Allyl-palladium compounds with fluorinated benzenethiolate ligands. X-ray crystal structure of [η3-C3H5)Pd(μ-S C6H4F-4)2Pd (η3-C3H5)]

Article abstract of DOI:10.1016/S0277-5387(01)00934-2

Treatment of the di-μ-chloride allyl-palladium complex [(η³-C₃H₅)Pd (μ-Cl)₂Pd(η³H₅)] with Pb(SR)₂ in acetone affords dinuclear fluorothiolate bridged complexes of the type [(η

Full text of DOI:10.1016/S0277-5387(01)00934-2

Polyhedron 20 (2001) 3119–3125
www.elsevier.com/locate/poly
Allyl–palladium compounds with fluorinated benzenethiolate
ligands. X-ray crystal structure of
[(h3-C3H5)Pd(m-SC6H4F-4)2Pd(h3-C3H5)]
Roc´ıo Redo´n a, Roger Cramer b, Sylvain Berne`s c, David Morales d, Hugo Torrens a,*
a DEPg, Facultad de Qu´ımica, UNAM, Cd. Uni6ersitaria, 04510 Mexico City, D.F., Mexico
b Department of Chemistry, Uni6ersity of Hawai’i at Ma¯noa, 2545 McCarthy Mall, Honolulu, HI 96822-2275, USA
c Centro de Qu´ımica, IC-UAP, Bl6d. 14 Sur 6303, San Manuel, 72570 Puebla Pue., Mexico
d Instituto de Qu´ımica, UNAM. Cd. Uni6ersitaria, 04510 Mexico City, D.F., Mexico
Received 25 October 2000; accepted 21 August 2001
Abstract
Treatment of the di-m-chloride allyl–palladium complex [(h3-C3H5)Pd(m-Cl)2Pd(h3-C3H5)] with Pb(SR)2 in acetone affords
dinuclear fluorothiolate bridged complexes of the type [(h3-C3H5)Pd(m-SR)2Pd(h3-C3H5)] (R=C6F5, 1; C6HF4-4, 2; C6H4F-2, 3;
C6H4F-3, 4 and C6H4F-4, 5). Complex 1 reacts with para-substituted phosphines P(C6H4X-4)3 to give the mononuclear
perfluorobenzenethiolate complexes [Pd(SC6F5)(h3-C3H5)(P(C6H4X-4)3)] (X=F, 6; CF3, 7; OCH3, 8 and CH3, 9). The single
crystal X-ray diffraction structure of [(h3-C3H5)Pd(m-SC6H4F-4)2Pd(h3-C3H5)] (5) has been resolved. © 2001 Published by
Elsevier Science Ltd.
Keywords: Palladium; Fluorothiolate; Allyl; NMR spectroscopy; Crystal structures
plexes, [(h3-C3H5)Pd(m-SR)2Pd(h3-C3H5)] (R=fluori-
1. Introduction
nated substituents), and the reactivity of [(h3-C3H5)-
Pd(m-SC6F5)2Pd(h3-C3H5)] towards para-substituted
phosphines. To the best of our knowledge, fluorothio-
late-containing derivatives of allyl complexes are repre-
sented by a single example: [(h3-C3H5)Ni(m-SC6F5)2-
Ni(h3-C3H5)] [10].
In this paper we discuss the synthesis and properties
of [(h3-C3H5)Pd(m-SR)2Pd(h3-C3H5)] (R=C6F5, 1;
C6HF4-4, 2; C6H4F-2, 3; C6H4F-3, 4 and C6H4F-4, 5)
and [Pd(SC6F5)(h3-C3H5)(P(C6H4X-4)3)] (X=F, 6;
CF3, 7; OCH3, 8 and CH3 9) and the single crystal
X-ray diffraction structure of compound 5.
The role of h3-allyl–palladium compounds in several
palladium-catalysed organic syntheses is now well es-
tablished [1]. Reviews focused on reactions such as
carbonyl allylation [2], carbonylation [3], allyl alkyla-
tion [4], decarbopalladation [5] or on their application
as enantioselective homogeneous catalysts [6] have been
published.
In contrast with other derivatives of allyl–palladium
complexes [1], those bearing sulfur-containing ligands
are relatively scarce [7–11], even though species with
the fragment [Pd(SR)(h3-allyl)] are potential precursors
of compounds with an organic-SR skeleton and, in-
deed, [Pd(SR)(h3-allyl-R%)L] affords R%CHꢀCHCH2SR
[9].
2. Experimental
As part of our continued interest in dinuclear com-
pounds with fluoroarylthiolato bridging units [12], we
have studied a series of allyl–palladium dinuclear com-
All manipulations were carried out under dry, oxy-
gen-free dinitrogen atmospheres using standard vacuum
and Schlenk-tube techniques.
Solvents were dried and degassed using standard
techniques [13], and thin layer chromatography (TLC)
* Corresponding author. Tel./fax: +52-5-622-3724.
E-mail address: torrens@servidor.unam.mx (H. Torrens).
0277-5387/01/$ - see front matter © 2001 Published by Elsevier Science Ltd.
PII: S0277-5387(01)00934-2

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R. Redo´n et al. / Polyhedron 20 (2001) 3119–3125
(Merck, 5×7.5 cm2 Kieselgel 60 F254) was used when
possible to monitor the progress of the reaction under
study.
2.1.4. [(p3-C3H5)Pd(v-SC6H4F-3)2Pd(p3-C3H5)] (4)
Yellow, yield 90%, m.p. 90 °C (turns green), 108 °C
(dec). Anal. Found: C, 38.4; H, 3.4; S, 10.5. Calc. for
C18H18F2Pd2S2: C, 39.4; H, 3.3; S, 11.7%. MS, m/z
calc.: 549, found: 549.
1H, 19F{1H} and 31P{1H} NMR spectra were
recorded on a Varian-360 spectrometer operating at
360.006, 338.70 and 145.76 MHz, respectively. Proton
spectra are referenced internally using the residual pro-
tio solvent resonance relative to SiMe4 (l=0), 19F
externally to CFCl3 (l=0) and 31P externally to 85%
H3PO4 (l=0) using the high frequency positive con-
vention. All chemical shifts (l) are quoted in ppm and
coupling constants (J) in Hz. Positive-ion FAB mass
spectra were recorded on a JEOL SX102 mass spec-
trometer operated at an accelerating voltage of 10 kV.
Samples were desorbed from a nitrobenzyl alcohol ma-
trix using 3 keV xenon atoms. Mass measurements in
FAB are performed at a resolution of 3000 using
magnetic field scans and the matrix ions as the refer-
ence material or, alternatively, by electric field scans
with the sample peak bracketed by two (polyethylene
glycol or cesium iodide) reference ions.
2.1.5. [(p3-C3H5)Pd(v-SC6H4F-4)2Pd(p3-C3H5)] (5)
Yellow, yield 97%, m.p. 93 °C (turns green), 113 °C
(dec). Anal. Found: C, 38.9; H, 3.5; S, 10.6. Calc. for
C18H18F2Pd2S2: C, 39.4; H, 3.3; S, 11.7%. MS, m/z
calc.: 549, found: 549.
2.2. Preparation of complexes
[Pd(v-SC6F5)(p3-C3H5)(P(C6H4X-4)3)] (X=F, 6; CF3,
7; CH3, 8; and OCH3, 9)
[(h3-C3H5)Pd(m-SC6F5)2Pd(h3-C3H5)] (0.2 g, 0.29
mmol) and P(C6H4X-4)3 (0.29 mmol) were dissolved in
25 ml of acetone and the resulting yellow solution was
magnetically stirred for 2 h and dried under vacuum.
The yellow solids were dissolved in 15 ml of acetone
and slow evaporation of these solutions at room tem-
perature afforded yellow crystals of compounds 6–9.
Elemental analyses were performed by Galbraith
Laboratories Inc., USA.
[(h3-C3H5)Pd(m-Cl)2Pd(h3-C3H5)] [14] and Pb(SR)2
[15,16] were prepared according to published methods.
All other materials were used as commercially supplied.
2.2.1. [Pd(SC6F5)(p3-C3H5)(P(C6H4F-4)3)] (6)
Yellow, yield 80%, m.p. 108 °C (dec). Anal. Found:
C, 47.5; H, 2.0; S, 4.7. Calc. for C27H17F8PPdS: C, 48.9;
H, 2.6; S, 4.8%. MS, m/z calc.: 662, found: 662.
2.1. Preparation of complexes
[(p3-C3H5)Pd(v-SR)2Pd(p3-C3H5)] (R=C6F5, 1;
C6HF4-4, 2; C6H4F-2, 3; C6H4F-3, 4 and C6H4F-4, 5)
2.2.2. [Pd(SC6F5)(p3-C3H5)(P(C6H4(CF3)-4)3)] (7)
Yellow, yield 81%, m.p. 111 °C (dec). Anal. Found:
C, 43.3; H, 1.9; S, 3.5. Calc. for C30H17F14PPdS: C,
44.3; H, 2.1; S, 3.9%. MS, m/z calc.: 812, found: 812.
[(h3-C3H5)Pd(m-Cl)2Pd(h3-C3H5)] (0.5 g, 1.37 mmol)
and Pb(SR)2 (1.37 mmol) were dissolved in 60 ml of
acetone and the resulting yellow solution was magneti-
cally stirred for 2 h. PbCl2 was filtered off and the
resulting clear solutions were dried under vacuum. The
yellow solids were dissolved in 15 ml of acetone and
slow evaporation of these solutions at room tempera-
ture afforded yellow crystals of compounds 1–5.
2.2.3. [Pd(SC6F5)(p3-C3H5)(P(C6H4(OCH3)-4)3)] (8)
Yellow, yield 90%, m.p. 107 °C (dec). Anal. Found:
C, 51.0; H, 3.4; S, 4.1. Calc. for C30H26F5O3PPdS: C,
51.6; H, 3.8; S, 4.6%. MS, m/z calc.: 699, found: 699.
2.2.4. [Pd(SC6F5)(p3-C3H5)(P(C6H4(CH3)-4)3)] (9)
Yellow, yield 95%, m.p. 108 °C (dec). Anal. Found:
C, 55.1; H, 3.9; S, 4.6. Calc. for C30H26F5PPdS: C, 55.4;
H, 4.0; S, 4.9%. MS, m/z calc.: 651, found: 651.
2.1.1. [(p3-C3H5)Pd(v-SC6F5)2Pd(p3-C3H5)] (1)
Yellow, yield 75%, m.p. 172 °C (dec). Anal. Found:
C, 30.8; H, 1.1; S, 9.7. Calc. for C18H10F10Pd2S2: C,
31.2; H, 1.5; S, 9.3%. MS, m/z calc.: 693, found: 693.
2.1.2. [(p3-C3H5)Pd(v-SC6HF4-4)2Pd(p3-C3H5)] (2)
Yellow, yield 87%, m.p. 145 °C (turns green), 180 °C
(dec). Anal. Found: C, 32.3; H, 1.8; S, 9.7. Calc. for
C18H12F8Pd2S2: C, 32.9; H, 1.8; S, 9.8%. MS, m/z calc.:
657, found: 657.
2.3. Single-crystal X-ray structure analysis
Crystallographic data for compound 5 are listed in
Table 1. Intensities were collected using graphite
monochromatised Mo Ka radiation in a Siemens P4/
PC diffractometer using ꢀ–2q scans at variable scan
speeds and were corrected for Lp effects. Absorption
corrections were not considered as necessary, due to the
thin needle shape of the crystal. The structure was
solved by interpretation of Patterson maps [17,18] and
anisotropically refined.
2.1.3. [(p3-C3H5)Pd(v-SC6H4F-2)2Pd(p3-C3H5)] (3)
Yellow, yield 95%, m.p. 112 °C (turns green), 122 °C
(dec). Anal. Found: C, 38.1; H, 3.4; S, 10.1. Calc. for
C18H18F2Pd2S2: C, 39.4; H, 3.3; S, 11.7%. MS, m/z
calc.: 549, found: 549.

R. Redo´n et al. / Polyhedron 20 (2001) 3119–3125
3121
3. Results and discussion
After full anisotropic refinement, large thermal
parameters of the central carbon atoms of the allyl
groups and peaks remaining in this vicinity suggested
that the allyl groups were disordered. The occupancy of
the central carbons was refined yielding a value near
50% and peaks corresponding to the alternate positions
of these carbons were added.
This model was successfully refined including an-
isotropic thermal parameters for the half carbon atoms.
The final model features 50/50 disordered central allyl
carbons atoms, two sets of half hydrogen atoms, and a
single position for the terminal carbon atoms. The
disordered model produced only a slightly lower R-
value. However, the disordered model does account for
the largest peaks in the difference map and also yields
smaller thermal parameters, indicating that the disor-
dered model is better.
Yields, FAB+ MS, melting points and analytical
data consistent with the given formulae for compounds
1–9 are shown in Section 2. Apart from the expected
characteristic absorptions corresponding to the fluori-
nated or the allylic moieties [14–16], the IR spectra do
not show any unusual features.
NMR data for compounds 1–5 are collected in Table
2, and those corresponding to compounds 6–9 are
1
shown in Table 3. H and 19F{1H} NMR spectra have
been simulated using gNMR-3 [19]. As expected, exper-
imental 31P{1H} NMR spectra exhibit single absorp-
tions only. The numbering used to denote the nuclei is
shown in Scheme 1.
3.1. Dinuclear complexes
The hydrogen atoms were placed in calculated posi-
tions. The weighting scheme gave satisfactory agree-
ment analyses.
Metathetical reaction of the palladium complex [(h3-
C3H5)Pd(m-Cl)2Pd(h3-C3H5)] with the anionic pseudo-
halogens (SR)− (R=C6F5, C6HF4-4, C6H4F-2,
C6H4F-3 and C6H4F-4) in acetone solutions allows the
preparation of the corresponding fluorothiolate-bridged
compounds [(h3-C3H5)Pd(m-SR)2Pd(h3-C3H5)] (R=
C6F5, 1; C6HF4-4, 2; C6H4F-2, 3; C6H4F-3, 4 and
C6H4F-4, 5), as shown in Reaction (1).
Table 1
Crystal data and details of the structure determination for [{Pd(m-
SC6H4F-4)(h3-allyl)}2] (5)
Crystal data
Empirical formula
Formula weight
Crystal system
Space group
C18H18F2Pd2S2
549.30
orthorhombic
Pnma (No. 62)
9.040(2)
20.639(2)
10.1150(10)
90
(1)
,
a (A)
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
Compounds 1–5 are yellow, diamagnetic, crystalline
solids that are soluble in acetone and dichloromethane.
All complexes are relatively stable in the solid state
although their solutions darken and eventually turn
black after 2–3 months. On heating, complexes 2–5
develop a green colour before reaching their decompo-
sition temperature. These transitions have not been
investigated further.
90
90
3
,
V (A )
1887.2(5)
4
0.000, 1.933
1072
Z
Dobs, Dcalc (g cm−3
F(000)
)
v(Mo Ka) (mm−1
)
2.1
Crystal size (mm)
0.7×0.1×0.1
Data collection
The 1H NMR spectra of the dinuclear complexes 1–5
(Table 2) at room temperature exhibit only one set of
resonances for the allyl group, i.e. three resonances with
the expected intensity ratio of 1:2:2. The assignments of
the Hb and Ha protons on the allyl ligand (Scheme 1)
were based upon their coupling with Ha, since the
anti-periplanar Hc should have a larger coupling con-
stant (11–17 Hz) than the syn-periplanar Hb proton
(6–8 Hz). Geminal coupling between the Hb and Hc
protons is not observed and so this coupling constant
must be small (B1 Hz). Small geminal coupling con-
stants have been reported for other allyl–metal com-
plexes [10].
Temperature (K)
293
,
Radiation (A)
q Range (°)
Mo Ka 0.71073
2.2–30.0
0.00+0.35 Tan(q)
Scan (type and range) (°)
Reference reflection(s)
Dataset
−1: 12 −29: 1;
−1: 14
3632, 2822, 0.036
1975
Total, unique data, Rint
Observed data [I\2.0|(I)]
Refinement
Nref, Npar
R, wR, S
2822, 122
0.0424, 0.0991, 0.99
w=1/[|2(Fo2)+(0.0411P)2+0.4713P] where P=(Fo2+2Fc2)/3
Maximum and average shift/error
0.04, 0.00
−0.63, 0.86
Minimum and maximum resd. dens.
−3
The shielding order for the allylic protons is lHb\
lHc\lHa, and while lHa and lHc span a range of
,
(e A
)

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R. Redo´n et al. / Polyhedron 20 (2001) 3119–3125
Table 2
NMR data of [(h3-C3H5)Pd(m-SR)2Pd(h3-C3H5)] (1–5), at 298 K
Compound
Ligand
Nucleus
allyl
l (ppm)
J (Hz)
1 [{Pd(m-SC6F5)(h3-C3H5)}2]
Ha
5.58 (2H, tt)
J
Ha–Hb=7.2, JHa–Hc=14.4
Hb
Hc
F2,6
3.81 (4H, d)
JHb–HcB1
3.03 (4H, d)
SR
−132.97 a (4F, m)
J
J
J
F2,6–F3,5=22.9,
F2,6–F4=2.5
F4–F3,5=20.7
F4
−162.77 a (2F, tt)
−165.27 a (4F, m)
5.59 (2H, tt)
3.82 (4H, d)
3.05 (4H, d)
F3,5
Ha
Hb
Hc
2 [{Pd(m-SC6HF4-4)(h3-C3H5)}2]
allyl
SR
J
Ha–Hb=6.8, JHa–Hc=12.5
JHb–HcB1
H4
6.82 (2H, tt)
J
J
J
H4–F2,6=8.9,
H4–F3,5=11.2
F2,6–F3,5=21.0
F2,6
F3,5
Ha
Hb
Hc
−133.37 a (4F, m)
−141.42 (4F, m)
5.52 a (2H, tt)
3.60 (4H, d)
3 [{Pd(m-SC6H4F-2)(h3-C3H5)}2]
allyl
SR
J
Ha–Hb=6.4, JHa–Hc=12.8
JHb–HcB1
2.96 (4H, d)
H3
H6
H4
H5
F2
Ha
Hb
Hc
H2
H6
H5
H4
F3
Ha
Hb
Hc
7.0 (2H, m)
J
J
J
H3–F2=8.1, JH3–H4=8.0
H6–H5=8.0
H4–H5=8.3, JH4–F2=6.4
7.03 (2H, m)
7.14 (2H, m)
7.80 (2H, t)
−105.84 (2F, s)
5.56 a (2H, tt)
3.62 (4H, d)
3.03 (4H, d)
7.48 (2H, d)
7.40 (2H, dd)
7.18 (2H, q)
6.86 (2H, tt)
−117.96 (2F, s)
5.52 a (2H, tt)
3.58 a (4H, d)
2.98 (4H, d)
4 [{Pd(m-SC6H4F-3)(h3-C3H5)}2]
allyl
SR
J
Ha–Hb=7.2, JHa–Hc=12.4
JHb–HcB1
J
J
J
J
H2–F3=7.7
H6–H5=8.0
H5–F3=5.8
H4–F3=8.0, JH4–H5=8.0
5 [{Pd(m-SC6H4F-4)(h3-C3H5)}2]
allyl
SR
JHa–Hb=6.0, JHa–Hc=12.0
JHb–HcB1
H2,6
7.66 (4H, q)
JH2,6–H3,5=8.8,
JH2,6–F4=5.6
JH3,5–F4=8.8
H3,5
F4
6.93 (4H, t)
−122.25 (2F, s)
a Broad absorption: d, doublet; m, multiplet; q, quartet; s, singlet; t, triplet.
Work aimed at investigating the dynamic behaviour of
compounds 1–5 is currently under way.
only 0.09 ppm, the range for lHb is 0.24 ppm, proba-
bly indicating a greater influence of the fluorinated
substituents on these nuclei.
1
The H NMR spectra of complexes 2–5 (and the 19F
3.1.1. X-ray crystal structure
NMR spectrum of complex 1) also show one set of
Fig. 1 shows the diagram corresponding to the com-
plex [(h3-C3H5)Pd(m-SC6H4F-4)2Pd(h3-C3H5)] (5), along
with the atomic numbering scheme. Table 4 collects
resonances for the two bridging thiolate ligands.
1
As noted in Table 2, some H and 19F resonances are
relatively broad, indicating either a dynamic process or
,
selected bond lengths (A) and angles (°).
a mixture of isomers. Mixtures of cis and trans isomers,
depending on the arrangement of the allyl groups with
respect to each other, have been reported for the related
nickel complex [(h3-C3H5)Ni(m-OAr)2Ni(h3-C3H5)] [10]
and the palladium complex [(h3-C3H5)Pd(m-SR)2Pd(h3-
C3H5)] [8]. On the other hand, it has been reported that
[(h3-C3H5)Ni(m-SC6F5)2Ni(h3-C3H5)] is not sensitive to
the relative orientation of the sulfur substituents [10].
Palladium atoms have an almost square-planar co-
ordination
geometry:
S1ꢁPd1ꢁC1A,
171.0(2)°;
S1ꢁPd2ꢁC3A, 171.6(3)°. The Pd1S2 and Pd2S2 planes
intersect at the sulfur bridging atoms with a dihedral
angle of 49.18°.
Substituents at the sulfur atoms show a syn–exo
arrangement relative to each other (see Fig. 1) with
aromatic-CꢁSꢁPd bond angles of 112.0(2) and

R. Redo´n et al. / Polyhedron 20 (2001) 3119–3125
3123
Table 3
NMR data of [Pd(SC6F5)(h3-C3H5)(P(C6H4X-4)3)] (6–9), at 298 K
Compound
Ligand
Nuclei
allyl
l (ppm)
J (Hz)
6 [Pd(SC6F5)(h3-C3H5)(P(C6H4F-4)3)]
Ha
5.45 (1H, tt)
J
J
J
Ha–Hb=12.8, JHa–Hc=7.2
Ha–Hd=12.8, JHa–He=7.6
Hb–Hd=1.8, JHb–P=7.2
Hb
He
Hc
3.50 (1H, t)
3.42 (1H, d)
3.22 (1H, t)
J
Hc–P=11.8
Hd
F2,6
2.74 (1H, d)
−134.51 (2F, dd)
SR
J
J
J
F2,6–F3,5=22.4,
F2,6–F4=2.3
F4–F3,5=20.4
F4
F3,5
H2,6
−162.44 (1F, t)
−164.91 (2F, m)
7.46 (6H, m)
PR3
JH2,6–P=6.1,
JH2,6–H3,5=8.2
JF4–H3,5=8.1
H3,5
F4
P
7.10 (6H, t)
−108.80 (3F, s)
24.18 (s)
7 [Pd(SC6F5)(h3-C3H5)(P(C6H4(CF3)-4)3)]
8 [Pd(SC6F5)(h3-C3H5)(P(C6H4(OCH3)-4)3)]
9 [Pd(SC6F5)(h3-C3H5)(P(C6H4(CH3)-4)3)]
allyl
Ha
5.50 (1H, tt)
J
J
J
Ha–Hb=12.6, JHa–Hc=7.0
Ha–Hd=12.6, JHa–He=7.7
Hb–Hd=1.8, JHb–P=7.2
Hb
He
Hc
Hd
F2,6
3.61 (1H, t)
3.49 (1H, d)
3.29 (1H, t)
2.80 (1H, d)
−133.68 (2F, dd)
J
Hc–P=11.7
SR
J
J
J
F2,6–F3,5=22.8,
F2,6–F4=2.6
F4–F3,5=20.4
F4
F3,5
H2,6
−163.22 (1F, t)
−164.89 (2F, m)
7.68 (6H, m)
PR3
JH2,6–P=6.3,
J
H2,6–H3,5=8.5
H3,5
CF3
P
7.62 (6H, t)
−68.82 (9F, s)
26.68 (s)
allyl
Ha
5.50 (1H, tt)
JHa–Hb=12.6, JHa–Hc=7.3
JHa–Hd=12.7, JHa–He=7.5
JHb–Hd=1.8, JHb–P=7.3
Hb
He
Hc
Hd
F2,6
3.61 (1H, t)
3.49 (1H, d)
3.29 (1H, t)
2.80(1H, d)
−133.68 (2F, dd)
J
Hc–P=11.9
SR
J
J
J
F2,6–F3,5=22.4,
F2,6–F4=2.3
F4–F3,5=20.6
F4
F3,5
H2,6
−163.22 (1F, t)
−164.89 (2F, m)
7.68 (6H, m)
PR3
JH2,6–P=6.3,
J
H2,6–H3,5=8.5
H3,5
CH3
P
7.62 (6H, t)
−68.82 (9F, s)
26.68 (s)
allyl
Ha
5.44 (1H, tt)
JHa–Hb=12.8, JHa–Hc=7.2
JHa–Hd=12.8, JHa–He=7.5
JHb–Hc=1.8, JHb–P=7.2
Hb
He
Hc
3.51 (1H, t)
3.39 (1H, d)
3.19 (1H, t)
J
Hc–P=11.9
Hd
F2,6
2.68 (1H, d)
−133.50 (2F, dd)
SR
J
J
J
F2,6–F3,5=22.6,
F2,6–F4=2.5
F4–F3,5=20.6
F4
F3,5
H2,6
−164.77 (1F, t)
−164.91 (2F, m)
7.35 (6H, m)
PR3
J
H2,6–P=6.2,
JH2,6–H3,5=8.6
H3,5
CH3
P
7.15 (6H, t)
2.34 (9H, s)
24.29 (s)
Broad absorption: d, doublet; m, multiplet; q, quartet; s, singlet; t, triplet.

3124
R. Redo´n et al. / Polyhedron 20 (2001) 3119–3125
Table 4
3
,
Selected bond distances (A) and angles (°) of [{Pd(m-SC6H4F-4)(h -
allyl)}2] (5)
Bond lengths
Pd1ꢁS1
Pd1ꢁC1
Pd1ꢁC2A
Pd1ꢁC2B
S1ꢁC5
2.3693(12)
2.150(3)
2.099(11)
2.121(16)
1.781(4)
1.385(6)
Pd2ꢁS1
Pd2ꢁC3
Pd2ꢁC4A
Pd2ꢁC4B
C5ꢁC6
2.3677(12)
2.131(4)
2.052(3)
2.174(19)
1.376(6)
1.365(6)
Scheme 1.
C5ꢁC10
F1ꢁC8
111.1(2)°, both of which are within the expected range
for a pyramidal environment around the sulfur atoms.
Similar structural features have recently been reported
for the complex [(dppe)Pd(m-SC6H4Me-4)2Pd(h3-C3-
H5)]ClO4 [11]. The allyl and the PdS2 planes in 5 form
angles of 5.17 and 20.18°.
Complex 5 shows a cis arrangement with both unsat-
urated moieties pointing in the same direction.
Allyl angles are 154.2(15) and 149.6(24)°. The CꢁCꢁC
angles in the allyl groups are within the range 141.46–
154.2°.
Bond angles
S1ꢁPd1ꢁS1a
S1ꢁPd1ꢁC1
S1ꢁPd2ꢁC3
S1ꢁPd2ꢁC4B
Pd2ꢁS1ꢁC5
C2AꢁPd1ꢁC2B
83.25(4)
104.87(11)
104.54(11)
137.53(9)
111.33(15)
27.5(8)
S1ꢁPd2ꢁS1a
S1ꢁPd1ꢁC1a
S1ꢁPd2ꢁC4A
Pd1ꢁS1ꢁC5
Pd1ꢁS1ꢁPd2
C4AꢁPd2ꢁC4B
83.31(4)
171.35(11)
136.79(12)
112.10(14)
85.71(4)
21.9(5)
indicate that the h3-ligand is rigid at room tempera-
ture—the spectra show a unique set of five resonances
of equal intensity for the allylic protons Ha to He
(Scheme 1). The shielding order for the allylic protons
is Hd\Hb\He\Hc\Ha, with a spin–spin cou-
pling pattern that is the same as that observed for the
chloride complex [PdCl(h3-C3H5)(P(C6H5)3)] [22], where
the nuclei trans to phosphine (Hb and Hc) are coupled
to 31P. The 31P{1H} NMR spectra of complexes 6–9
show a single resonance.
3.2. Monometallic complexes
Reaction of the fluorothiolate dinuclear complex
[(h3-C3H5)Pd(m-SC6F5)2Pd(h3-C3H5)] (1) with P(C6H4-
X-4)3 (X=F, CF3, OCH3 and CH3) (1:1 molar ratio) in
acetone yields the corresponding mononuclear pe-
rfluorobenzenethiolato compounds: [Pd(SC6F5)(h3-
C3H5)(P(C6H4X-4)3)] (X=F, 6; CF3, 7; OCH3, 8 and
CH3, 9), as shown in Reaction (2). The related com-
pounds [Pd(OC6H4CN-4)(h3-C3H5)(PCy3)] [20] and
[Pd(OAr)(h3-C4H7)(PPh3)] [21] are also known.
Both the proton chemical shifts of allylic nuclei and
1H–31P spin–spin coupling constants do not seem to be
sensitive to the nature of the para-substituent on the
phosphine ligand.
Although the fragment [PdX(h3-allyl)] has been
shown to promote the addition of the X ligand to the
allylic skeleton when X=OPh [21] and SR [9], no such
reaction was observed under the conditions used in this
work.
(2)
Compounds 6–9 are yellow, diamagnetic, crystalline
solids, which are soluble in acetone and
dichloromethane. These complexes are relatively stable
in the solid state and in solution for several months.
4. Supplementary material
Crystallographic data (excluding structure factors)
for the reported structure have been deposited with the
1
The H NMR spectra of complexes 6–9 (Table 3)
Fig. 1. Structure of [(h3-C3H5)Pd(m-SC6H4F-4)2Pd(h3-C3H5)] (5) with thermal ellipsoids at 30% probability level. H atoms are omitted for clarity.

R. Redo´n et al. / Polyhedron 20 (2001) 3119–3125
3125
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