3. A view of the hydrogen bond interactions in ligand b.

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J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
Fig. 4. An ORTEP drawing of the molecular structure for 4a with labeling scheme (50% probability). Hydrogen atoms have been omitted for clarity.
Selected bond lengths and angles (at the metal): Pd(1)–N(1) 2.039(6); Pd(1)–C(6) 2.044(8); Pd(1)–P(1) 2.261(2); Pd(1)–S(1) 2.337(2); S(1)–C(8) 1.769(8);
N(2)–C(8) 1.303(10); N(3)–C(8) 1.330(10); N(1)–N(2) 1.372(8); N(1)–C(7) 1.286(9); C(1)–C(7) 1.465(11); P(1)–C(23) 1.827(7); P(1)–C(11) 1.821(8); P(1)–
C(17) 1.822(8); N(1)–Pd(1)–C(6) 80.6(3); C(6)–Pd(1)–P(1) 97.5(2); P(1)–Pd(1)–S(1) 99.74(8); N(1)–Pd(1)–S(1) 82.22(18); N(1)–Pd(1)–P(1) 177.67(18); C(1)–
Pd(1)–S(1) 162.8(8). Pd(2)–N(4) 2.032(6); Pd(2)–C(43) 2.051(7); Pd(2)–P(2) 2.251(2); Pd(2)–S(2) 2.331(2); S(2)–C(45) 1.763(9); N(5)–C(45) 1.306(10);
N(6)–C(45) 1.332(10); N(4)–N(5) 1.365(8); N(4)–C(44) 1.309(9); C(38)–C(44) 1.479(11); P(2)–C(25) 1.827(7); P(2)–C(26) 1.821(8); P(2)–C(32) 1.822(8);
N(4)–Pd(2)–C(43); C(43)–Pd(2)–P(2) 97.6(2); P(2)–Pd(2)–S(2) 98.62(8); N(4)–Pd(2)–S(2) 82.3(2); N(4)–Pd(2)–P(2) 178.53(19); C(43)–Pd(2)–S(2) 163.7(2).
Universidad of Santiago of Compostela using
a
(CDCl3, d ppm, J Hz): 8.64 (s, 1H, NH), 7.59 (br, 1H,
NHMe), 7.68 (dd, 2H, H2, H6, 3J(H2H3) = 9.1,
4J(H2F) = 5.3), 7.08 (t, 2H, H3, H5, 3J(H3F) = 9.1,
Carlo Erba Elemental Analyzer Model EA1108. IR spec-
tra 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-66V spectro-
photometers. 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 WM-250 spectrometers. All chemical shifts are
reported downfield from standards. The FAB mass spec-
tra were recorded with a Fisons Quatro mass spectrometer
with a Cs ion gun; 3-nitrobenzyl alcohol was used as the
matrix.
3
3J(H5F) = 9.1), 3.27 (d, 3H, NHMe, J(HH) = 5.0), 2.25
(s, 3H, MeC@N). FAB-MS: m/z 226 [MH]+.
The thiosemicarbazones b–d were synthesized following
a similar procedure.
3.2.2. 4-FC6H4C(Me)@NN(H)C(@S)NHPh (b)
Yield: 163 mg, 95%. Anal. Found: C, 62.7; H, 4.8; N,
14.7; S, 11.1; C15H14N3FS (287.4 g/mol) requires C, 62.7;
H, 4.9; N, 14.6; S, 11.2%. IR (cmꢀ1): m(N–H) 3307s,
1
3237m; m(C@N) 1618w; m(C@S) 840s. H NMR (CDCl3,
d ppm, J Hz): 9.35 (s, 1H, NH), 8.76 (s, 1H, NHPh),
3.2. Syntheses
7.74 (dd, 2H, H2, H6, 3J(H2H3) = 9.1, 4J(H2F) = 5.3),
3
7.68 (d, 2H, H20, H60, J(HH) = 7.9), 7.41 (t, 2H, H30,
3
3
3.2.1. Preparation of 4-FC6H4C(Me)
@NN(H)C(@S)NHMe (a)
H50, J(HH) = 7.9), 7.25 (t, 1H, H40, J(HH) = 7.9), 7.12
(t, 2H, H3, H5, 3J(H3F) = 9.1, 3J(H5F) = 9.1), 2.33 (s,
3H, MeC@N). FAB-MS: m/z 288 [MH]+.
40-Fluoroacetophenone (131 mg, 9.51 mmol) and hydro-
chloric acid (35%, 0.65 cm3) 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 precipi-
tated was filtered off, washed with cold water, and dried
in air. Yield: 204 mg, 95%. Anal. Found: C, 53.5; H, 5.2;
N, 18.6; S, 14.0; C10H12N3FS (225.3 g/mol) requires C,
53.3; H, 5.4; N, 18.6; S, 14.2%. IR (cmꢀ1): m(N–H)
3.2.3. 2-ClC6H4C(Me)@NN(H)C(@S)NHPh (c)
Yield: 177 mg, 97%. Anal. Found: C, 59.5; H, 4.8; N,
14.0; S, 10.5; C15H14ClN3S (303.8 g/mol) requires C, 59.3;
H, 4.6; N, 13.8; S, 10.6%. IR (cmꢀ1): m(N–H) 3296s,
1
3201m; m(C@N) 1594m; m(C@S) 800w. H NMR (CDCl3,
d ppm, J Hz): 9.34 (s, 1H, NH), 8.75 (br, 1H, NHPh),
7.43 (m, 4H, H3, H4, H5, H6), 2.35 (s, 3 H, MeC@N).
FAB-MS: m/z 304 [M]+.
1
3353m, 3219m; m(C@N) 1619w; m(C@S) 836m. H NMR

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
2897
Fig. 5. An ORTEP drawing of the molecular structure for 4c with labeling scheme (50% probability). Hydrogen atoms have been omitted for clarity.
Selected bond lengths and angles (at the metal): Pd(1)–N(1) 2.020(7); Pd(1)–C(6) 2.040(10); Pd(1)–P(1) 2.274(2); Pd(1)–S(1) 2.322(3); S(1)–C(8) 1.743(10);
N(2)–C(8) 1.319(11); N(3)–C(8) 1.375(11); N(1)–N(2) 1.384(10); N(1)–C(7) 1.279(11); C(1)–C(7) 1.475(12); P(1)–C(16) 1.820(9); P(1)–C(18) 1.816(9); P(1)–
C(24) 1.826(9); N(1)–Pd(1)–C(6) 80.6(3); C(6)–Pd(1)–P(1) 98.6(2); P(1)–Pd(1)–S(1) 97.31(9); N(1)–Pd(1)–S(1) 83.7(2); N(1)–Pd(1)–P(1) 177.4(2); C(1)–
Pd(1)–S(1) 163.7(2).
Fig. 6. Hydrogen bond interactions in compound 4a.

2898
J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
Fig. 7. Hydrogen bond interactions in compound 4c.
3J(H2H3) = 8.3, 4J(H2F) = 5.5), 6.58 (td, 1H, H3,
3
4
3J(H3F) = 8.8, J(H3H2) = 8.3, J(H3H5) = 2.8), 5.03 (q,
1H, NHMe, 3J(NH–H) = 5.1), 3.00 (d, 3H, NHMe,
3J(H–NH) = 5.1), 1.82 (s, 3H, MeC@N). FAB-MS: m/z
1319 [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 cm3) to give a clear solution, which
was heated to 60 ꢁC under nitrogen for 24 h. After this
had cooled to room temperature, the yellow precipitate
was filtered off, washed with ethanol, and dried. Yield:
272 mg, 93%.
Fig. 8. An ORTEP drawing of compound 4a showing the parallel
arrangement of the cyclometallated units and the phosphine ligand, with
exception of the phosphine phenyl rings.
Compounds 1b and 1c were synthesized following a sim-
ilar procedure.
3.2.4. Preparation of [Pd{4-FC6H3C(Me)
@NN@C(S)NHMe}]4 (1a)
3.2.5. [Pd{4-FC6H3C(Me)@NN@C(S)NHPh}]4 (1b)
Method 1. Yield: 204 mg, 85%. Anal. Found: C, 45.9; H,
3.1; N, 10.7; S, 8.3; C60H48F4N12Pd4S4 (1567.0 g/mol)
requires C, 46.0; H, 3.1; N, 10.7; S, 8.2%. IR (cmꢀ1):
m(N–H) 3409m, m(C@N) 1582m. 1H NMR (CDCl3, d
Method 1. To a stirred solution of potassium tetrachlo-
ropalladate (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 4-FC6H4C(Me)@NN(H)C(@S)NHMe (a) (152 mg,
0.67 mmol, 10% excess). The mixture was stirred for 48 h
at room temperature under nitrogen. The yellow precipi-
tate was filtered off, washed with ethanol and dried. Yield:
192 mg, 95%. Anal. Found: C, 36.5; H, 3.1; N, 12.5; S 9.8;
C40H40F4N12Pd4S4 (1318.8 g/mol) requires C, 36.4; H, 3.1;
N, 12.7; S, 9.7%. IR (cmꢀ1): m(N–H) 3439m; m(C@N)
3
ppm, J Hz): 7.52 (d, 2H, H20, H60, J(HH) = 7.9), 7.34
(t, 2H, H30, H50, 3J(HH) = 7.9), 7.21 (dd, 1H, H5,
3J(H5F) = 8.8, 4J(H5H3) = 2.8), 6.90 (dd, 1H, H2,
3J(H2H3) = 8.8, 4J(H2F) = 5.1), 7.05 (t, 1H, H40,
3J(HH) = 7.9), 6.83 (s, 1H, NHPh), 6.70 (td, 1H, H3,
3
4
3J(H3F) = 8.8, J(H3H2) = 8.8, J(H3H5) = 2.8), 1.89 (s,
3H, MeC@N). FAB-MS: m/z 1568 [M–H]+.
Method 2. Yield: 435 mg, 98%. Method 3. Yield: 295 mg,
85%.
1
1586m. H NMR (CDCl3, d ppm, J Hz): 7.16 (dd, 1 H,
H5, 3J(H5F) = 8.8, 4J(H5H3) = 2.8), 6.74 (dd, 1H, H2,

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
2899
3.2.6. [Pd{2-ClC6H3C(Me)@NN@C(S)NHPh}]4 (1c)
3.2.10. [{Pd{4-FC6H3C(Me)@NN@C(S)NHMe]}2(l-
Ph2PCH@CHPPh2)] (3a)
Method 2. Yield: 406 mg, 92%. Anal. Found: C, 43.9; H,
2.9; N, 10.3; S, 8.0; C60H48Cl4N12Pd4S4 (1632.9 g/mol)
requires C, 44.1; H, 3.0; N, 10.3; S, 7.9%. IR (cmꢀ1):
Yield: 31.3 mg, 65%. Anal. Found: C, 52.0; H, 3.9; N,
7.7; S, 5.9; C46H42F2N6P2Pd2S2 (1055.8 g/mol) requires
C, 52.3; H, 4.0; N, 8.0; S, 6.1%. IR (cmꢀ1): m(N–H)
1
m(N–H) 3409m, m(C@N) 1558s. H NMR (CDCl3, d ppm,
3
1
J Hz): 7.49 (d, 2H, H20, H60, J(HH) = 7.9), 7.34 (d, 2H,
3421m; m(C@N) 1585m. H NMR (CDCl3, d ppm, J Hz):
H30, H50, 3J(HH) = 7.9), 7.30
(d, 1H, H5,
7.10 (dd, 1H, H2, 3J(H2H3) = 8.3, 4J(H2F) = 5.5), 6.57
3
3J(H5H4) = 7.9), 7.08 (t, 1H, H40, J(HH) = 7.9), 7.03 (d,
1H, H3, 3J(H3H4) = 7.9), 6.93 (s, 1H, NHPh), 6.66 (t,
1H, H4, 3J(H4H3) = 7.9, 3J(H4H5) = 7.9), 2.24 (s, 3H,
MeC@N). FAB-MS: m/z 1634 [M–H]+.
(td,
1H,
H3,
3J(H3F) = 8.3,
3J(H3H2) = 8.3,
4J(H3H5) = 2.3), 6.01 (m, 1H, H5), 2.96 (d, 3H, NHMe,
3J(H–NH) = 4.6), 2.50 (s, 3H, MeC@N). 31P–{1H} NMR
(CDCl3, d ppm): 31.9s.
Method 3. Yield: 251 mg, 69%.
3.2.11. [{Pd{4-FC6H3C(Me)@NN@C(S)NHPh]}2-
(l-Ph2PCH@CHPPh2)] (3b)
3.2.7. Preparation of [{Pd[4-FC6H3C(Me)@NN@
C(S)NHMe]}2(l-Ph2P(CH2)2PPh2)] (2a)
Yield: 27.3 mg, 60%. Anal. Found: C, 56.8; H, 3.7; N,
6.9; S, 5.3; C56H46F2N6P2Pd2S2 (1179.9 g/mol) requires
C, 57.0; H, 3.9; N, 7.1; S, 5.4%. IR (cmꢀ1): m(N–H)
The diphosphine Ph2P(CH2)2PPh2 (18 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: 32.2 mg, 67%. Anal. Found: C, 52.1; H, 4.1;
N, 7.7; S, 5.9; C46H44F2N6P2Pd2S2 (1057.8 g/mol) requires
C, 52.2; H, 4.2; N, 7.9; S, 6.1%. IR (cmꢀ1): m(N–H) 3426s;
1
3412w; m(C@N) 1586m. H NMR (CDCl3, d ppm, J Hz):
3
7.46 (d, 2H, H20, H60, J(HH) = 7.9), 7.11 (dd, 1H, H2,
3J(H2H3) = 8.8, 4J(H2F) = 5.5), 6.97 (t, 1H, H40,
3J(HH) = 7.9), 6.65 (s, 1H, NHPh), 6.54 (td, 1H, H3,
3J(H3F) = 8.3, 3J(H3H2) = 8.3, 4J(H3H5) = 2.3), 6.09
(m, 1H, H5), 2.46 (s, 3H, MeC@N). 31P–{1H} NMR
(CDCl3, d ppm): 32.5s.
1
m(C@N) 1589s. H NMR (CDCl3, d ppm, J Hz): 7.09 (dd,
1H, H2, 3J(H2H3) = 8.3, 4J(H2F) = 5.5), 6.58 (td, 1H, H3,
3J(H3F) = 8.3 Hz, 3J(H3H2) = 8.3 Hz, 4J(H3H5) = 2.3),
5.87 (m, 1H, H5), 2.99 (d, 3H, NHMe, 3JH–NH = 4.6 Hz),
2.77 (br, 2H, P(CH2)2P), 2.51 (s, 3H, MeC@N). 31P–{1H}
NMR (CDCl3, d ppm): 32.1s.
3.2.12. [{Pd{2-ClC6H3C(Me)@NN@C(S)NHPh]}2-
(l-Ph2PCH@CHPPh2)] (3c)
Yield: 25.0 mg, 56%. Anal. Found: C, 55.3; H, 3.8; N,
6.9; S, 5.3; C56H46Cl2N6P2Pd2S2 (1212.8 g/mol) requires
C, 55.5; H, 3.8; N, 6.9; S, 5.3%. IR (cmꢀ1): m(N–H)
Compounds 2b, 2c, 3a, 3c, 4a, 4c, 5a and 5c were synthe-
sized analogously.
1
3412m; m(C@N) 1552m. H NMR (CDCl3, d ppm, J Hz):
3
7.43 (d, 2H, H20, H60, J(HH) = 7.9), 6.98 (t, 1H, H40,
3
3J(HH) = 7.9), 6.81 (d, 1H, H3, J(H3H4) = 7.9), 6.65 (s,
3.2.8. [{Pd{4-FC6H3C(Me)@NN@C(S)NHPh]}2(l-Ph2-
P(CH2)2PPh2)] (2b)
1H, NHPh), 6.35 (m, 1H, H5), 6.26 (t, 1H, H4,
3
3J(H4H3) = 7.9, J(H4H5) = 7.9), 2.83 (s, 3H, MeC@N).
Yield: 36.1 mg, 80%. Anal. Found: C, 56.8; H, 4.0; N,
6.9; S, 5.3; C56H48F2N6P2Pd2S2 (1181.9 g/mol) requires
C, 56.9; H, 4.1; N, 7.1; S, 5.4%. IR (cmꢀ1): m(N–H)
31P–{1H} NMR (CDCl3, d ppm): 32.5s.
1
3417m; m(C@N) 1588m. H NMR (CDCl3, d ppm, J Hz):
3.2.13. [{Pd{4-FC6H3C(Me)@NN@C(S)NHMe]}2-
(l-Ph2P(CH2)3PPh2)] (4a)
3
7.51 (d, 2H, H20, H60, J(HH) = 7.9), 7.12 (dd, 1H, H2,
4
3J(H2H3) = 8.8 Hz, J(H2F) = 5.5), 6.98 (t, 1H, H40,
Yield: 27.1 mg, 56%. Anal. Found: C, 52.6; H, 4.3; N,
7.7; 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)
3J(HH) = 7.9), 6.71 (s, 1H, NHPh), 6.57 (td, 1H, H3,
3J(H3F) = 8.3, 3J(H3H2) = 8.3, 4J(H3H5) = 2.3), 6.03
(m, 1H, H5), 2.82 (br, 2H, P(CH2)2P), 2.46 (s, 3H,
MeC@N). 31P–{1H} NMR (CDCl3, d ppm): 31.5s.
1
3427m; m(C@N) 1583m. H NMR (CDCl3, d ppm, J Hz):
7.01 (dd, 1H, H2, 3J(H2H3) = 8.3, 4J(H2F) = 5.5), 6.51
(td,
1H,
H3,
3J(H3F) = 8.3,
3J(H3H2) = 8.3,
3.2.9. [{Pd{2-ClC6H3C(Me)@NN@C(S)NHPh]}2-
(l-Ph2P(CH2)2PPh2)] (2c)
4J(H3H5) = 2.8), 5.97 (ddd, 1H, H5, 3J(H5F) = 9.2,
4J(H5P) = 4.2, 4J(H3H5) = 2.8), 4.78 (q, 1H, NHMe,
3
Yield: 31.9 mg, 71%. Anal. Found: C, 55.5; H, 4.0; N,
7.0; S, 5.2; C56H48Cl2N6P2Pd2S2 (1214.9 g/mol) requires
C, 55.4; H, 4.0; N, 6.9; S, 5.3%. IR (cmꢀ1): m(N–H)
3J(NH–H) = 5.1), 2.99 (d, 3H, NHMe, J(H–NH) = 5.1),
2.53 (m, 2H, PCH2CH2CH2P), 2.35 (s, 3H, MeC@N),
2.09 (br, 1H, PCH2CH2CH2P). 31P–{1H} NMR (CDCl3,
d ppm): 27.1s.
1
3400m; m(C@N) 1557m. H NMR (CDCl3, d ppm, J Hz):
3
7.50 (d, 2H, H20, H60, J(HH) = 7.9), 7.00 (t, 1H, H40,
3J(HH) = 7.9), 6.87 (dd, 1H, H3, 3J(H3H4) = 7.9,
4J(H3H5) = 0.9), 6.68 (s, 1H, NHPh), 6.40 (t, 1H, H4,
3.2.14. [{Pd{4-FC6H3C(Me)@NN@C(S)NHPh]}2-
(l-Ph2P(CH2)3PPh2)] (4b)
Yield: 35.3 mg, 77%. Anal. Found: C, 57.0; H, 4.1; N,
6.9; S, 5.2; C57H50F2N6P2Pd2S2 (1196.0 g/mol) requires
C, 57.2; H, 4.2; N, 7.0; S, 5.4%. IR (cmꢀ1): m(N–H)
3
3J(H4H3) = 7.9, J(H4H5) = 7.9), 6.28 (m, 1H, H5), 2.84
(br, 5H, MeC@N, P(CH2)2P). 31P–{1H} NMR (CDCl3, d
ppm): 31.5s.

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J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
1
3419m; m(C@N) 1587m. H NMR (CDCl3, d ppm, J Hz):
7.52 (d, 2H, H20, H60, 3J(HH) = 7.9 Hz), 7.08 (dd, 1H,
C, 56.0; H, 4.2; N, 6.8; S, 5.2%. IR (cmꢀ1): m(N–H)
1
3406m; m(C@N) 1557m. H NMR (CDCl3, d ppm, J Hz):
H2, 3J(H2H3) = 8.3, J(H2F) = 5.5), 6.99 (t, 1H, H40,
7.47 (d, 2H, H20, H60, J(HH) = 7.9), 6.98 (t, 1H, H40,
4
3
3J(HH) = 7.9), 6.72 (s, 1H, NHPh), 6.54 (td, 1H, H3,
3J(H3F) = 8.3, 3J(H3H2) = 8.3, 4J(H3H5) = 2.8), 6.02
3J(HH) = 7.9), 6.84 (dd, 1H, H3, 3J(H3H4) = 7.9,
4J(H3H5) = 0.9), 6.75 (s, 1H, NHPh), 6.44 (t, 1H, H4,
3J(H4H3) = 7.9, 3J(H4H5) = 7.9), 6.35 (ddd, 1H, H5,
(ddd,
1H,
H5,
3J(H5F) = 9.2,
4J(H5P) = 4.2,
4J(H3H5) = 2.8), 2.59 (m, 2H, PCH2CH2CH2P), 2.43 (s,
3H, MeC@N), 2.21 (br, 1H, PCH2CH2CH2P). 31P–{1H}
NMR (CDCl3, d ppm): 26.8s.
3J(H5H4) = 7.9, J(H5P) = 4.6, J(H5H3) = 0.9), 2.82 (s,
3H, MeC@N), 2.34 (m, H, PCH2CH2CH2CH2P), 1.81
(br, 2H, PCH2CH2CH2CH2P). 31P–{1H} NMR (CDCl3,
d ppm): 28.7s.
4
4
3.2.15. [{Pd{2-ClC6H3C(Me)@NN@C(S)NHPh]}2-
(l-Ph2P(CH2)3PPh2)] (4c)
3.3. Crystal structures
Yield: 18.5 mg, 41%. Anal. Found: C, 55.9; H, 4.2; N, 6.9;
S, 5.1; C57H50Cl2N6P2Pd2S2 (1228.9 g/mol) requires C, 55.7;
H, 4.1; N, 6.8; S, 5.2%. IR (cmꢀ1): m(N–H) 3392m; m(C@N)
Crystals of ligand b and of complexes 4a Æ 3CHCl3 and
4c Æ CHCl3 were mounted on a glass fiber and transferred
to the diffractometer. For b room temperature X-ray data
was collected on a CAD4 Enraf Nonius diffractometer
using graphite monochromated Cu Ka radiation by the
omega/2-theta method. Three dimensional, room tempera-
ture X-ray data, 4a and 4d, were collected with Bruker
SMART CCD diffractometer by the omega scan method,
using monochromated Mo Ka radiation. All the measured
reflections were corrected for Lorentz and polarization
effects and for absorption by semiempirical methods based
1
1556m. H NMR (CDCl3, d ppm, J Hz): 7.50 (d, 2H, H20,
3
3
H60, J(HH) = 7.9), 7.00 (t, 1H, H40, J(HH) = 7.9), 6.85
(dd, 1H, H3, 3J(H3H4) = 7.9, 4J(H3H5) = 0.9), 6.73 (s,
1H, NHPh), 6.45 (t, 1H, H4, 3J(H4H3) = 7.9,
3J(H4H5) = 7.9), 6.32 (ddd, 1H, H5, 3J(H5H4) = 7.9,
4J(H5P) = 4.6, 4J(H5H3) = 0.9), 2.81 (s, 3H, MeC@N),
2.57 (m, 2H, PCH2CH2CH2P), 2.24 (br, 1H,
PCH2CH2CH2P). 31P–{1H} NMR (CDCl3, d ppm): 26.8s.
3.2.16. [{Pd{4-FC6H3C(Me)@NN@C(S)NHMe]}2-
(l-Ph2P(CH2)4PPh2)] (5a)
on symmetry-equivalent and repeated reflections [Tmax/
Tmin = 0.8539/0.3554 (b), 0.9214/0.7798 (4a) and 0.8795/
0.7785 (4c)]. The structures were solved by direct methods
and refined by full matrix least squares on F2. Hydrogen
atoms were included in calculated positions and refined
Yield: 11.3 mg, 43%. Anal. Found: C, 53.2; H, 4.6; N,
7.5; S, 5.8; C48H48F2N6P2Pd2S2 (1085.9 g/mol) requires
C, 53.1; H, 4.5; N, 7.7; S, 5.9%. IR (cmꢀ1): m(N–H)
3428s; m(C@N) 1584m. 1H NMR (CDCl3, d ppm, J
Hz): 7.02 (dd, 1H, H2, 3J(H2H3) = 8.3, 4J(H2F) = 5.5),
6.51 (td, 1H, H3, 3J(H3F) = 8.3, 3J(H3H2) = 8.3,
4J(H3H5) = 2.8), 6.01 (ddd, 1H, H5, 3J(H5F) = 9.2,
4J(H5P) = 4.2, 4J(H3H5) = 2.8), 4.76 (br, 1H, NHMe),
2.97 (d, 3H, NHMe, 3J(H–NH) = 4.6), 2.35 (s, 3H,
MeC@N), 2.28 (br, 2H, PCH2CH2CH2CH2P), 1.74 (br, 2
H, PCH2CH2CH2CH2P). 31P–{1H} NMR (CDCl3, d
ppm): 28.7s.
in riding mode. Refinement converged at
a final
R1 = 0.0407 (b), 0.0658 (4a) and 0.0676 (4c) (observed data,
F), and wR2 = 0.1271 (b), 0.1983 (4a) and 0.2127 (4c) (all
unique data, F2), with allowance for thermal anisotropy
of all non-hidrogen atoms. Minimum and maximum final
electron densities: ꢀ0.228 and 0.234 (b), ꢀ1.337 and
1.496 (4a), ꢀ1.596 and 0.913 e Aꢀ3 (4c). The structure solu-
˚
tions and refinements were carried out with the SHELX-97
[45] program package.
3.2.17. [{Pd{4-FC6H3C(Me)@NN@C(S)NHPh]}2-
(l-Ph2P(CH2)4PPh2)] (5b)
4. Supplementary data
Yield: 29.4 mg, 64%. Anal. Found: C, 57.7; H, 4.4; N,
6.8; S, 5.2; C58H52F2N6P2Pd2S2 (1210.0 g/mol) requires
C, 57.6; H, 4.3; N, 6.9; S, 5.3%. IR (cmꢀ1): m(N–H)
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 Nos. 291906 (b), 291907 (4a),
291908 (4c). Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK.
1
3421m; m(C@N) 1587m. H NMR (CDCl3, d ppm, J Hz):
3
7.49 (d, 2H, H20, H60, J(HH) = 7.9), 7.09 (dd, 1H, H2,
3J(H2H3) = 8.3, 4J(H2F) = 5.5), 6.96 (t, 1H, H40,
3J(HH) = 7.9), 6.75 (s, 1H, NHPh), 6.54 (td, 1H, H3,
3J(H3F) = 8.3, 3J(H3H2) = 8.3, 4J(H3H5) = 2.3), 6.06
(m, 1H, H5), 2.44 (s, 3H, MeC@N), 2.35 (br, 2H,
PCH2CH2CH2CH2P), 1.81 (br, 2H, PCH2CH2CH2CH2P).
31P–{1H} NMR (CDCl3, d ppm): 28.7s.
Acknowledgements
We thank the DGESIC (Ministerio de Ciencia y
´
Tecnologıa) Proyecto BQU2002-04533-C02-01 and the
3.2.18. [{Pd{2-ClC6H3C(Me)@NN@C(S)NHPh]}2-
(l-Ph2P(CH2)4PPh2)] (5c)
Xunta de Galicia, incentive PGIDIT03PXIC20912PN, for
´
financial support. J. Martınez acknowledges a fellowship
´
Yield: 22.3 mg, 49%. Anal. Found: C, 55.8; H, 4.1; N,
6.9; S, 5.3; C58H52Cl2N6P2Pd2S2 (1242.9 g/mol) requires
from the Ministerio de Ciencia y Tecnologıa (Grant No.
PB98-0638-C02-01/02).

J. Martı´nez et al. / Journal of Organometallic Chemistry 691 (2006) 2891–2901
2901
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