Synthesis and structure of Pd and Pt complexes with doubly stabilized phosphorus ylides

Article abstract of DOI:10.1002/ejic.200600599

The doubly stabilized P-ylide ligands Ph₃P=C(CO ₂Me)-C(=S)N(H)Ph (L1), Ph₃P=C(CN)C(=S)N(H)Ph (L2), and Ph₃P=C(CN)-[(E)-C(CO₂Me)=CH(CO₂Me)] (L3) have been prepared and fully characterized. T

Full text of DOI:10.1002/ejic.200600599

FULL PAPER
DOI: 10.1002/ejic.200600599
Synthesis and Structure of Pd and Pt Complexes with Doubly Stabilized
Phosphorus Ylides
Marta Carbó,[a] Nérida Marín,[a] Rafael Navarro,[a] Tatiana Soler,[b] and
Esteban P. Urriolabeitia*[a]
Keywords: Ylides / Metallacycles / Palladium / Platinum / Coordination modes
∧
∧
The doubly stabilized P-ylide ligands Ph3P=C(CO2Me)-
C(=S)N(H)Ph (L1), Ph3P=C(CN)C(=S)N(H)Ph (L2), and
Ph3P=C(CN)–[(E)-C(CO2Me)=CH(CO2Me)] (L3) have been
prepared and fully characterized. The X-ray structures of L1
and L2 are reported. The reactivity of L1, L2, and L3 towards
cationic PdII and PtII precursors with two vacant coordination
(Ln)]ClO4, [M(C X)(Ln)2]ClO4, and [M(µ-Ln)(C X)]2(ClO4)2
∧
(C X = ancillary ligands) were obtained. The ylides Ln coor-
dinate to the metal center through their heteroatoms (O, N,
S), while the C bonding of Ln has not been observed in any
of the cases studied.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
∧
sites has been studied. Adducts of general formula [M(C X)-
subject of intensive research, their coordination chemistry
and bonding properties towards transition metals are
scarcely represented.[7] Representative examples are the re-
action of HgII halides HgX2 (X = Cl, Br, I) or different
UVI salts with Ph3P=C[C(O)Me][C(O)Ph] (ABPPY), which
results in the formation of mono- and dinuclear complexes
with the O(acetyl)-bonded ABPPY ylide.[7a,7d] It is remark-
able that the reactivity of the same HgX2 precursors
towards Ph3P=C(H)C(O)Ph (BPPY) results in C-bonded
mono- and polynuclear complexes.[8] On the other hand,
the reaction of [PtCl2(NCC6F5)2] with Ph3P=C(H)CO2Me
gives the imine-ylide complex [PtCl2{NH=C(C6F5)-
C(=PPh3)C(O)Me}2],[7b] in which the generated doubly sta-
bilized ylide remains bonded to the Pt center through the
imine N atom. As can be observed, all complexes with dou-
bly stabilized ylides share a common feature, namely their
bonding to the metal through the heteroatoms. Aiming to
expand the knowledge on the bonding properties of doubly
stabilized P-ylides, we have studied the reactivity of
Ph3P=C(CO2Me)C(=S)N(H)Ph] (L1),[3a] Ph3P=C(CN)C-
(=S)N(H)Ph (L2),[3a] and Ph3P=C(CN)–[(E)-C(CO2-
Me)=CH(CO2Me)] (L3)[3b] towards orthometalated bis-sol-
vato derivatives of PdII and PtII. We have found different
stoichiometries and different bonding modes for each ylide
(monodentate, didentate, chelating, bridging), and we have
also found that in none of the cases studied does the ylide
bond to the metal center through the ylidic Cα atom.
Introduction
We have recently shown that the α-stabilized P-ylides
Ph3P=C(H)R [R = CN, C(O)RЈ; RЈ = Me, Ph, OMe,
NMe2] behave as versatile ligands towards PdII and PtII pre-
cursors, and several coordination modes of these ylides have
been characterized. Thus, the ylide can coordinate to the
metal center through the Cα atom, the carbonyl oxygen, or
the N atom of the cyano group. We have even characterized
situations in which the same ylide shows a combination of
bonding modes.[1] An interesting fact is that, in spite of the
presence of several potential donor atoms on the same
ylide, they always behave as ambidentate ligands,[1] that is,
using only one donor atom each time. Further replacement
of the ylidic H atom by other functional groups increases
the functionality of the ylides and should expand their
bonding capabilities. In this context, we have now focused
our attention on doubly stabilized P-ylides. The introduc-
tion of an additional stabilizing functional group can be
achieved through several simple synthetic procedures: acyl-
ation,[2] reactivity towards alkynes or other unsaturated
compounds,[3] reactivity of iminophosphoranes with al-
kynes,[4] retro-Wittig reactions,[5] and other less common
processes.[6]
While the chemistry of P-ylide compounds with two sta-
bilizing groups, and their organic applications, has been the
[a] Departamento de Compuestos Organometálicos, Instituto de
Ciencia de Materiales de Aragón, Universidad de Zaragoza-
C.S.I.C,
Results and Discussion
Plaza de San Francisco s/n, 50009 Zaragoza, Spain
Fax: +34-976-761187
Synthesis and Reactivity of L1
E-Mail: esteban@unizar.es
[b] Servicio Técnicos de Investigación, Facultad de Ciencias Fase
II,
The ylide Ph3P=C(CO2Me)C(=S)N(H)Ph (L1) was pre-
03690 San Vicente de Raspeig, Alicante, Spain
pared following reported methods[3a] by treatment of
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M. Carbó, N. Marín, R. Navarro, T. Soler, E. P. Urriolabeitia
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Ph3P=C(H)CO2Me[9b]
with
phenyl
isothiocyanate transoid arrangement of the P=C and C=O bonds, as usu-
(PhNCS). Since in the original work this compound was ally observed in ester-stabilized ylides.[2f,14] The atoms P(1),
poorly characterized, and also for comparative purposes, C(19), C(20), O(1), C(22), S(1), and N(1) are nearly copla-
a complete characterization of L1 was performed. The IR nar, since the maximum deviation of the best least-squares
spectrum of L1 shows an intense absorption at 1629 cm–1, plane is 0.13 Å (C20). The P=Cα bond length is elongated
attributed to the C=O stretch, and two very intense absorp- [P(1)–C(19) 1.751(2) Å] and both Cα–C bond lengths are
tions at 1526 and 1107 cm–1, assigned to the stretch of the identical [C(19)–C(22) 1.436(3), C(19)–C(20) 1.437(3) Å].
C=N and C=S bonds of the thioamide group, respec- These values are shorter than the standard value for a
tively.[10] The N–H stretch was not observed in the IR spec- C(sp2)–C(sp2) single bond (1.478 Å),[15] but are longer than
1
trum. The H NMR spectrum of L1 shows a very broad those found in free[2f,16] or O-bonded[9a,17] ylides [range:
singlet at δ = 12.25 ppm due to the NH proton. This 1.366–1.394 Å] containing a single functional group. The
strongly deshielded position can be easily explained by tak- C(22)–S(1) bond length [1.690(2) Å] is identical to that
ing into account the formation of an intramolecular hydro- found in related ylides [1.693(2) Å],[11] and is slightly longer
gen bond between the NH group and the carbonyl oxygen, than usual values for C=S double bonds [1.671 Å].[15] All
as depicted in Figure 1. The formation of this hydrogen these facts also show an extensive delocalization of the yl-
bond could also account for the lack of observation of the idic charge density through the chain of atoms O(1)–C(20)–
νNH band in the IR spectrum, which is shifted to lower C(19)–C(22)–S(1), probably due to the simultaneous pres-
energies with respect to its expected position (about ence of two delocalizing groups. In good agreement with
3400 cm–1)[10] and is probably hidden under the polyethyl- the NMR spectroscopic data, an intramolecular hydrogen
ene absorptions (2800–3000 cm–1). A similar intramolecular bond between the NH proton and the carbonyl oxygen can
H
bond has been found in the related N-ylide be established and characterized with the following param-
H5C5NC[C(O)Ph]C(S)N(H)Ph.[11] The 31P{1H} NMR
spectrum of L1 shows the presence of a single signal at δ =
11.33 ppm, and the 13C{1H} NMR spectrum also shows a
good agreement with the proposed structure. Key features
are the signal due to the P=C carbon at δ = 71.48 ppm (d,
1JP,C = 143.1 Hz), and that due to the C=S carbon at δ =
189.01 ppm (d, J = 16.6 Hz).[12] These observations agree
with the structures depicted in Figure 1 for L1. The X-ray
structure of L1 has also been determined.
A molecular drawing of L1 is shown in Figure 2, the
most relevant parameters concerning data collection and
structure solution and refinement are given in the Experi-
mental Section, and selected bond lengths and angles are
collected in Table 1. The molecular skeleton of L1 is very
similar to that reported previously for the closely related
ylide H5C5NC[C(O)Ph]C(S)N(H)Ph.[11] Key features are
the cisoid arrangement of the P=C and C=S bonds, also
Figure 2. Thermal ellipsoid plot of L1. Non-hydrogen atoms are
observed in other thiocarbonyl stabilized ylides,[13] and the drawn at the 50% probability level.
Figure 1. Resonance forms for ligand L1.
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Pd and Pt Complexes with Doubly Stabilized Phosphorus Ylides
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eters: H(1A)···O(1) 1.939(3) and N(1)···O(1) 2.642(3) Å; the Pd atom through the S atom of the thioamide unit and
N(1)–H(1A)···O(1) 138.14(15)°. The intramolecular P(1)– through the carbonyl oxygen of the resonance-stabilized
S(1) distance is 3.034 Å, which is shorter than those found CO2Me group, and that the ylidic Cα atom is not involved
in other ylides[13] and is much shorter than the sum of the in bonding with the metal atom. This bonding mode also
van der Waals radii (3.60 Å).[18] The P(1)–C(19)–C(22)–S(1) implies that the NH···O hydrogen bond is broken, and
torsion angle is –8.9° and the P(1)–C(19)–C(22) bond angle hence explains the increase in the NH stretch, since the
is 115.19(15)°, a value smaller than expected for an sp2- ylide must rotate around the Cα–C(S) bond to adopt the
hybridised carbon.
final bonding mode.
The NMR spectra of 1–5 give additional structural infor-
mation. The 1H NMR spectra show that the molecular
plane behaves as a symmetry plane, excluding the C coordi-
nation of L1, and also show a broad signal (δ = 7.20–
7.50 ppm) due to the NH proton. This shift can be ex-
plained by the cleavage of the H bond after coordination of
L1. The 13C{1H} NMR spectra of 1–5 show a doublet at δ
= 72 ppm (1JP,C = 104 Hz) due to the ylidic C atom, and
the 31P{1H} NMR spectra show the presence of a peak at
δ = 19–20 ppm. All these data confirm the absence of an
interaction between the Cα atom and the Pd center,[9a] and
therefore the S,O bonding mode of L1. This should, in prin-
ciple, give two geometric isomers but, according to the
NMR spectroscopic data, only one of them is obtained. A
tentative structure, depicted in Scheme 1, can be proposed
taking into account the hard/soft nature of the donor atoms
bonded directly to the Pd atom and the antisymbiotic ef-
fect[19] shown by the Pd center. This reasoning has been
successfully applied in the coordination chemistry of α-sta-
bilized ylides.[1a] In agreement with this, it is sensible to sup-
pose that trans to the aryl C atom (soft donor) the oxygen
atom of L1 (hard donor) would be more stabilized than the
S atom (soft donor).[20]
Table 1. Selected bond lengths [Å] and angles [°] for L1.
P(1)–C(19)
P(1)–C(1)
C(19)–C(22)
C(20)–O(1)
O(2)–C(21)
C(22)–S(1)
1.751(2)
1.805(2)
1.436(3)
1.216(3)
1.438(3)
1.690(2)
120.4(2)
P(1)–C(13)
P(1)–C(7)
C(19)–C(20)
C(20)–O(2)
C(22)–N(1)
N(1)–C(23)
1.801(2)
1.817(2)
1.437(3)
1.334(3)
1.340(3)
1.420(3)
O(1)–C(20)–O(2)
O(2)–C(20)–C(19) 113.3(2)
O(1)–C(20)–C(19) 126.2(2)
C(20)–O(2)–C(21) 118.6(2)
N(1)–C(22)–C(19) 117.89(19) N(1)–C(22)–S(1)
122.22(17)
C(19)–C(22)–S(1) 119.85(17) C(22)–N(1)–C(23) 127.9(2)
The resonance forms shown in Figure 1 suggest that
there are at least four potential donor atoms for L1 (two O
atoms, one S, and the Cα). We thus explored the reactivity
∧
of L1 towards the bis-solvate complexes [Pd(C X)(thf)2]-
ClO4 (see Scheme 1), prepared as usual by reaction of the
corresponding dinuclear chlorido-bridged derivatives with
AgClO4 (1:2 molar ratio) in thf. Treatment of freshly pre-
∧
pared solutions of [M(C X)(thf)2]ClO4 with L1 (1:1 molar
ratio) in thf at 25 °C resulted in the formation of the cat-
∧
ionic derivatives [Pd(C X)(L1)]ClO4 (1–5), which show ele-
mental analyses and mass spectra (FAB+) in good agree-
ment with the proposed stoichiometry. The IR spectra of
1–5 show several remarkable features: (i) a notable decrease
in the position of the νCO absorption with respect to free
L1; (ii) a shift of the νCN absorption to high energies with
respect to free L1, while the νCS band is found shifted to
lower energies; and (iii) a weak band due to the NH group.
All these facts suggest strongly that ligand L1 is bonded to
The S,O-chelating bonding mode can be transformed
into an S-monodentate mode by simple addition of L li-
gands. Thus, complex 4 reacts with PPh3 (1:1 molar ratio)
in CDCl3 to give 6 (see Scheme 2). The NMR spectroscopic
data of 6 show that the intramolecular H bond has been
restored, since the signal attributed to the NH proton ap-
Scheme 1.
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M. Carbó, N. Marín, R. Navarro, T. Soler, E. P. Urriolabeitia
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Scheme 2.
pears at δ = 11.61 ppm, a position close to that found in than expected (usually about δ = 205 ppm).[12,21] The X-ray
free L1 (δ = 12.25 ppm). A plausible structure for 6 is structure of L2 has also been determined.
shown in Scheme 2, taking into account the known reluc-
The molecular skeleton of L2 (Figure 4 and Table 2) is
tance of PPh3 ligands to coordinate trans to metalated Caryl very similar to that reported for L1, and the geometrical
atoms.
parameters of the P–Cα–C(S)–N–C unit are nearly the same
as those found in L1. For instance, the P–Cα [1.7401(17) Å],
Cα–Cβ(S) [1.432(2) Å], and Cβ–S [1.6831(17) Å] bond
lengths are identical, within experimental error, to the cor-
responding values found in L1 [1.751(2), 1.436(3), and
Synthesis and Reactivity of L2
The exchange of the CO2Me group for the CN group 1.690(2) Å, respectively], and similar conclusions can be de-
promotes notable differences of reactivity. The ylide rived from a comparison of the bond angles. Thus, ligand
Ph3P=C(CN)C(=S)N(H)Ph (L2) was prepared following re- L2 also shows an extensive delocalization of the charge den-
ported methods[3a] by reaction of Ph3P=C(H)CN[3d] with sity, as can be deduced from the spectroscopic data. The
PhNCS. The IR spectrum of L2 shows intense absorptions C(1)–N(1) bond length [1.152(2) Å] is slightly longer than
at 3262 (NH), 2159 (CN), and 1524 and 1108 cm–1 (thio- those reported for typical CϵN bonds (1.136 Å),[15] but is
amide).[21] The shifts of the CN[22] and thioamide bands similar to those found in other cyano-stabilized ylides
suggest an extensive delocalization of the charge density, which contain additional stabilizing groups.[22] This elong-
and this fact agrees with the presence of the resonance ation can be related to the presence of an intermolecular
1
forms shown in Figure 3. The H NMR spectrum of L2 hydrogen bond between the N(2)–H(2) dipole of one mole-
shows a singlet at δ = 8.49 ppm due to the NH proton. This cule and the N(1)–C(1) group of another molecule. As a
signal is shifted upfield when compared with L1 meaning, result of this, L2 forms dimers in the crystal. This H bond
probably, that a similar hydrogen bond is not present in is characterized by the following parameters: N(1)···N(2)
solution. The ylidic Cα atom appears in the 13C{1H} NMR 3.009(3),
N(1)···H(2)
2.251(3) Å;
N(1)···H(2)–N(2)
spectrum as a doublet at δ = 49.62 ppm (1JP,C = 162 Hz), 152.23(2)°. The intramolecular P(1)–S(1) distance is
while the CS atom (δ = 189.68 ppm) appears at higher field 3.090 Å, slightly longer than that found in L1, but is shorter
Figure 3. Resonance forms for ligand L2.
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Pd and Pt Complexes with Doubly Stabilized Phosphorus Ylides
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than the sum of the van der Waals radii (3.60 Å),[18] while spectra of 7–12 show the νCN stretch in the 2195–2206 cm–1
the torsion angle P(1)–C(2)–C(3)–S(1) is –10.29°.
region, and the νCS stretch in the 1027–1064 cm–1 range.
With these data, two structures can be envisaged: a mono-
nuclear one with L2 as a Cα,S-chelate,[23] and a binuclear
compound with the ylide acting as an N,S- or Cα,S-bridging
ligand. In this case, chelation through the N-cyano and S
atoms is discarded because of the constraint imposed by the
nitrile group. The measurement of ΛM in solution could be
a convenient tool to determine the nuclearity of complexes
7–12, through the determination of the slope of the Onsager
equation.[24] However, 7–12 are extremely insoluble in the
usual noncoordinating solvents and they only show a mod-
erate solubility in strongly coordinating solvents such as
dmso or acetonitrile. This means that in solution the sol-
vent could be incorporated into the coordination sphere of
the metal, with concomitant changes of nuclearity or bond-
ing modes of the ylide. The IR spectrum of 11 in MeCN
Figure 4. Thermal ellipsoid plot of L2. Non-hydrogen atoms are shows the absorption of the νCS stretch at 1102 cm–1, vir-
drawn at the 50% probability level.
tually at the same position as in free L2 (1108 cm–1), while
the νCN stretch appears at 2181 cm–1 and two new bands at
2293 and 2248 cm–1 are also seen. These facts suggest that
Table 2. Selected bond lengths [Å] and angles [°] for L2.
MeCN is bonded to the Pd atom replacing the S atom,
P(1)–C(2)
P(1)–C(16)
C(1)–N(1)
C(2)–C(3)
C(3)–N(2)
N(1)–C(1)–C(2) 176.82(18)
C(1)–C(2)–P(1) 119.83(12)
N(2)–C(3)–C(2) 117.30(15)
C(2)–C(3)–S(1) 119.34(13)
C(3)–N(2)–H(2) 117.3(14)
1.7401(17)
1.8036(17)
1.152(2)
1.432(2)
1.356(2)
P(1)–C(10)
P(1)–C(22)
C(1)–C(2)
S(1)–C(3)
1.7945(18)
1.8047(17)
1.409(2)
1.6831(17)
1.421(2)
121.22(15)
118.16(12)
123.35(13)
126.39(15)
114.1(14)
which is no longer bonded, and that the environment of the
C(H)–CN group is the same in solution and in the solid
state.
N(2)–C(4)
The NMR spectra of 7–12 provide additional valuable
information. Key features of the NMR spectra are: (i) the
behavior of the molecular plane as a symmetry plane; (ii)
the low-field shift of δ(P) in the 31P{1H} NMR spectrum
C(1)–C(2)–C(3)
C(3)–C(2)–P(1)
N(2)–C(3)–S(1)
C(3)–N(2)–C(4)
C(4)–N(2)–H(2)
1
with respect to L2; (iii) the similarity of δ(Cα) and JP,C
values in 7–12 and in free L2.[23] According to our previous
The reaction of [M(C X)(thf)2]ClO4 with L2 (1:1 molar experience,[23] all these observations exclude the C coordi-
∧
ratio, thf, room temp.) gives complexes of stoichiometry nation of the ylide and strongly suggest the N-cyano bond-
∧
[M(C X)(L2)](ClO4) (7–12, Scheme 3). Their mass spectra ing of L2 to the Pd atom. In conclusion, we propose a dinu-
(FAB+) show intense peaks due to a mononuclear stoichi- clear structure with an N,S-bridging ylide ligand for com-
ometry, and those of 10 and 12 show additional peaks at plexes 7–12, as depicted in Scheme 3. Finally, and as ex-
1968 and 1480 amu, respectively, with the correct isotopic plained for L1, the absence of symmetry in L2 should also
+
∧
distribution for an [M2(C X)2(L2)2(ClO4)] stoichiometry, result in two geometric isomers after coordination. For sim-
and suggesting that 7–12 are dinuclear in nature. The IR ilar reasons to those reported for complexes 1–5, and also
Scheme 3.
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due to the previously described coordinating behavior of show the presence of peaks due to the stoichiometry
+
cyano ylides,[23] we propose the bonding of the N atom of [M(C X)(L3)] , with the correct isotopic distribution. We
∧
the ylide trans to the orthometalated C atom.
have not observed peaks due to species of higher nuclearity,
as observed for L2. The use of the ESI-MS as an identifica-
tion tool of the nuclearity of the species in solution is a
well established fact.[25] In the case of complexes 13–18, the
analysis of their NCMe solutions only showed, once again,
peaks due to the [M(C X)(L3)] stoichiometry. This fact
suggests that these complexes are mononuclear in nature.
Additional proof can be derived from molar conductivity
measurements[24] and from NMR diffusion experiments.[26]
Synthesis and Reactivity of L3
The ylide Ph3P=C(CN)C(CO2Me)=C(H)CO2Me (L3)
was prepared following the procedure reported by Trippett
et al.[3b] by reaction of Ph3P=C(H)CN[3d] with DMAD (di-
methylacetylenedicarboxylate) in refluxing MeOH, as a yel-
low solid stable to the air and to moisture. The yield for
L3 has been improved with respect to methods reported
previously (65% of analytic and spectroscopically pure
product vs. 43%). In addition, L3 has been fully charac-
terized spectroscopically because very few details were given
in the original report.[3b] The IR spectrum of L3 shows ab-
sorptions of all expected functional groups, at 2169 (νCN),
1744, 1689 (νCOO), and 1531 (νCC) cm–1. The NMR param-
eters of L3 follow a close relationship with those reported
for L1 and L2. For instance, the 13C{1H} NMR spectrum
shows the signal due to Cα at δ = 32.27 ppm as a doublet
(1JP,C = 130 Hz) that is strongly downfield shifted with re-
+
∧
1
spect to the starting ylide. The H NMR spectrum shows
the expected signals, although the (E)- or (Z)-configuration
of the C=C double bond is not defined. A 1D-NOESY ex-
periment performed for L3 shows a small, but detectable,
NOE in the signals of the OMe groups when the signal due
to the =CH proton (δ = 4.81 ppm) is irradiated, which
clearly agrees with an (E) configuration.
Figure 5. Resonance forms for ligand L3.
The ligand L3 is multidentate, as is evident from the reso-
Since these complexes are adequately soluble in the usual
nance forms shown in Figure 5. Plausible donor atoms are organic solvents, the value of the molar conductivity can be
the Cα atom, the cyano N atom, the carbonyl oxygens, and determined. For complex 13, the values determined for ΛM
even the C=C double bond. The reactivity of L3 towards are 114.0 (acetone, c = 2×10–4 ) and 81.7 Ω–1 cm2 mol–1
bis-solvate derivatives of PdII and PtII has been studied. The (MeNO2, c = 1×10–3 ). These values are typical of 1:1
reaction of [M(C X)(thf)2]ClO4 with L3 (1:1 molar ratio, electrolytes[3b] and mean that 13–18 could be mononuclear
∧
thf, room temp.) gives solids of stoichiometry with L3 acting as a chelating ligand. The IR spectra of 13–
∧
[M(C X)(L3)](ClO4) (13–18), as derived from their elemen- 18 show two relevant features: (i) an increase of the νCN
tal analyses (Scheme 4). The mass spectra (FAB+) of 13–18 stretch; and (ii) a slight decrease of one of the νCO stretches,
Scheme 4.
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Pd and Pt Complexes with Doubly Stabilized Phosphorus Ylides
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both with respect to L3. As we have seen, the increase of slightly different. In this case, when the reaction is carried
the νCN stretch could be due either to the C(ylide) or the out in a 1:1 molar ratio, a low yield of 19 is obtained to-
N(cyano) bonding to the metal, while the decrease of the gether with some decomposition to Pt0. The yield of 19
νCO indicates the coordination of the oxygen of one car- improves up to 80% when the reaction is performed with a
bonyl group. Interestingly, the IR spectra of 13–18 in solu- 1:2 (Pt/L3) molar ratio (see Scheme 5). Even when a sub-
tion are virtually the same as in the solid state, thereby sug- stoichiometrict amount of L3 is employed, complex 19 is
gesting that the bonding mode of the ylide remains the the only species isolated. The characterization of 19 is
1
same in solution. The NMR spectra of 13–18, measured in straightforward. The H NMR spectrum shows the incor-
nonbonding solvents (CDCl3) and compared with L3, show poration of two L3 ligands per cyclometalated unit since
similar features to those described for L1 and L2. The small only one peak is observed for the Me of the tolyl groups
variations of δ(P), δ(Cα), and 1JP,C mean that the P=C moi- while the peaks due to the ligand appear duplicated. The
ety in coordinated L3 is not involved in bonding with the 31P{1H} NMR spectrum shows the presence of three sing-
Pd atom. According to the IR and NMR spectroscopic lets with relative intensities 1:1:1 at δ = 19.97 (L3), 19.69
data, the ylide L3 coordinates to the metal center in 13–18 (L3), and 18.09 ppm.
through the N atom of the cyano group and through one
The reluctance of Cα to bond to the metal center is a
oxygen atom of one carbonyl group. The mass spectra and recurrent fact throughout the bonding modes of L1–L3. A
the conductivity measurements suggest, in addition, that plausible explanation for this lack of reactivity could be
the complexes are mononuclear and that L3 acts as a che- centered on the fact that the charge density of Cα is delocal-
lating ligand. The pulsed gradient spin-echo (PGSE) NMR ized throughout the molecular skeleton, including the two
diffusion methods (DOSY) have proved to be a valuable stabilizing groups. This should lead to a decrease of the
tool for the determination of relative molecular sizes in formal charge of Cα, which becomes a poor donor and
solution.[26] We have compared the diffusion coefficients of which cannot compete against the heteroatoms present in
one representative of 13–18 with those obtained for other the same molecule (N, S, O, ...).
mononuclear complexes with the same ligands. We have
shown that complexes 1–5 behave as mononuclear in solu-
tion. The determination of the value of D for 3 [8-mq as
Conclusions
ancillary ligand, see Equation (1)] gives a value of
5.93×10–10 m2 s–1 (2 m, CDCl3, 300 K, δ = 1.7 ms, ∆ =
The ylides L1, L2, and L3, all of which contain two stabi-
100 ms). This value fits very well with that determined lizing groups at the ylidic Cα atom, have been prepared and
for complex 16 (8-mq as ancillary ligand, characterized. The X-ray crystal structures of L1 and L2
D
=
5.92×10–10 m2 s–1) under the same experimental conditions have been determined; they show extensive delocalization
(2 m, CDCl3, 300 K, δ = 1.8 ms, ∆ = 100 ms). Thus, it is of the ylidic charge density. Ligands L1–L3 coordinate to
sensible to suppose that 13–18 are also mononuclear PdII and PtII solvates in a variety of forms. Ligand L1
(Scheme 4), even taking into account the geometric con- bonds as a chelate through the S atom and the resonance-
straint imposed by the cyano group. Two factors could con- stabilized C=O group; ligand L2 coordinates as a bridging
tribute to the stabilization of the chelating mode of L3. The ligand through the S atom and the cyano N atom; and li-
first one could be the formation of a highly flexible eight- gand L3 can coordinate as a chelate, through the cyano N
membered ring, and the second one is the possible bent atom and one oxygen of a C=O group, or as a monodentate
coordination of the CN group, as has been shown pre- ligand through the cyano N atom. In spite of the presumed
viously.[27]
nucleophilic properties of Cα, this atom does not coordinate
The behavior of the cyclometalated complex [Pt{o- to the metal center in any of the cases studied due to delo-
CH2C6H4P(o-tol)2}(S)2]ClO4 (S = solvent) towards L3 is calization of its charge density.
Scheme 5.
Eur. J. Inorg. Chem. 2006, 4629–4641
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4635

M. Carbó, N. Marín, R. Navarro, T. Soler, E. P. Urriolabeitia
FULL PAPER
rated to dryness. Treatment of the residue with Et2O (25 mL) and
vigorous stirring gave 1 as a yellow solid, which was filtered,
washed with additional Et2O (10 mL), and air dried. Yield: 0.060 g
(34.1%). Complex 1 was recrystallized from CH2Cl2/Et2O to give
yellow crystals of 1·0.5CH2Cl2, which were used for analytic and
spectroscopic purposes. The amount of CH2Cl2 was determined by
integration of the signal in the 1H NMR spectrum.
C37H36ClN2O6PPdS·0.5CH2Cl2 (852.06): calcd. C 52.86, H 4.38, N
3.29, S 3.76; found C 52.93, H 4.31, N 3.12, S 3.83. MS (FAB+):
Experimental Section
CAUTION: Perchlorate salts of metal complexes with organic li-
gands are potentially explosive. Only small amounts of these mate-
rials should be prepared and they should be handled with great
caution. See J. Chem. Educ. 1973, 50, A335–A337.
General Methods: Solvents were dried and distilled under argon
using standard procedures before use. Elemental analyses were car-
ried out with a Perkin–Elmer 2400-B microanalyser. IR spectra
(4000–400 cm–1) were recorded with a Perkin–Elmer Spectrum One
IR spectrophotometer from nujol mulls between polyethylene
sheets. 1H (300.13, 400.13 MHz), 13C{1H} (75.47, 100.61 MHz),
and 31P{1H} (121.49, 161.97 MHz) NMR spectra were recorded in
CDCl3, CD2Cl2, or [D6]DMSO solutions at 25 °C (other tempera-
tures are specified) with Bruker ARX300 and Avance400 spectro-
meters (δ in ppm, J in Hz). The 1H and 13C{1H} NMR spectra were
referenced using the solvent signal as internal standard whereas
31P{1H} NMR spectra were externally referenced to H3PO4 (85%).
m/z (%) 709 (15) [M – ClO ]+. IR: ν = 1066 (νCS), 1575 (νCN), 1596
˜
4
(νCO), 3260 (νNH) cm–1. 1H NMR (CDCl3): δ = 2.81 (s, 6 H,
NMe2), 3.08 (s, 3 H, OMe), 4.03 (s, 2 H, CH2N), 6.58–6.61 (m, 2
H, Ho, NPh), 6.77–6.82 (m, 2 H, C6H4), 6.98–7.00 (m, 2 H, C6H4),
7.21 (m, 3 H, Hm, Hp, NPh), 7.27 (br. s, 1 H, NH), 7.67–7.96 (m,
15 H, PPh3) ppm. 13C{1H} NMR (CD2Cl2): δ = 51.16 (NMe2),
1
52.80 (OMe), 71.53 (d, JP,C = 103.6, P=C), 71.81 (CH2N), 122.42
(d, 1JP,C = 91.3, Cipso, PPh3), 123.17, 125.33, 126.00, 133.49, 137.83,
142.57 (C6H4), 126.06 (Cmeta), 128.20 (Cpara), 129.40 (Cortho), 148.65
(Cipso) (NPh), 130.69 (d, 2JP,C = 12.5, Cortho), 133.67 (d, 3JP,C = 9.9,
1
The H SELNO-1D and SELRO-1D NMR experiments were per-
C
meta), 134.71 (Cpara) (PPh3), 172.49 (d, 2JP,C = 10.2, C=O), 186.70
formed with optimized mixing times (D8, P15) depending on the
irradiated signal. ESI/APCI mass spectra were recorded using an
Esquire 3000 ion-trap mass spectrometer (Bruker Daltonik GmbH,
Bremen, Germany) equipped with a standard ESI/APCI source.
Samples were introduced by direct infusion with a syringe pump.
Nitrogen served both as the nebulizer gas and the dry gas. Helium
served as cooling gas for the ion trap and collision gas for MSn
experiments. Other mass spectra (positive ion FAB) were recorded
from CH2Cl2 solutions on a V. G. Autospec spectrometer. The
starting materials Ph3P=C(H)CO2Me,[9b] Ph3P=C(H)CN,[3d] [Pd(µ-
Cl)(C6H4CH2NMe2-C2,N)]2,[28] [Pd(µ-Cl){SC6H4C(H)MeNMe2-
C2,N}]2,[28] [Pd(µ-Cl)(NC13H8-C10,N)]2,[29] [Pd(µ-Cl)(CH2NC9H6-
2
(d, JP,C = 4.1, CS) ppm. 31P{1H} NMR (CDCl3): δ = 19.29 ppm.
Synthesis of 2: Complex 2 was obtained following the same syn-
thetic procedure as reported for 1. [Pd(µ-Cl){(S)-C6H4CH(Me)
NMe2-C2,N}]2 (0.060 g, 0.103 mmol) was treated with AgClO4
(0.043 g, 0.207 mmol) and L1 (0.097 g, 0.207 mmol) in thf to give
2 as an orange solid. Yield: 0.113 g (66.3%). Complex 2 was recrys-
tallized from CH2Cl2/Et2O to give orange crystals of 2·0.5CH2Cl2,
which were used for analytic and spectroscopic purposes. The
amount of CH2Cl2 was determined by integration of the signal in
the 1H NMR spectrum. C38H38ClN2O6PPdS·0.5CH2Cl2 (866.09):
calcd. C 53.39, H 4.54, N 3.23, S 3.70; found C 53.28, H 4.34, N
C8,N)]2,[30]
[Pd(µ-Cl)(C6H4-2-NC5H4-C2,N)],[31]
[M(µ-Cl)(o-
3.39, S 3.88. MS (FAB+): m/z (%) 723 (30) [M – ClO4+]. IR: ν =
˜
CH2C6H4)P(o-tol)2]2 (M
=
Pd,[32] Pt[33]), and [Pd(µ-Br)(η3-
1080 (νCS), 1575 (νCN), 1600 (νCO), 3220 (νNH) cm–1. 1H NMR
C3H5)]2,[34] were prepared following reported methods. Other rea-
gents such as DMAD (MeO2C-CϵC-CO2Me) or PhN=C=S were
purchased from commercial sources (Aldrich) and used without
further purification.
3
(CDCl3): δ = 1.63 (d, JH,H = 6.3, 3 H, Me), 2.63 (s, 3 H, NMe2),
2.87 (s, 3 H, NMe2), 3.08 (s, 3 H, OMe), 4.03 (q, 1 H, CH), 6.59
(m, 2 H, Ho, NPh), 6.83 (m, 2 H, C6H4), 6.92–7.03 (m, 2 H, C6H4),
7.22 (m, 3 H, Hm, Hp, NPh), 7.25 (br. s, 1 H, NH), 7.65–7.96 (m,
15 H, PPh3) ppm. 31P{1H} NMR (CDCl3): δ = 19.25 ppm.
Ph3P=C(CO2Me)C(=S)N(H)Ph (L1): The ylide L1 was prepared
following the method described in the literature by Bestmann and
Pfohl[3a] by reaction of Ph3P=C(H)CO2Me with PhNCS in toluene
(66% yield). The characterization of L1 is reported here since no
data were given in the original paper. C28H24NO2PS (469.54):
calcd. C 71.62, H 5.15, N 2.98, S 6.83; found C 71.45, H 5.11, N
Synthesis of 3: Complex 3 was obtained following the same syn-
thetic procedure as reported for 1. [Pd(µ-Cl)(CH2NC9H6-C8,N)]2
(0.061 g, 0.107 mmol) was treated with AgClO4 (0.044 g,
0.212 mmol) and L1 (0.101 g, 0.215 mmol) in thf to give 3 as a
yellow solid. Yield: 0.122 g (69.5%). C38H32ClN2O6PPdS (817.57):
calcd. C 55.83, H 3.94, N 3.42, S 3.92; found C 56.26, H 3.74, N
2.84, S 6.77. MS (FAB+): m/z (%) 469 (18) [M+]. IR: ν = 1107
˜
(νCS), 1526 (νCN), 1584 (Ph), 1629 (νCO) cm–1. H NMR (CDCl3):
1
3.14, S 4.10. MS (FAB+): m/z (%) 717 (27) [M – ClO ]+. IR: ν =
3
4
˜
4
δ = 3.00 (s, 3 H, OMe), 7.03 (tt, JH,H = 7.2, JH,H = 0.9, 1 H, Hp,
1065 (νCS), 1564 (νCN), 1599 (νCO), 3216 (νNH) cm–1. 1H NMR
(CD2Cl2): δ = 3.21 (s, 3 H, OMe), 3.36 (s, 2 H, CH2Pd), 6.57 (br.,
2 H, Ho, NPh), 7.21 (br. s, 3 H, NH, NC9H6), 7.51–7.60 [m, 4 H,
Hm, Hp (NPh), NC9H6], 7.66–7.80 [m, 10 H, Hm, Hp (PPh3) +
3
NPh), 7.24 (t, JH,H = 7.2, 2 H, Hm, NPh), 7.32–7.51 (m, 9 H,
PPh3), 7.69 (dd, 2 H, Ho, NPh), 7.73–7.82 (m, 6 H, Ho, PPh3),
12.25 (s, 1 H, NH) ppm. 13C{1H} NMR (CDCl3): δ = 49.67 (OMe),
1
71.47 (d, JP,C = 143.1, P=C), 123.71 (Cmeta, NPh), 124.31 (Cpara
,
3
3
NC9H6], 7.90–7.97 (m, 6 H, Ho, PPh3), 8.41 (d, JH,H = 8.1, 1 H,
NPh), 128.20 (Cortho, NPh), 128.36 (d, JP,C = 12.7, Cmeta, PPh3),
NC9H6), 8.66 (br. s, 1 H, NC9H6) ppm. 13C{1H} NMR (CD2Cl2):
1
4
128.50 (d, JP,C = 97, Cipso, PPh3), 131.12 (d, JP,C = 2.6, Cpara
,
1
2
δ = 21.60 (PdCH2), 52.69 (OMe), 70.63 (d, JP,C = 106.1, P=C),
PPh3), 132.94 (d, JP,C = 9.3, Cortho, PPh3), 140.38 (Cipso, NPh),
1
2
2
125.08 (d, JP,C = 93, Cipso, PPh3), 121.98, 124.56, 126.87, 128.25,
168.93 (d, JP,C = 16.4, C=O), 189.01 (d, JP,C = 16.6, C=S) ppm.
31P{1H} NMR (CDCl3): δ = 11.33 ppm.
137.92, 138.88, 147.42, 149.08, 152.21 (NC9H6), 126.21 (Cmeta),
128.93 (Cpara), 129.42 (Cortho), 148.99 (Cipso) (NPh), 130.65 (d, 2JP,C
Synthesis of 1: AgClO4 (0.045 g, 0.217 mmol) was added to a
3
= 11.1, Cortho), 133.60 (d, JP,C = 9.5, Cmeta), 134.59 (Cpara) (PPh3)
suspension
of
[Pd(µ-Cl)(C6H4CH2NMe2-C2,N)]2
(0.060 g,
ppm; the CO and CS signals were not observed. 31P{1H} NMR
0.108 mmol) in dry thf (20 mL) under an Ar atmosphere. The re-
sulting suspension was stirred for 20 min at room temperature with
exclusion of light, and then filtered through a Celite pad in order
to remove the AgCl. The ylide L1 (0.102 g, 0.217 mmol) was added
to this freshly prepared solution of the solvate derivative. The re-
sulting solution was stirred for 30 min and then the solvent evapo-
(CD2Cl2): δ = 19.69 ppm.
Synthesis of 4: Complex 4 was obtained following the same syn-
thetic procedure as reported for 1. [Pd(µ-Cl)(C6H4-2-NC5H4-
C2,N)]2 (0.062 g, 0.105 mmol) was treated with AgClO4 (0.044 g,
0.212 mmol) and L1 (0.101 g, 0.215 mmol) to give 4 as a yellow
4636
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 4629–4641

Pd and Pt Complexes with Doubly Stabilized Phosphorus Ylides
FULL PAPER
solid. Yield: 0.088 g (50.3%). C39H32ClN2O6PPdS (829.58): calcd.
C 56.47, H 3.89, N 3.38, S 3.86; found C 56.46, H 3.76, N 3.33, S
(FAB+): m/z (%) 437 (100) [M + H]+. IR: ν = 1108 (νCS), 1524
˜
1
(νC=N), 2159 (νCN), 3262 (νNH) cm–1. H NMR (CDCl3): δ = 7.09
4.21. MS (FAB+): m/z (%) 729 (30) [M – ClO ]+. IR: ν = 1080
(t, 1 H, Hpara, Ph), 7.28 (t, 3JHmHp = 3JHmHo = 7.5, 2 H, Hmeta, Ph),
˜
4
(νCS), 1578 (νCN), 1600 (νCO), 3259 (νNH) cm–1. 1H NMR (CD2Cl2): 7.41–7.52 [m, 8 H, Hmeta(PPh3) + Hortho(Ph)], 7.56–7.60 (m, 3 H,
3
4
δ = 3.21 (s, 3 H, OMe), 6.64 (dd, JH,H = 5.7, JH,H = 1.6, 2 H,
Hpara, PPh3), 7.71–7.80 (m, 6 H, Hortho, PPh3), 8.49 (br. s, 1 H, NH)
Ho, NPh), 7.02 (td, JH,H = 7.5, JH,H = 1.2, 1 H, Phpy), 7.04 (s, 1 ppm. 13C{1H} NMR (CD2Cl2): δ = 49.62 (d, JP,C = 162, P=C),
3
4
1
3
4
1
H, NH), 7.14 (td, JH,H = 6.6, JH,H = 1.8, 1 H, Phpy), 7.24–7.27
120.99 (d, JP,C = 20.7, Cipso, PPh3), 124.02 (Cmeta, Ph), 125.16
[m, 4 H, Hm+Hp (NPh) + Phpy], 7.32 (td, 3JH,H = 6.6, 4JH,H = 0.9, (Cpara, Ph), 125.29 (CN), 128.47 (Cortho, Ph), 128.96 (d, JP,C = 13,
3
3
4
2
1 H, Phpy), 7.55 (d, JH,H = 7.5, 1 H, Phpy), 7.68–7.99 (m, 17 H,
Cmeta, PPh3), 132.65 (d, JP,C = 2.8, Cpara, PPh3), 133.75 (d, JP,C =
PPh3 + Phpy), 8.45 (d, JH,H = 5.0, 1 H, Phpy) ppm. 13C{1H} 9.8, Cortho, PPh3), 139.47 (d, JP,C = 1.5, Cipso, Ph), 189.68 (d, JP,C
3
4
2
1
NMR (CD2Cl2): δ = 53.09 (OMe), 71.67 (d, JP,C = 102.8, P=C),
= 15.4, C=S) ppm. 31P{1H} NMR (CDCl3): δ = 14.80 (s, C=PPh3)
119.59, 123.32, 124.74, 125.77, 130.06, 134.20, 137.82, 140.10,
146.47, 147.07, 164.27 (Phpy), 122.18 (d, JP,C = 91, Cipso, PPh3),
ppm.
1
Synthesis of 7: AgClO4 (0.053 g, 0.257 mmol) was added to a
126.16 (Cmeta), 128.44 (Cpara), 129.50 (Cortho), 149.73 (Cipso) (NPh),
130.77 (d, 2JP,C = 12.4, Cortho), 133.68 (d, 3JP,C = 9.7, Cmeta), 134.78
(Cpara) (PPh3), 186.47 (d, 2JP,C = 4.4, C=S) ppm; the CO signal was
not observed. 31P{1H} NMR (CD2Cl2): δ = 19.27 ppm.
suspension
of
[Pd(µ-Cl)(C6H4CH2NMe2-C2,N)]2
(0.071 g,
0.128 mmol) in 20 mL of freshly distilled thf under argon. The re-
sulting mixture was stirred at room temperature with exclusion of
light for 30 min, then filtered through a Celite pad. This freshly
prepared solution was treated with a stoichiometric amount of L2
(0.112 g, 0.257 mmol) giving, after a few seconds, a deep yellow
precipitate of 7. This suspension was stirred at room temperature
for an additional 20 min, then the yellow solid was filtered, washed
with thf (5 mL) and Et2O (20 mL), dried by suction, and sub-
Reaction of 4 with PPh3: PPh3 was added in small portions to a
suspension of 4 in CD2Cl2 (0.6 mL) in an NMR tube. NMR spec-
tra were measured each time, until complete transformation of 4.
At this point, complete dissolution had occurred. The amount of
PPh3 required matched a 1:1 molar ratio (4:PPh3), and gave com-
plex 6 as a single isomer in 100% spectroscopic yield. Selected
sequently
identified
as
7.
Yield:
0.141 g
(70.5%).
1
NMR spectroscopic data of 6: H NMR (CD2Cl2): δ = 3.00 (s, 3
C36H33ClN3O4PPdS (776.57): calcd. C 55.68, H 4.28, N 5.41, S
H, OMe), 6.31 (t, 3JH,H = 6.9, 1 H, Phpy), 6.46–6.59 (m, 6 H, NPh
+ Phpy), 6.91 (t, 3JH,H = 7.2, 1 H, Phpy), 7.24–7.74 (m, 33 H, PPh3
4.13; found C 55.81, H 4.50, N 5.11, S 4.03. MS (FAB+): m/z (%)
676 (100) [M/2 – ClO ]+. IR: ν = 1060 (νCS), 1558 (νC=N), 2196
˜
4
+ Phpy), 7.89 (br. s, 1 H, Phpy), 7.96 (td, 3JH,H = 7.5, JH,H = 1.5,
(νCN), 3203 (νNH) cm–1. H NMR ([D6]DMSO): δ = 2.24 (s, 6 H,
4
1
1 H, Phpy), 11.61 (s, 1 H, NH) ppm. 31P{1H} NMR (CD2Cl2): δ NMe2), 3.53 (s, 2 H, CH2N), 6.26 (d, 3JH,H = 7.5, 1 H, C6H4), 6.64
3
3
= 17.65 (P=C), 38.09 ppm (Pd–PPh3).
(m, 1 H, C6H4), 6.76 (d, JH,H = 6.6, 1 H, C6H4), 6.84 (t, JH,H
6.9, 1 H, C6H4), 7.13–7.19 (m, 3 H, Ho+Hp, Ph), 7.28 (t, JH,H
=
=
3
Synthesis of 5: Complex 5 was obtained following the same syn-
thetic procedure as reported for 1. [Pd(µ-Cl)(bhq-C,N)]2 (bhq =
NC13H8; 0.066 g, 0.102 mmol) was treated with AgClO4 (0.042 g,
0.205 mmol) and L1 (0.096 g, 0.205 mmol) to give 5 as a yellow
solid. Yield: 0.115 g (65.7%). Complex 5 was recrystallized from
CH2Cl2/Et2O to give crystals of 5·0.5CH2Cl2 (determined by
NMR), which were used for analytic and spectroscopic purposes.
C41H32ClN2O6PPdS·0.5CH2Cl2 (896.07): calcd. C 55.62, H 3.71, N
3.13, S 3.58; found C 55.36, H 3.88, N 2.87, S 3.74. MS (FAB+):
7.2, 2 H, Hm, Ph), 7.73–7.93 (m, 15 H, PPh3), 10.33 (s, 1 H, NH)
ppm. 31P{1H} NMR ([D6]DMSO): δ = 20.22 (s, C=PPh3) ppm.
Synthesis of 8: Complex 8 was prepared following a synthetic pro-
cedure similar to that reported for 7. Thus, [Pd(µ-Cl)(bhq-C,N)]2
(bhq = C13H8N, 0.078 g, 0.122 mmol) was treated with AgClO4
(0.050 g, 0.244 mmol) and L2 (0.110 g, 0.244 mmol), in thf
(20 mL), to give 8 as a yellow solid. Yield: 0.110 g (55%).
C40H29ClN3O4PPdS (820.58): calcd. C 58.55, H 3.56, N 5.12, S
3.91; found C 58.85, H 3.41, N 4.76, S 3.82. MS (FAB+): m/z (%)
m/z (%) 753 (10) [M – ClO ]+. IR: ν = 1060 (νCS), 1586 (br., νCN
˜
4
+ νCO), 3225 (νNH) cm–1. 1H NMR (CD2Cl2): δ = 3.28 (s, 3 H,
720 (27) [M/2 – ClO ]+. IR: ν = 1056 (νCS), 1568 (νC=N), 2195
˜
4
3
4
3
OMe), 6.68 (dd, JH,H = 5.7, JH,H = 1.8, 2 H, Ho, NPh), 7.19 (d,
(νCN), 3188 (νNH) cm–1. 1H NMR ([D6]DMSO): δ = 6.66 (d, JH,H
3JH,H = 7.2, 1 H, NC13H8), 7.28 (m, 3 H, Hm+Hp, NPh), 7.34 (t, = 9, 1 H, bhq), 6.79 (t, JH,H = 9, 1 H, bhq), 7.00–7.24 (m, 5 H,
3
3JH,H = 7.5, 1 H, NC13H8), 7.38 (s, 1 H, NH), 7.63 (m, 2 H, Ph), 7.57 (d, JH,H = 6, 1 H, bhq), 7.65–7.69 (m, 2 H, bhq), 7.76–
3
3
NC13H8), 7.67–7.73 [m, 7 H, Hm (PPh3) + NC13H8], 7.76–7.82 [m,
4 H, Hp (PPh3) + NC13H8], 7.90–7.98 (m, 6 H, Ho, PPh3), 8.42 (dd,
8.01 (m, 16 H, PPh3 + 1 H bhq), 8.54 (br. d, JH,H = 9, 2 H, bhq),
10.58 (br. s, 1 H, NH) ppm. 31P{1H} NMR ([D6]DMSO), δ = 21.08
(s, C=PPh3) ppm.
4
3
3JH,H = 8.1, JH,H = 1.2, 1 H, H4, NC13H8), 8.66 (dd, JH,H = 5.1,
1 H, H2, NC13H8) ppm. 13C{1H} NMR (CD2Cl2): δ = 53.12
Synthesis of 9: Complex 9 was prepared following a synthetic pro-
cedure similar to that reported for 7. Thus, [Pd(µ-Cl)(NC5H5-2-
C6H4-C,N)]2 (0.080 g, 0.134 mmol) was treated with AgClO4
(0.056 g, 0.269 mmol) and L2 (0.117 g, 0.269 mmol), in thf
(20 mL), to give 9 as a yellow solid. Yield: 0.140 g (70%).
C38H29ClN3O4PPdS (796.56): calcd. C 57.30, H 3.67, N 5.27, S
4.02; found C 57.09, H 3.20, N 5.08, S 3.65. MS (FAB+): m/z (%)
(OMe), 72.07 (d, 1JP,C = 103.0, P=C), 122.31 (d, 1JP,C = 91.2, Cipso
,
PPh3), 122.40, 122.46, 124.01, 124.06, 127.49, 128.96, 131.22,
134.44, 137.89, 138.31, 141.93, 146.27, 153.71 (NC13H8), 126.09
(Cmeta), 128.30 (Cpara), 129.45 (Cortho), 147.33 (Cipso) (NPh), 130.71
(d, 2JP,C = 12.5, Cortho), 133.74 (d, 3JP,C = 9.4, Cmeta), 134.69 (Cpara
)
2
2
(PPh3), 172.82 (d, JP,C = 10.0, C=O), 186.38 (d, JP,C = 4.7, C=S)
ppm. 31P{1H} NMR (CD2Cl2): δ = 19.62 ppm.
696 (100) [M/2 – ClO ]+. IR: ν = 1059 (νCS), 1538 (νC=N), 2197
˜
4
Ph3P=C(CN)C(S)N(H)Ph (L2): PhN=C=S (0.543 mL, 0.614 g, (νCN), 3196 (νNH) cm–1. 1H NMR ([D6]DMSO): δ = 6.48 (d, JH,H
3
3
3
4.55 mmol) was added to a suspension of Ph3P=C(H)CN (1.370 g,
4.55 mmol) in freshly distilled toluene (50 mL). The resulting mix-
ture was refluxed for 1 h and then stirred for 72 h at 25 °C to give
a yellow suspension. This suspension was evaporated to dryness
and the residue treated with Et2O (50 mL) to give L2 as a white
solid. Yield: 1.122 g (56.5%). C27H21N2PS (436.52): calcd. C 74.29,
H 4.85, N 6.41, S 7.34; found C 74.78, H 4.84, N 7.11, S 7.63. MS
= 6, 1 H, Phpy), 6.84 (t, JH,H = 6, 1 H, Phpy), 6.88 (t, JH,H = 6,
3
1 H, Phpy), 7.00 (t, JH,H = 9, 1 H, Phpy), 7.15 (m, 4 H, Ho+Hm,
Ph), 7.33 (t, 3JH,H = 6, 1 H, Hp, Ph), 7.50 (d, 3JH,H = 9, 1 H, Phpy),
8.08–7.56 (m, 17 H, PPh3 + Phpy), 8.19 (s, 1 H, Phpy), 10.53 (s, 1
1
H, NH) ppm. 13C{1H} NMR ([D6]DMSO): δ = 50.80 (d, JP,C
=
2
137.7, P=C), 117.65 (d, JP,C = 14.7, CN), 119.03 (NPh, Cmeta),
121.60 (d, 1JP,C = 93.9, Cipso, PPh3), 122.75, 124.14, 124.48, 125.65,
Eur. J. Inorg. Chem. 2006, 4629–4641
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4637

M. Carbó, N. Marín, R. Navarro, T. Soler, E. P. Urriolabeitia
FULL PAPER
133.36, 136.46, 140.05, 145.39, 147.35, 149.56, 163.04 (Phpy),
1
15 H, PPh3) ppm. 13C{1H} NMR (CDCl3): δ = 32.27 (d, JP,C
=
3
125.37 (NPh, Cortho), 128.37 (Cpara, PPh3), 129.23 (NPh, Cpara),
129.9, P=C), 49.36 (OMe), 51.01 (OMe), 97.74 (d, JP,C = 6.6,
=CH), 120.26 (d, JP,C = 91.8, Cipso, PPh3), 120.44 (d, JP,C = 15.4,
PPh3), 139.23 (Cipso, NPh), 183.27 (d, JP,C = 14.5, C=S) ppm. CN), 128.04 (d, JP,C = 12.8, Cmeta, PPh3), 132.37 (d, JP,C = 2.8,
2
1
2
129.69 (d, 3JP,C = 12.7, Cmeta, PPh3), 134.05 (d, JP,C = 10.0, Cortho
,
2
3
4
2
2
31P{1H} NMR ([D6]DMSO): δ = 20.92 (C=PPh3) ppm.
Cpara, PPh3), 132.58 (d, JP,C = 10.3, Cortho, PPh3), 150.90 (d, JP,C
= 8.8, =C), 165.15 (COO), 167.35 (COO) ppm. 31P{1H} NMR
Synthesis of 10: Complex 10 was prepared following a synthetic
procedure similar to that reported for 7. Thus, [Pt(µ-Cl)[o-
CH2C6H4P(o-MeC6H4)2]]2 (0.103 g, 0.096 mmol) was treated with
AgClO4 (0.040 g, 0.193 mmol) and L2 (0.084 g, 0.193 mmol), in thf
(20 mL), to give 10 as a yellow solid. Yield: 0.0461 g (23%).
C48H41ClN2O4P2PtS (1034.42): calcd. C 55.73, H 4.00, N 2.71, S
3.10; found C 55.47, H 3.71, N 2.94, S 2.61. MS (FAB+): m/z (%)
934 (37) [M/2 – ClO ]+. IR: ν = 1027 (νCS), 1530 (νC=N), 2199
(CDCl3): δ = 19.95 ppm.
Synthesis of 13: AgClO4 (0.0935 g, 0.451 mmol) was added to a
suspension
of
[Pd(µ-Cl)(C6H4CH2NMe2-C2,N)]2
(0.124 g,
0.225 mmol) in thf (20 mL) under Ar. The resultant mixture was
stirred at room temperature for 20 min with exclusion of light, then
filtered through a Celite pad. The freshly prepared solution of the
bis(solvate) was treated with L3 (0.200 g, 0.451 mmol) to give a
yellow solution, which was stirred for an additional 30 min. The
yellow solution was then evaporated to dryness and the yellow resi-
due was treated with Et2O (30 mL) and stirred continuously to give
13 as a yellow solid. Yield: 0.316 g (89.5%). C35H34ClN2O8PPd
(783.49): calcd. C 53.65, H 4.37, N 3.57; found C 53.50, H 4.59, N
˜
4
1
(νCN), 3180 (νNH) cm–1. H NMR ([D6]DMSO): δ = 2.11 (s, 6 H,
Me), 2.78 (s, 2 H, PtCH2), 7.95–6.87 (m, 32 H, PPh3 + C6H4),
10.90 (br. s, 1 H, NH) ppm. 31P{1H} NMR ([D6]DMSO): δ = 20.25
∧
(C=PPh3), 32.09 (1JPtP = 3843, C P–Pt) ppm.
Synthesis of 11: Complex 11 was prepared following a synthetic
procedure similar to that reported for 7. Thus, [Pd(µ-Br)(η3-
C3H5)]2 (0.0664 g, 0.146 mmol) was treated with AgClO4 (0.061 g,
0.292 mmol) and L2 (0.127 g, 0.292 mmol), in thf (20 mL), to give
3.24. MS (FAB+): m/z (%) 683 (100) [M – ClO ]+. IR: ν = 1557
˜
4
(νCC), 1698 (νCOO), 1732 (νCOO), 2192 (νCN) cm–1. 1H NMR
(CDCl3, 213 K): δ = 2.26 (s, 3 H, NMe2), 2.70 (s, 3 H, NMe2), 3.60
(br., 2 H, CH2N), 3.63 (s, 3 H, OMe), 3.76 (br. s, 3 H, OMe), 4.81
11 as
a
green-yellow solid. Yield: 0.159 g (79.4%).
3
3
(s, 1 H, =CH), 6.38 (d, JH,H = 7.2, 1 H, C6H4), 6.68 (t, JH,H
=
=
C30H26ClN2O4PPdS (683.44): calcd. C 52.72, H 3.83, N 4.10, S
3
3
7.8, 1 H, C6H4), 6.80 (d, JH,H = 7.2, 1 H, C6H4), 6.91 (t, JH,H
4.69; found C 51.95, H 4.15, N 3.72, S 4.53. MS (FAB+): m/z (%)
7.2, 1 H, C6H4), 7.59–7.77 (m, 15 H, PPh3) ppm. 13C{1H} NMR
583 (47) [M/2 – ClO ]+. IR: ν = 1027 (νCS), 1530 (νC=N), 2181
˜
4
1
(CDCl3): δ = 33.66 (d, JP,C = 127.8, P=C), 51.13 (OMe), 52.88
1
(νCN), 3240 (νNH) cm–1. H NMR ([D6]DMSO): δ = 2.98 (br. s, 2
(OMe), 52.20 (NMe2), 72.93 (CH2N), 102.62 (d, 3JP,C = 5.1, =CH),
H, CH2), 4.17 (br. s, 2 H, CH2), 5.37 (m, 1 H, CH), 6.91 (m, 2 H,
Ph), 7.12–7.18 (m, 3 H, Ph), 7.39–7.87 (m, 15 H, PPh3), 10.70 (br.
s, 1 H, NH) ppm. 31P{1H} NMR ([D6]DMSO): δ = 20.13 (s,
C=PPh3) ppm.
1
120.54 (d, JP,C = 92, Cipso, PPh3), 121.88, 125.19, 130.17, 134.62,
150.12 (C6H4, one of the quaternary C atoms was not observed),
125.79 (d, 2JP,C = 15.37, CN), 129.96 (d, 3JP,C = 12.7, Cmeta, PPh3),
2
133.96 (d, JP,C = 10.4, Coho, PPh3), 134.44 (s, Cpara, PPh3), 149.86
2
3
Synthesis of 12: Complex 12 was prepared following a synthetic
procedure similar to that reported for 7. Thus, [Pd(µ-Cl)-
{(S)-C6H4CH(Me)NMe2-C2,N}]2 (0.0731 g, 0.126 mmol) was
treated with AgClO4 (0.052 g, 0.252 mmol) and L2 (0.110 g,
0.252 mmol), in thf (20 mL), to give 12 as a yellow solid. Yield:
0.120 g (60%). C37H35ClN3O4PPdS (790.59): calcd. C 56.21, H
4.46, N 5.31, S 4.05; found C 56.28, H 4.15, N 4.86, S 4.81. MS
(d, JP,C = 7.4, =C), 165.90 (COO), 168.20 (d, JP,C = 11.1, COO)
ppm. 31P{1H} NMR (CDCl3): δ = 20.18 (C=PPh3) ppm.
Synthesis of 14: Complex 14 was prepared following a synthetic
procedure similar to that reported for 13. Thus, [Pd(µ-Cl)(bhq-
C,N)]2 (bhq = C13H8N, 0.144 g, 0.225 mmol) was treated with
AgClO4 (0.0932 g, 0.45 mmol) and L3 (0.200 g, 0.45 mmol), in thf
(20 mL), to give 14 as a yellow solid. Yield: 0.167 g (45%).
C39H30ClN2O8PPd (827.50): calcd. C 56.61, H 3.65, N 3.38; found
C 56.26, H 3.98, N 2.96. MS (ESI, positive ions): m/z = 726.9 [M –
(FAB+): m/z (%) 690 (40) [M/2 – ClO ]+. IR: ν = 1064 (νCS), 1542
˜
4
1
(νC=N), 2206 (νCN), 3232 (νNH) cm–1. H NMR ([D6]DMSO): δ =
3
1.18 (d, JH,H = 6, 3 H, Me), 2.09 (s, 3 H, NMe2), 2.34 (s, 3 H,
ClO ]+. IR: ν = 1557 (νCC), 1698 (νCOO), 1733 (νCOO), 2212 (νCN
)
3
3
˜
NMe2), 3.72 (d, JH,H = 6, 1 H, CH), 6.30 (d, JH,H = 6.9, 1 H,
C6H4), 6.66 (m, 2 H, C6H4), 6.85 (t, 3JH,H = 7.5, 1 H, C6H4), 7.13–
7.36 (m, 5 H, Ph), 7.73–7.92 (m, 15 H, PPh3), 10.23 (br. s, 1 H,
NH) ppm. 13C{1H} NMR ([D6]DMSO): δ = 15.13 (Me), 43.91
4
cm–1. H NMR (CDCl3): δ = 3.51 (s, 3 H, OMe), 3.71 (br. s, 3 H,
1
3
OMe), 4.85 (s, 1 H, =CH), 6.94 (d, JH,H = 6.3, 1 H, bhq), 7.25 (t,
3
3JH,H = 7.8, 1 H, bhq), 7.47 (m, 1 H, bhq), 7.53 (d, JH,H = 8.1, 1
3
1
H, bhq), 7.57–7.82 [m, 17 H, PPh3 + 2 H(bhq)], 8.23 (d, JH,H
=
(NMe2), 48.63 (NMe2), 51.29 (d, JP,C = 134.7, P=C), 71.92 (CH),
7.8, 1 H, bhq), 8.74 (br. s, 1 H, bhq) ppm. 13C{1H} NMR (CDCl3):
δ = 34.84 (d, JP,C = 127.7, P=C), 51.20 (OMe), 53.22 (OMe),
102.81 (d, JP,C = 4.6, =CH), 120.37 (d, JP,C = 91.8, Cipso, PPh3),
2
1
118.05 (d, JP,C = 15.9, CN), 121.55 (d, JP,C = 24.5, Cipso, PPh3),
122.50 (s, Cpara, NPh), 124.02, 125.46, 128.98, 135.06, 142.98,
152.54 (C6H4), 124.95 (Cmeta, NPh), 128.48 (Cortho, NPh), 129.68
1
3
1
3
2
121.93, 123.48, 126.69, 128.35, 128.63, 129.54, 131.85, 133.43,
(d, JP,C = 12.7, Cmeta, PPh3), 133.97 (d, JP,C = 10.2, Cortho, PPh3),
2
2
137.69, 140.29, 143.19, 148.97, 153.55 (bhq), 126.49 (d, JP,C
=
133.98 (Cpara, PPh3) 139.44 (Cipso, NPh), 183.71 (d, JP,C = 13.7,
3
2
C–S) ppm. 31P{1H} NMR ([D6]DMSO): δ = 20.40 (s, C=PPh3)
15.37, CN), 130.08 (d, JP,C = 13.0, Cmeta, PPh3), 134.05 (d, JP,C
2
= 10.4, Cortho, PPh3), 134.47 (s, Cpara, PPh3), 149.86 (d, JP,C = 7.4,
ppm.
=C), 165.68 (COO), 168.68 (COO) ppm. 31P{1H} NMR (CDCl3):
Ph3P=C(CN)-[(E)-C(CO2Me)=CH(CO2Me)] (L3): A suspension
of Ph3P=C(H)CN (1.000 g, 3.32 mmol) and DMAD (MeO2C–
CϵC–CO2Me) (0.41 mL, 0.472 g, 3.32 mmol) in MeOH (20 mL)
was refluxed for 20 min under argon. Once cooled, the reaction
mixture was further stirred at room temperature for 18 h to give a
yellow suspension. The precipitated solid of L3 was filtered, washed
with MeOH (10 mL) and Et2O (20 mL), and dried by suction.
δ = 20.28 (C=PPh3) ppm.
Synthesis of 15: Complex 15 was prepared following a synthetic
procedure similar to that reported for 13. Thus, [Pd(µ-Cl)(NC5H5-
2-C6H4-C,N)]2 (0.074 g, 0.124 mmol) was treated with AgClO4
(0.052 g, 0.25 mmol) and L3 (0.110 g, 0.25 mmol), in thf (20 mL),
to give 15 as
a pale-yellow solid. Yield: 0.190 g (95%).
Yield: 0.951 g (64.6%). IR: ν = 1531 (νCC), 1689 (νCOO), 1744
C37H30ClN2O8PPd (803.48): calcd. C 55.31, H 3.76, N 3.49; found
C 55.26, H 3.98, N 3.17. MS (ESI, positive ions): m/z 702.9 [M –
˜
(νCOO), 2169 (νCN) cm–1. 1H NMR (CDCl3): δ = 3.46 (s, 3 H,
OMe), 3.54 (br. s, 3 H, OMe), 4.81 (s, 1 H, =CH), 7.51–7.70 (m, ClO ]+. IR: ν = 1558 (νCC), 1698 (νCOO), 1732 (νCOO), 2192 (νCN
)
˜
4
4638
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 4629–4641

Pd and Pt Complexes with Doubly Stabilized Phosphorus Ylides
FULL PAPER
cm–1. 1H NMR (CDCl3): δ = 3.49 (s, 3 H, OMe), 3.63 (s, 3 H,
C6H4), 7.24–7.75 (m, 15 H, PPh3) ppm. 13C{1H} NMR (CDCl3):
3
1
OMe), 4.84 (s, 1 H, =CH), 6.63 (d, JH,H = 7.8, 1 H, Phpy), 6.87 δ = 18.91 (Me), 34.45 (d, JP,C = 127.3, P=C), 46.15 (NMe2), 51.16
3
3
4
(t, JH,H = 7.2, 1 H, Phpy), 7.05 (t, JH,H = 7.2, 1 H, Phpy), 7.13
(OMe), 51.49 (NMe2), 53.16 (OMe), 74.85 (CHN), 102.70 (d, JP,C
(t, 3JH,H = 6.6, 1 H, Phpy), 7.29 (d, 3JH,H = 7.5, 1 H, Phpy), 7.56 –
= 4.9, =CH), 119.85 (d, JP,C = 91.9, Cipso, PPh3), 122.15, 122.92,
1
7.78 [m, 17 H, PPh3 + 2 H (Phpy)], 7.85 (m, 1 H, Phpy) ppm.
125.10, 125.34, 152.21 (C6H4; C2 was not observed), 125.95 (d, 2JP,C
1
3
2
13C{1H} NMR (CDCl3): δ = 34.79 (d, JP,C = 126.8, P=C), 51.18 = 16.2, CN), 130.03 (d, JP,C = 12.9, Cmeta, PPh3), 133.99 (d, JP,C
3
(OMe), 52.85 (OMe), 102.77 (d, JP,C = 4.9, =CH), 118.97, 123.10,
= 10.4, Cortho, PPh3), 134.42 (d, 4JP,C = 2.3, Cpara, PPh3), 149.78 (d,
3
123.71, 125.68, 129.48, 133.63, 140.04, 149.93, 145.12, 149.77,
2JP,C = 7.6, =C), 165.82 (CO2), 168.04 (d, JP,C = 10.8, CO2) ppm.
1
2
150.06 (Phpy), 120.33 (d, JP,C = 92, Cipso, PPh3), 126.25 (d, JP,C 31P{1H} NMR (CDCl3): δ = 20.17 (s, C=PPh3) ppm.
3
2
= 15.8, CN), 130.07 (d, JP,C = 13.0, Cmeta, PPh3), 133.92 (d, JP,C
= 10.3, Cortho, PPh3), 134.72 (s, Cpara, PPh3), 149.72 (d, JP,C = 7.4,
Synthesis of 19: Complex 19 was prepared following a synthetic
procedure similar to that reported for 13. Thus, [Pt(µ-Cl){o-
CH2C6H4P(o-MeC6H4)2}]2 (0.103 g, 0.096 mmol) was treated with
AgClO4 (0.040 g, 0.192 mmol) and L3 (0.170 g, 0.384 mmol), in thf
(20 mL), to give 19 as a yellow solid. Yield: 0.161 g (80.2%).
C71H64ClN2O12P3Pt (1460.76): calcd. C 58.38, H 4.42, N 1.92;
found C 59.05, H 4.29, N 1.65. MS (FAB+): m/z (%) 941 (100)
2
2
3
=C), 165.89 (d, JP,C = 5.1, COO), 168.38 (d, JP,C = 11.6, COO)
ppm. 31P{1H} NMR (CDCl3): δ = 20.24 (C=PPh3) ppm.
Synthesis of 16: Complex 16 was prepared following a synthetic
procedure similar to that reported for 13. Thus, [Pd(µ-
Cl)(NC9H6CH2-C,N)]2 (0.0718 g, 0.126 mmol) was treated with
AgClO4 (0.0524 g, 0.253 mmol) and L3 (0.112 g, 0.253 mmol), in
thf (20 mL), to give 16 as a yellow solid. Yield: 0.189 g (94%).
C36H30ClN2O8PPd (791.47): calcd. C 54.63, H 3.82, N 3.53; found
C 54.37, H 3.92, N 3.18. MS (ESI, positive ions): m/z = 690.9 [M –
[M – ylide – ClO ]+. IR: ν = 1564 (νCC), 1699 (νCOO), 1733 (νCOO),
˜
4
2198 (νCN) cm–1. 1H NMR (CDCl3): δ = 2.26 (s, 6 H, Me), 3.19 (s,
3 H, OMe), 3.48 (s, 2 H, PtCH2), 3.50 (s, 6 H, 2 OMe), 3.69 (s, 3
H, OMe), 4.80 (s, 1 H, =CH), 4.85 (s, 1 H, =CH), 6.85–7.76 (m,
42 H, PPh3 + C6H4) ppm. 13C{1H} NMR (CDCl3): δ = 12.19
ClO ]+. IR: ν = 1557 (νCC), 1698 (νCOO), 1731 (νCOO), 2200 (νCN
)
˜
4
cm–1. H NMR (CDCl3): δ = 3.46 (br. s, 2 H, CH2Pd), 3.49 (s, 3 (PtCH2), 23.08 (d, JP,C = 7.0, Me), 33.94 (d, JP,C = 127.7, P=C),
1
3
1
1
H, OMe), 3.69 (br. s, 3 H, OMe), 4.81 (s, 1 H, =CH), 7.40 (m, 2
H, 8-mq), 7.66 (m, 17 H, PPh3 + 8-mq), 8.22 (br. s, 2 H, 8-mq)
34.31 (d, JP,C = 128.3, P=C), 51.10 (OMe), 51.20 (OMe), 52.21
(OMe), 52.78 (OMe), 102.44 (d, 4JP,C = 6.5, =CH), 103.25 (d, 4JP,C
1
1
1
ppm. 13C{1H} NMR (CDCl3): δ = 25.58 (PdCH2), 34.50 (d, JP,C
= 5.2, =CH), 120.29 (d, JP,C = 92.1, Cipso, PPh3), 120.62 (d, JP,C
3
2
2
= 127.5, P=C), 51.16 (OMe), 52.97 (OMe), 102.41 (d, JP,C = 2.9,
= 92.1, Cipso, PPh3), 124.04 (d, JP,C = 15.9, CN), 125.07 (d, JP,C
1
3
=CH), 120.41 (d, JP,C = 91.9, Cipso, PPh3), 121.87, 124.30, 126.60,
= 16.2, CN), 126.04 (d, JP,C = 10.8, C6H4), 129.77 (d, JP,C = 12.9,
3
128.20, 128.47, 129.31, 138.50, 150.51, 150.27 (8-mq), 130.05 (d, Cmeta, PPh3), 130.13 (d, JP,C = 12.9, Cmeta, PPh3), 131.30 (d, JP,C
2
3JP,C = 12.9, Cmeta, PPh3), 133.97 (d, JP,C = 10.3, Cortho, PPh3),
= 8.9, C6H4), 131.71 (d, JP,C = 11.6, C6H4), 133.33 (d, JP,C = 5.0,
2
134.89 (Cpara, PPh3), 145.99 (d, JP,C = 4.8, =C), 166.01 (COO), C6H4), 133.34 (d, JP,C = 25.5, C6H4), 133.88 (d, 2JP,C = 10.4, Cortho
,
3
4
4
168.60 (d, JP,C = 10.4, COO) ppm. 31P{1H} NMR (CDCl3): δ = PPh3), 134.40 (d, JP,C = 2.6, Cpara, PPh3), 134.74 (d, JP,C = 1.9,
2
20.12 (C=PPh3) ppm.
Cpara, PPh3), 141.59 (d, JP,C = 10.7, C6H4), 149.18 (d, JP,C = 30.9,
2
1
=C), 149.29 (d, JP,C = 30.3, =C), 157.26 (d, JP,C = 27.0, C6H4),
Synthesis of 17: Complex 17 was prepared following a synthetic
procedure similar to that reported for 13. Thus, [Pd(µ-Br)(η3-
C3H5)]2 (0.066 g, 0.145 mmol) was treated with AgClO4 (0.060 g,
0.290 mmol) and L3 (0.120 g, 0.29 mmol), in thf (20 mL), to give
17 as an orange solid. Yield: 0.154 g (77%). C29H27ClNO8PPd
(690.36): calcd. C 50.45, H 3.94, N 2.03; found C 50.23, H 3.91, N
3
165.83 (COO), 165.99 (COO), 167.68 (d, JP,C = 13.9, COO),
167.82 (d, JP,C = 15.9, COO) ppm. 31P{1H} NMR (CDCl3): δ =
3
∧
18.09 (1JPt,P = 4605, C P–Pt), 19.69 (C=PPh3), 19.97 (C=PPh3)
ppm.
Crystallography. Data Collection: X-ray quality crystals were grown
by slow vapor diffusion of Et2O into a CH2Cl2 solution of the
1.98. MS (FAB+): m/z (%) 590 (47) [M – ClO ]+. IR: ν = 1557
˜
4
(νCC), 1695 (νCOO), 1732 (νCOO), 2192 (νCN) cm–1. 1H NMR corresponding crude compound. A single crystal of dimensions
(CDCl3): δ = 2.22 (br., 2 H, CH2, allyl), 2.73 (d, 3JH,H = 10.5, 2 H, 0.25×0.18×0.16 mm3 (L1) or 0.30×0.24×0.06 mm3 (L2) was
CH2, allyl), 3.48 (s, 3 H, OMe), 3.71 (br. s, 3 H, OMe), 4.76 (s, 1 mounted at the end of a quartz fiber in a random orientation and
H, =CH), 5.33 (q, 1 H, CH, allyl), 7.50 (m, 15 H, PPh3) ppm.
covered with epoxy. Data collection was performed on a Bruker
1
13C{1H} NMR (CDCl3): δ = 33.99 (d, JP,C = 127.2, P=C), 51.14 Smart CCD diffractometer using graphite-monochromated Mo-Kα
3
(OMe), 52.74 (OMe), 62.89 (CH2 allyl), 102.33 (d, JP,C = 4.6, radiation (λ = 0.71073 Å). A hemisphere of data was collected in
=CH), 115.67 (CH allyl), 120.40 (d, 1JP,C = 92, Cipso, PPh3), 127.63
each case based on three ω-scan runs (starting ω = –30°) at values
φ = 0°, 90° and 180° with the detector at 2θ = 30°. For each of
these runs, frames (606, 435, and 230, respectively) were collected
at 0.3° intervals and 10 s per frame. The diffraction frames were
integrated using the program SAINT[35] and the integrated inten-
sities were corrected for absorption with SADABS.[36]
2
3
(d, JP,C = 12.4, CN), 130.20 (d, JP,C = 12.9, Cmeta, PPh3), 133.90
2
4
(d, JP,C = 10.4, Cortho, PPh3), 134.35 (d, JP,C = 5.5, Cpara, PPh3),
2
3
150.00 (d, JP,C = 7.6, =C), 165.92 (COO), 168.21 (d, JP,C = 11.3,
COO) ppm. 31P{1H} NMR (CDCl3): δ = 20.27 (C=PPh3) ppm.
Synthesis of 18: Complex 18 was prepared following a synthetic
procedure similar to that reported for 13. Thus, [Pd(µ-Cl){(S)-
C6H4CH(Me)NMe2-C2,N}]2 (0.0725 g, 0.125 mmol) was treated
with AgClO4 (0.052 g, 0.250 mmol) and L3 (0.111 g, 0.25 mmol),
in thf (20 mL), to give 18 as a yellow solid. Yield: 0.1964 g (98.2%).
C36H36ClN2O8PPd (797.52): calcd. C 54.22, H 4.55, N 3.51; found
C 54.20, H 4.47, N 3.30. MS (ESI, positive ions): m/z = 696.9 [M –
Structure Solution and Refinement: The structures were solved and
developed by Patterson and Fourier methods.[37] All non-hydrogen
atoms were refined with anisotropic displacement parameters. The
hydrogen atoms were placed at idealized positions and treated as
riding atoms. Each hydrogen atom was assigned an isotropic dis-
placement parameter equal to 1.2-times the equivalent isotropic
displacement parameter of its parent atom. The structures were
refined to Fo2, and all reflections were used in the least-squares
calculations.[38]
ClO ]+. IR: ν = 1558 (νCC), 1698 (νCOO), 1732 (νCOO), 2199 (νCN
)
˜
4
cm–1. 1H NMR (CDCl3): δ = 1.45 (d, 3JH,H = 6.0, 3 H, CMe), 2.52
(s, 3 H, NMe2), 2.70 (s, 3 H, NMe2), 3.48 (s, 3 H, OMe), 3.67–3.74
3
(br. s, 4 H, OMe+CH), 4.81 (s, 1 H, =CH), 6.37 (d, JH,H = 7.8, 1
Crystallographic Data for L1: C28H24NO2PS, M = 469.51, T =
3
H, C6H4), 6.67–6.73 (m, 2 H, C6H4), 6.92 (t, JH,H = 7.8, 1 H, 291(2) K, monoclinic C2/c, a = 26.710(3), b = 9.5585(1), c =
Eur. J. Inorg. Chem. 2006, 4629–4641
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4639

M. Carbó, N. Marín, R. Navarro, T. Soler, E. P. Urriolabeitia
FULL PAPER
20.620(2) Å, β = 114.396(2)°, V = 4794.4(9) Å3, Z = 8, Dcalcd.
=
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1991, 47, 1927.
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1.301 Mgm–3, µ = 0.228 mm–1, a total of 15869 reflections were
collected, of which 5764 [Rint = 0.0366] independent reflections
were used in the refinement of 299 parameters and 0 restraints. The
final R factors were R1 = 0.0516, wR2 = 0.1129 for I Ͼ 2σ(I) and
R1 = 0.0940, wR2 = 0.1303 for all reflections, Goof = 1.022.
[8]
[9]
Crystallographic Data for L2: C27H21N2PS, M = 436.49, T =
100(1) K, monoclinic P21/c, a = 11.1040(2), b = 12.2318(2), c =
16.2397(2) Å, β = 94.980(1)°, V = 2197.38(6) Å3, Z = 4, Dcalcd.
=
1.319 Mgm–3, µ = 0.238 mm–1, a total of 37050 reflections were
collected, of which 5033 [Rint = 0.0546] independent reflections
were used in the refinement of 284 parameters and 0 restraints. The
final R factors were R1 = 0.0433, wR2 = 0.1048 for I Ͼ 2σ(I) and
R1 = 0.0548, wR2 = 0.1095 for all reflections, Goof = 1.061.
[10]
[11]
[12]
[13]
CCDC-612165 (for L1) and -612166 (for L2) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments
Funding by the Dirección General de Investigación Científica y
Técnica (DGICYT) Spain (projects CTQ2005-01037 and
CTQ2005-03141) is gratefully acknowledged. T.S. thanks the
MECD (Spain) for a postdoctoral fellowship.
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Eur. J. Inorg. Chem. 2006, 4629–4641

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Eur. J. Inorg. Chem. 2006, 4629–4641
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