Synthesis, structure, and reactivity of Pd complexes with mixed P,S-Bis(ylide), ylide-sulfide, and ylide-methanide ligands

Article abstract of DOI:10.1002/ejic.201201465

The coordination properties of the ylide-sulfonium salts [Ph ₃P=C(H)COCH₂S(R¹)R²]X [R¹ = R² = Et, X = Br (2); R¹ = Me, R² = Ph, X = ClO₄ (5)], the phosphonium-sulfide salt [Ph₃PCH ₂COCH₂SEt]Br (3) and the neutral ylide-sulfide [Ph ₃P=C(H)COCH₂SPh] (4) towards Pd^II have been studied. Four different bonding modes have been characterized. The reactions of the ylide-sulfonium salts 2 and 5 with PdCl₂(NCMe)₂ and NEt₃ afford the chelating bis(ylide) complexes cis-[PdCl ₂{Ph₃PC(H)COC(H)S(R¹)R²-κC,C}] [R¹ = R² = Et (6); R¹ = Me, R² = Ph (7)], which are obtained selectively in the meso form (RS/SR). This bonding mode is characterized, including by X-ray crystallography, in the acetylacetonate (acac) complexes [Pd(acac-O,O′){Ph₃PC(H)COC(H) S(R¹)R²-κC,C}]ClO₄ [R¹ = R² = Et (8); R¹ = Me, R² = Ph (9)], which were obtained by reaction of the respective precursor 6 or 7 with AgClO₄ and Tl(acac). On the other hand, the C,S-chelating bonding mode has been characterized in [PdCl₂{Ph₃PC(H)COCH₂SR- κC,S}] [R = Et (10); R = Ph (11)], obtained by reaction of the phosphonium-sulfide salt 3 with PdCl₂(NCMe)₂ and NEt ₃ or by reaction of the ylide-sulfide 4 with PdCl₂(NCMe) ₂, respectively. Furthermore, the tridentate bonding mode μ-S:κC,C,S has been determined in the dinuclear derivative [PdCl{Ph₃PC(H)COC(H)SPh-μ-S:κC,C,S}]₂ (13), synthesized by reaction of the ylide-sulfide 4 with PdCl₂(NCMe) ₂ and NEt₃. Compound 13 reacts with PPh₃ to afford the κC,C-chelate [PdCl{Ph₃PC(H)COC(H)SPh-κC,C} PPh₃] (14) after cleavage of the sulfide bridge. Compound 14 was obtained as a single diastereoisomer, which was characterized as the D,L form (RR/SS). Copyright

Full text of DOI:10.1002/ejic.201201465

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DOI:10.1002/ejic.201201465
Synthesis, Structure, and Reactivity of Pd Complexes with
Mixed P,S-Bis(ylide), Ylide–Sulfide, and Ylide–Methanide
Ligands
Elena Serrano,[a] Tatiana Soler,[b] and Esteban P. Urriolabeitia*[c]
Keywords: Ylides / Phosphorus / Sulfur / Palladium / Conformational preferences
The coordination properties of the ylide–sulfonium salts
[Ph3P=C(H)COCH2S(R1)R2]X [R1 = R2 = Et, X = Br (2); R1
Me, R2 = Ph, X = ClO4 (5)], the phosphonium–sulfide salt
[Ph3PCH2COCH2SEt]Br (3) and the neutral ylide–sulfide
[Ph3P=C(H)COCH2SPh] (4) towards PdII have been studied.
Four different bonding modes have been characterized. The
or 7 with AgClO4 and Tl(acac). On the other hand, the C,S-
chelating bonding mode has been characterized in
[PdCl2{Ph3PC(H)COCH2SR-κC,S}] [R = Et (10); R = Ph (11)],
obtained by reaction of the phosphonium–sulfide salt 3 with
PdCl2(NCMe)2 and NEt3 or by reaction of the ylide–sulfide 4
with PdCl2(NCMe)2, respectively. Furthermore, the tri-
dentate bonding mode μ-S:κC,C,S has been determined in
=
reactions of the ylide–sulfonium salts
2 and 5 with
PdCl2(NCMe)2 and NEt3 afford the chelating bis(ylide) com- the dinuclear derivative [PdCl{Ph3PC(H)COC(H)SPh-μ-
plexes cis-[PdCl2{Ph3PC(H)COC(H)S(R1)R2-κC,C}] [R1 = R2 =
Et (6); R1 = Me, R2 = Ph (7)], which are obtained selectively in
the meso form (RS/SR). This bonding mode is characterized,
including by X-ray crystallography, in the acetylacetonate
(acac) complexes [Pd(acac-O,OЈ){Ph3PC(H)COC(H)S(R1)R2-
κC,C}]ClO4 [R1 = R2 = Et (8); R1 = Me, R2 = Ph (9)], which
were obtained by reaction of the respective precursor 6
S:κC,C,S}]2 (13), synthesized by reaction of the ylide–sulfide
4 with PdCl2(NCMe)2 and NEt3. Compound 13 reacts with
PPh3 to afford the κC,C-chelate [PdCl{Ph3PC(H)COC(H)SPh-
κC,C}PPh3] (14) after cleavage of the sulfide bridge. Com-
pound 14 was obtained as a single diastereoisomer, which
was characterized as the D,L form (RR/SS).
ylide carbon atoms (Figure 1). These species have been
studied in depth in our group owing to their unique proper-
ties.[7c,9] In particular, we have been interested in the dia-
stereoselective coordination of stabilized bis(ylides), be-
cause – in spite of the presence of two prochiral centers in
the free ylide – their bonding always affords a single dia-
Introduction
The reactivity of stabilized ylides as ligands for transition
metals has undergone an impressive development during re-
cent years, and they display diverse chemical behaviors. The
most studied topic, as evidenced by the number of reviews
in the recent literature on this subject,[1,2] has been their
versatility as ligands and their ability to act in different
bonding modes.[3–8] When the ylide behaves as a mono-
dentate ligand, its coordination mode can be tuned as a
function of the metal, the bonding position, and the trans
atom.[3,4] Ylides can also behave as polydentate ligands,
either by using the ylide carbon atom and one heteroatom[5]
or by using two carbon atoms.[1,6–8]
Bis(ylides) are a specific class of polydentate ylides, in
which the two carbon atoms bonded to the metal atom are
[a] Centro Universitario de la Defensa, Academia General Militar,
50090 Zaragoza, Spain
[b] Servicios Técnicos de Investigación, Facultad de Ciencias Fase
II,
03690 San Vicente de Raspeig, Alicante, Spain
[c] Instituto de Síntesis Química y Catálisis Homogénea, CSIC-
Universidad de Zaragoza,
50009 Zaragoza, Spain
Fax: +34-976-761187
E-mail: esteban@unizar.es
Homepage: www.unizar.es/icma/depart/quicorga/grupos/
grupo2_chapo/g2_chapo.htm
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201201465.
Figure 1. Selective coordination of bis(ylides) and phenomena re-
sponsible for this selectivity.
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stereoisomer in the meso form. This type of bonding occurs is sensible to assume that the reaction gave the hypothetical
regardless of the heteroatom involved (P, As, N, or S from ylide–sulfide [Ph3PC(H)COCH2SEt] and ethyl bromide,
the respective phosphonium, arsonium, pyridinium, or which could react with water to give EtOH and HBr, and
sulfonium units) and the type of substituents at the hetero- the latter would be responsible for the protonation of the
atom (alkyl or aryl groups).[7,9]
ylide moiety.
A closer inspection of this specific bonding mode with
molecular modeling (DFT methods) revealed the existence
of strong conformational preferences on the free ylides,
which are the true reason for the stereoselective coordina-
tion. However, the ultimate origin of the conformational
preferences lies in two different phenomena. In the case of
P- or As-ylides, 1,4-E···O intramolecular interactions (Fig-
ure 1) can be established,[9c,9e,9f] whereas for N-ylides, 1,6-
CH···O intramolecular hydrogen bonds have been charac-
terized.[9c,9d] The case of the sulfur ylides is more compli-
cated, and the DFT studies have shown that both phenom-
ena can be operating at the same time.[9a,9b] Furthermore,
we have pointed out that the conformational preferences
can display a cooperative behavior, which means that they
are not mutually exclusive.[9a,9c]
Scheme 1. Synthesis of precursors containing the SEt2 and SEt
units.
The mass spectra and elemental analyses of 2 and 3 are
The studies of sulfur-containing bis(ylides) carried out in agreement with the structures shown in Scheme 1. The
up to now involved only SMe2 derivatives, and this fact lim- IR spectrum of 2 shows an intense band at 1555 cm–1,
its the prospects of available systems. The change of the which is attributed to the resonance-stabilized carbonyl
substituents at the sulfur atom, for instance by introducing group,[3,4] whereas that of 3 shows the absorption due to
ethyl or aryl groups, changes in turn the availability of pro- the CO stretch at 1709 cm–1; it is shifted to higher energy
tons to establish hydrogen bonds and also the electron den- as it corresponds to a phosphonium group. The NMR spec-
sity around the sulfur atom. Therefore, it is clear that both tra of 2 are in keeping with the presence of an ylide moiety,
facts could be reflected in the different intramolecular inter- as can be inferred from the value of the 2JP,H coupling con-
1
actions that stabilize the meso form, namely, the hydrogen stant in the H NMR spectrum (21.8 Hz), the 31P chemical
bonds and the electrostatic interactions. To determine in de- shift (δ = 15.10 ppm) in the 31P NMR spectrum, and the
1
tail the effect of the change of the substituents on the estab- value of the JP,C coupling constant in the 13C NMR spec-
lishment of intramolecular interactions, we have prepared trum (107.4 Hz). All the values are diagnostic for the pres-
new mixed bis(ylides) of sulfur and phosphorus [Ph3PC(H)- ence of a stabilized P-ylide in 2. Moreover, the presence of
COC(H)SEt2] and [Ph3PC(H)COC(H)SMePh]. In this con- the CH2SEt2 moiety is easily deduced from the correspond-
tribution, we describe their bonding properties towards Pd ing resonances. On the other hand, inspection of the NMR
complexes, as well as those of the ylide–sulfides spectroscopic data of 3 suggest that a phosphonium group
[Ph3P=C(H)COCH2SR] (R = Et, Ph), which, in spite of is present, as the values of the 2JP,H and 1JP,C coupling con-
their similarity with the mixed bis(ylides), show a different stants decrease (11.4 and 62.46 Hz, respectively) and the 31
P
chemical reactivity.
chemical shift (δ = 20.61 ppm) indicates that the P nucleus
is deshielded with respect to that of 2.
The synthesis of sulfonium salts by the reaction of alkyl
halides with sulfides and quaternization of the sulfur atom
fails when aryl sulfides are used as reagents, probably be-
cause of the delocalization of the sulfur lone pairs on the
Results and Discussion
Synthesis of the Precursors
The reaction of the ylide Ph3P=C(H)COCH2Br (1)[10] aryl functional groups. Thus, the reaction of 1 with SPh2 or
with an excess of SEt2 (1:40 molar ratio) gives one of two with thioanisol (PhSMe) does not afford the expected ylide–
different products depending on the reaction conditions sulfonium salts, and 1 is recovered in both cases. Therefore,
(Scheme 1). When the reaction is carried out in refluxing alternative methods have been used. The synthesis of the
methanol,
the
hygroscopic
ylide–sulfonium
salt ylide–sulfide 4 was carried out by the method reported by
[Ph3P=C(H)COCH2SEt2]Br (2) is obtained in good yield as Alcázar et al.,[12] by the reaction of 1 with thiophenol and
a white solid. However, when the reaction of 1 with SEt2 KOH (1:1:1 molar ratio) in MeOH (Scheme 2).
(1:40 molar ratio) is carried out in tetrahydrofuran (THF),
On the other hand, the removal of the bromide anion in
the phosphonium–sulfide salt [Ph3PCH2COCH2SEt]Br (3) 1 with a halide scavenger such as TlClO4 in a CH2Cl2/
was obtained. In addition to the expected dealkylation pro- Me2CO mixture seems to produce an electrophilic methyl-
cess, well known in sulfonium salts,[11] we also observe the ene group that is reactive enough to react with thioanisol
protonation of the ylide moiety with concomitant forma- and to afford the ylide–sulfonium salt 5 (Scheme 2). The
tion of the phosphonium–sulfide salt 3. The presence of use of other classical reagents for the elimination of halides,
adventitious water could be responsible for this behavior. It such as AgClO4, was not so efficient, and TlClO4 proved
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Scheme 2. Synthesis of precursors containing the SPh or the
SPhMe units.
to be the best option. We then explored the possibility to
prepare ylide–sulfonium salts from SPh2 by using this
method. However, despite many attempts, no derivatives
could be obtained.
Scheme 3. Reactivity of the ylide–sulfonium salts 2 and 5 to give
bis(ylide) derivatives 6–9.
SEt2 moiety. Additional NMR observations that support
this are the presence of a peak at δ = 24.87 ppm in the 31P
NMR spectrum, downfield shifted with respect to that of
2, or the presence of a doublet peak in the 13C NMR spec-
The characterization of the keto-stabilized P-ylide moie-
ties in 4 and 5 was performed by applying the same key
features as those described for 2 and 3, that is, the position
of the CO stretch in the IR spectra (1547 and 1548 cm–1,
1
2
1
trum at δ = 27.10 ppm with a JP,C coupling constant of
respectively), the value of the JP,H and JP,C coupling con-
stants (see Experimental Section, H and 13C NMR spec-
1
49.5 Hz. All these data are in good agreement with data
reported in the literature for C,C-coordinated bis(ylides).[7,9]
The characterization of the meso form as that adopted by
the obtained diastereoisomer comes from the detection of
a strong NOE on the peak at δ = 4.30 ppm (CHS) when the
signal due to the CHP proton (δ =3.68 ppm) is irradiated. A
parallel analysis of the NMR spectroscopic data of 9 can
be performed, except that in this case two sets of signals
(10:1 molar ratio) are observed in all spectra, owing to the
presence of the sulfur atom as an additional stereogenic
center. This is responsible for the formation of two dia-
stereomeric species and the splitting of the NMR spectro-
tra), and the chemical shift of the P atom (δ = 15.96 and
15.02 ppm, respectively). It is also remarkable that the
methylene CH2S protons appear as a singlet signal in 4 but
as diastereotopic signals in 5, which reflects the asymmetry
imposed by the sulfur atom.
Reactivity of the Ylide–Sulfonium Salts [Ph3PC(H)-
COCH2SR1R2]Br [R1 = R2 = Et (2); R1 = Me, R2 = Ph
(5)]
The reaction of the mixed ylide–sulfonium salts scopic data, as the C,C-bonding of the bis(ylide) keeps the
[Ph3P=C(H)COCH2SEt2]Br (2) or [Ph3P=C(H)COCH2- meso configuration.
SMePh]ClO4 (5) with PdCl2(NCMe)2 in the presence of
The X-ray crystal structures of 8 and 9 have been deter-
equimolar amounts (1:1:1 molar ratio) of a weak base mined and provide additional structural information. The
(NEt3) affords the corresponding mononuclear derivatives molecular diagrams of the cationic parts are shown in Fig-
cis-[PdCl2{Ph3PC(H)COC(H)SR1R2-κC,C}] [R1 = R2 = Et ures 2 and 3, respectively, together with selected bond
(6); R1 = Me, R2 = Ph (7); Scheme 3). Although the analyti- lengths and angles. In both cases the Pd atom is located in
cal and IR data of 6 and 7 are in good agreement with the a distorted square-planar environment, surrounded by the
bis(ylide) structures proposed in Scheme 3, no reliable two oxygen atoms of the acac ligand and the two α-carbon
NMR parameters could be gathered owing to their low sol- atoms of the bis(ylide) ligand. As expected, the bis(ylide) is
ubility in common NMR solvents. Therefore, complexes 6 C,C-bonded and forms a strained four-membered ring. The
and 7 were transformed into the more soluble acetyl- sum of the angles around the Pd atom is virtually 360°,
acetonate (acac) complexes [Pd(acac){Ph3PC(H)COC(H) although individual values deviate notably in some cases
SR1R2-κC,C}]ClO4 [R1 = R2 = Et (8); R1 = Me, R2 = Ph from the theoretical value of 90°. For example, the bite
(9)] by their one-pot reaction with AgClO4 and Tl(acac) in angles subtended by the bis(ylide) ligands C(6)–Pd(1)–C(8)
a 1:1:1 molar ratio, as shown in Scheme 3.
or C(21)–Pd(1)–C(19) in 8 and 9 are 69.59(8) and 69.07(9)°,
The NMR spectroscopic data of 8 shows the presence of respectively. The Pd–Cα bond lengths in 8 [2.066(5) and
a single set of signals, which suggests that 8 is obtained as 2.063(5) Å] are identical and are also identical, within ex-
a single isomer. The C,C-coordination of the bis(ylide) is perimental error, to those found in the structurally
easily inferred from the observation of a doublet signal in related mononuclear [Pd(Cl)(PPh3){η2-[Ph3PC(H)C(O)-
1
2
the H NMR spectrum at δ = 3.68 ppm with a small JP,H C(H)NC5H5]}]ClO4 [2.080(3) Å][9c] or dinuclear [Pd(μ-
coupling constant (5.1 Hz), assigned to the CHP proton, Cl)(Ph3PC(H)C(O)C(H)PPh3)]2(ClO4)2 [range 2.053(11)–
and from the inequivalence of the two ethyl groups of the 2.078(11) Å][7c] derivatives. However, the respective Pd–Cα
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bond lengths in 9 are different [2.084(2) and 2.052(2) Å],
The two structures also reveal a noteworthy fact, that
although both of them fall in the usual range of bond the cisoid–cisoid conformation is adopted by the two C,C-
lengths found in the literature for this type of bond.
chelating ylide fragments. Thus, the small values found for
the dihedral angles O(1)–C(7)–C(8)–P(1) [–5.57(7)°] and
O(1)–C(7)–C(6)–S(1) [9.57(8)°] for 8, and O(1)–C(20)–
C(19)–P(1) [–1.33(6)°] and O(1)–C(20)–C(21)–S(1) [–
8.74(7)°] for 9 are similar to those found in structurally re-
lated cisoid arrangements.[9] In the same way, the short in-
tramolecular distances between the phosphorus atom and
the carbonyl oxygen atom [3.071(2) for 8 and 3.062(2) Å for
9] are similar to values found in other bis(ylide) com-
plexes,[9] and both of them are shorter than the sum of the
van der Waals radii (3.35 Å),[13] which strongly suggests the
existence of P···O interactions. The same facts are observed
when the intramolecular sulfur–oxygen distances are exam-
ined, as both of them [2.976(2) for 8 and 2.979(2) Å for 9]
are shorter than the sum of the van der Waals radii (3.37 Å)
and fall in the range observed in bis(ylide) complexes,[9]
which indicates the presence of an S···O interaction.
The arrangement of the ethyl groups of the SEt2 frag-
ment in 8, or that of the methyl and phenyl units of the
PhSMe moiety in 9, with respect to the O atom, has been
produced in such a way that one of the C–S vectors is
pointing towards the oxygen atom. This is reflected in the
angles C29–S1···O1 [154.87(3) Å] in 8 and C22–S1···O1
[153.35(3) Å] in 9; these values are similar to those found
in the literature for related environments.[9b,14] Moreover,
this structural arrangement correlates well with the pres-
ence of short S···O intramolecular distances and suggests
an incipient nucleophilic attack of the oxygen atom to the
sulfonium atom.[15]
Figure 2. Molecular drawing of the cationic part of 8. Thermal
ellipsoids are drawn at the 50% probability level. Selected bond
lengths [Å] and angles [°]: Pd1–O3 2.0588(18), Pd1–C6 2.061(2),
Pd1–C8 2.065(2), Pd1–O2 2.0691(17), S1–C6 1.779(2), P1–C8
1.782(2), C6–C7 1.494(3), C7–O1 1.227(3), C7–C8 1.496(3); O3–
Pd1–C6 167.64(8), O3–Pd1–C8 98.24(8), C6–Pd1–C8 69.54(9), O3–
Pd1–O2 91.07(7), C6–Pd1–O2 100.73(8), C8–Pd1–O2 167.30(8),
C7–C6–S1 110.77(16), C7–C6–Pd1 86.36(14), S1–C6–Pd1
121.78(13), O1–C7–C8 126.6(2), O1–C7–C6 127.6(2), C8–C7–C6
103.81(19), C7–C8–P1 115.86(16), C7–C8–Pd1 86.15(13), P1–C8–
Pd1 124.53(13).
Therefore, a close analogy has been found in the reactiv-
ity of the ylide–sulfides 2 and 5, studied in this work, and
previous results obtained in our group with related spe-
cies.[9a] The deprotonation occurs in all cases under smooth
reaction conditions, and the bonding of the resulting bis(yl-
ide) takes place with full diastereoselectivity, which allows
for the selective synthesis of the meso form (RS/SR). These
results suggest that the conformational preferences on the
bis(ylide) skeleton are still established even when different
substituents are present. This is not unexpected for the
phosphorus atom, as in this part of the molecule the P···O
interaction is mainly responsible for the conformation
adopted (Figure 1). However, it is more remarkable at the
sulfur atom, because here, in addition to the S···O interac-
tion, intramolecular C–H···O hydrogen-bonding interac-
tions are established, which should be sensitive to the pres-
ence of different substituents (methyl vs. ethyl vs. phenyl),
Figure 3. Molecular drawing of the cationic part of 9. Thermal
ellipsoids are drawn at the 50% probability level. Selected bond as shown in Figure 1. Therefore, this is a noteworthy result,
lengths [Å] and angles [°]: Pd1–O2 2.0415(19), Pd1–O3 2.0477(15),
as it shows the generality of the scope of intramolecular
Pd1–C21 2.051(2), Pd1–C19 2.086(2), P1–C19 1.774(2), C19–C20
interactions as a source of conformational preferences.
1.484(3), C20–O1 1.230(3), C20–C21 1.474(3), C21–S1 1.764(2);
O2–Pd1–O3 91.75(7), O2–Pd1–C21 97.28(8), O3–Pd1–C21
170.93(8), O2–Pd1–C19 166.21(9), O3–Pd1–C19 102.00(8), C21–
Pd1–C19 68.97(9), C20–C19–P1 115.80(18), C20–C19–Pd1
Reactivity of the Sulfide Salts [Ph3PCH2COCH2SEt]Br (3)
80.51(13), P1–C19–Pd1 123.18(14), O1–C20–C21 125.8(2), O1–
and [Ph3PC(H)COCH2SPh] (4)
C20–C19 127.2(2), C21–C20–C19 104.71(19), C20–C21–S1
113.86(16), C20–C21–Pd1 81.95(13), S1–C21–Pd1 113.47(12),
C21–S1–C23 108.88(11), C21–S1–C22 99.75(12), C23–S1–C22
101.89(12).
In addition to the κC,C-bonding mode observed for P,S-
bis(ylides) in 6–9, other coordination modes have been
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characterized. The reaction of the phosphonium–sulfide formation of the corresponding diastereoisomers (RCRS/
salt [Ph3PCH2COCH2SEt]Br (3) with PdCl2(NCMe)2 in the SCSS and RCSS/SCRS) in 1:1 (11) and 6.7:1 (12) molar ra-
presence of a weak base such as NEt3 (1:1:1 molar ratio) tios. The different steric requirements of the SEt and SPh
occurs with proton abstraction at the methylene group adja- units are probably responsible for the observed differences.
cent to the phosphonium unit, formation of the ylide–
The C,C-bis(ylide) and C(ylide)–S(sulfide) bonding
sulfide [Ph3P=C(H)COCH2SEt], and C,S-coordination of modes described in the preceding sections can be further
the latter to give the chelate complex PdCl2{Ph3PC(H)- expanded by combining the coordinating abilities of all po-
COCH2SEt-κC,S} (10; Scheme 4). The ylide–sulfide inter- tential donor atoms in this type of system. The deproton-
mediate was not detected in the reaction of 1 with SEt2, but ation of the methylene unit of the ylide–sulfide [Ph3PC(H)-
it is reasonable to postulate its formation in the light of its COCH2SPh] (4) would generate the anion [Ph3PC(H)-
coordinating behavior. According to the same pattern of COC(H)SPh]–, which in principle displays three donor
reactivity, the ylide–sulfide [Ph3PC(H)COCH2SPh] (4) re- atoms: the ylide C, the methanide C, and the sulfide S
acts with PdCl2(NCMe)2 in MeOH (1:1 molar ratio) to give atoms. We have constated that this deprotonation takes
the C,S-chelate PdCl2{Ph3PC(H)COCH2SPh-κC,S} (12; place under very mild reaction conditions. Therefore, the
Scheme 4). Complex 12 has been characterized in solution, reaction of 4 with NEt3 in MeOH at room temperature,
but no NMR spectroscopic data could be obtained for 10 followed by the addition of PdCl2(NCMe)2 (1:1:1 molar ra-
because of its insolubility. Therefore, 10 was transformed tio), affords the dinuclear derivative 13 shown in Scheme 5.
into the more soluble acac derivative 11 by its reaction with The sulfur bridge present in 13 can be broken by the ad-
AgClO4 and Tl(acac) in a 1:1:1 molar ratio, and 11 was dition of neutral ligands, as shown by the reaction of 13
properly characterized.
with PPh3 (1:2 molar ratio), which affords mononuclear 14
in good yield.
Scheme 5. Reactivity of the ylide–sulfide 4 to give ylide–methanide
complexes.
The elemental analysis of 13 is in keeping with the stoi-
chiometry shown in Scheme 5 and confirms the presence of
one anionic ylide–methanide unit and a chlorido ligand per
palladium atom. The dimeric nature of 13 is inferred from
its mass spectrum, in which there is a peak at m/z = 1099.2
with the correct isotopic distribution for the cationic species
[Pd2(Ph3PCHCOCHSPh)2Cl]+. The C-coordination of the
Scheme 4. Reactivity of the ylide–sulfides 3 and 4 to give κC,S
chelates.
The C-bonding of the ylide fragment is inferred from the ylide is clear from the position of the carbonyl stretch in
shift to high energy of the carbonyl stretch in the solid- the IR spectrum (1595 cm–1) of 13, which is shifted to high
state IR spectra of 10–12, which appears in the range 1650– energy with respect to the stretch of the free ylide 4. This
1670 cm–1, typical of this bonding mode.[7,9] Additional evi- position also suggest that a four-membered C,C-chelate has
dence for the C-coordination in 11 and 12 come from the been formed, as it falls in the same wavenumber range as
2
observation of an almost negligible JP,H coupling constant those previously observed in 6–9 (range 1550–1610 cm–1) or
1
for the CHP signal in the H NMR spectra, the downfield in related complexes,[7] and it is quite different than that
shift of the 31P peak due to the CHP nucleus with respect found for five-membered C,X-chelates; for instance, 10–12
to the ylide precursor, and the presence of a doublet peak show the C=O stretch in the range 1650–1680 cm–1. The
in the 13C NMR spectra attributed to the ylide CHP carbon C,C-chelation of the ligand can also be inferred from the
1
atom with a JP,C coupling constant of ca. 55–57 Hz. Ad- NMR spectra of 13, by following the change with respect
ditionally, the S-coordination of the sulfide group is clearly to 4 of the same key parameters previously analyzed; that
2
1
reflected in the fact that the NMR spectra of 11 and 12 is, δ(CHP) and JP,H in the H NMR spectrum, δ(CHP) in
1
show two sets of signals each, which are attributed to the the 31P NMR spectrum, and δ(CHP) and JP,C in the 13C
Eur. J. Inorg. Chem. 2013, 2129–2138
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NMR spectrum. In addition, the coordination of the SPh whereas the ylide–sulfides [Ph3PC(H)COCH2SR] act as
moiety can be deduced from the deshielding experienced by C,S-chelates. The ylide–methanide [Ph3PC(H)COC(H)-
the protons of the aromatic ring on 13 compared with those SPh]– bonds as a μ-S:κ2C,C (C,C-chelate and S-bridge) or
of 4. This change is more relevant in the Hortho nuclei (from κ2C,C-chelate, and the latter also shows total diastereo-
δ = 7.35 ppm in 4 to δ = 7.70 ppm in 13), but it is also selectivity, although it forms the d,l pair. The bonding be-
noticeable in the Hmeta and Hpara protons (from δ = 7.06– havior of bis(ylides) [Ph3PC(H)COC(H)SR2] is the same as
7.17 ppm in 4 to δ = 7.20–7.26 ppm in 13). All experimental that observed for the bis(ylide) [Ph3PC(H)COC(H)SMe2]
data suggest that the anion [Ph3PC(H)COC(H)SPh]– is co- and is due to the presence of conformational preferences
ordinated to the Pd center as a C,C,S-tridentate ligand. We based on the establishment of 1,4-P···O, 1,4-S···O, and 1,6-
have previously shown that the anion [Ph3PC(H)COC(H)- C–H···O intramolecular contacts. This work shows that
SMe]– behaves as a C,C-chelate and S-bridging ligand.[9a] these contacts, and therefore the concomitant conforma-
Given that the spectral changes seen for [Ph3PC(H)COC- tional preferences, take place irrespective of the nature of
(H)SPh]– follow the same tendencies as those reported for the substituents at the S atom (alkyl or aryl); this expands
[Ph3PC(H)COC(H)SMe]– and assuming a similar reactivity the number of available substrates with which they can be
owing to close relationship of the two anions, we suggest operative. This wide scope is important for the design of
the same bonding behavior for both of them. Therefore, complexes with a given configuration.
we propose for 13 the structure shown in Scheme 5. It is
remarkable that the proposed dinuclear structure for 13 dis-
plays up to six stereogenic centers, whereas their NMR
spectra show a single set of signals in each case. We have
previously shown that the four-membered C,C-ring is
formed with full diastereoselectivity and that, once formed,
Experimental Section
Safety Note: Caution! Perchlorate salts of metal complexes with
organic ligands are potentially explosive. Only small amounts of
this ring is very stable and does not undergo conforma-
these materials should be prepared, and they should be handled
tional changes.[9a] Therefore, the most reactive point of the
with great caution.
molecule seems to be the S-bridge, and a rapid Pd–S bond-
General Methods: Solvents were dried and distilled before use by
using standard procedures. Elemental analyses (CHNS) were car-
forming and -breaking mechanism could explain the equili-
bration of the different diastereoisomers. The measurement
ried out with a Perkin–Elmer 2400-B microanalyzer. Infrared spec-
of the NMR spectra at low temperature (CD2Cl2, 188 K)
tra (4000–380 cm–1) were recorded with a Perkin–Elmer Spectrum
points to a fast dynamic process as it shows a broadening
of the signals, although not their complete splitting.
One IR spectrophotometer. 1H, 13C, and 31P NMR spectra were
recorded with Bruker AV300 and AV400 spectrometers (δ in ppm,
J in Hz) at 1H operating frequencies of 300.13 and 400.13 MHz,
The reactivity of 13 to give 14 (Scheme 5) also suggests
the weakness of the Pd–S bonds and the bridging system.
The incorporation of a PPh3 ligand is evident from the pres-
ence of two peaks in the 31P NMR spectrum of 14, whereas
the PPh3 ligand trans to the C-ylide arrangement is inferred
from the appearance of the ylide CHP carbon atom as a
1
respectively. H and 13C NMR spectra were referenced to the sol-
vent signal as an internal standard, and 31P NMR spectra were
referenced to H3PO4 (85%). ESI+ mass spectra were recorded with
an Esquire 3000 ion-trap mass spectrometer (Bruker Daltonic
GmbH) equipped with a standard ESI/atmospheric pressure chemi-
cal ionization (APCI) source. Samples were introduced by direct
infusion with a syringe pump. Nitrogen served both as the nebulizer
gas and the dry gas. The mass spectra (MALDI+) were recorded
from CHCl3 solutions with a MALDI-TOF Microflex (Bruker)
spectrometer {trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propen-
ylidene]malononitrile (DCTB) as matrix}. The starting stabilized
ylide Ph3P=C(H)COCH2Br (1) was synthesized according to pub-
lished methods.[10]
2
doublet of doublets with a JP,C coupling constant value
(58.6 Hz) in the range found in structurally related situa-
tions.[7,9] The nonbonded SPh unit is easily characterized
1
by the shielding observed in the H NMR spectrum for all
peaks assigned to the Ph ring on going from 13 to 14. Fi-
nally, the anti disposition of the methanide CHS and ylide
CHP protons is proposed by analogy with related structur-
ally characterized complexes.[9a] As previously explained,
NOESY experiments are not informative in this case, be-
cause the absence of an NOE between the CHP and CHS
nuclei is not a proof of their relative transoid disposition.[16]
[Ph3PC(H)COCH2SEt2]Br (2): To
a solution of Ph3PC(H)-
COCH2Br (1) (0.201 g, 0.506 mmol) in MeOH, SEt2 (2.18 mL,
20.24 mmol) was added, and the mixture was heated to reflux un-
der Ar for 24 h. After this time, the solvent was evaporated to dry-
ness, and the brown residue was extracted with CH2Cl2 (2ϫ
30 mL). The combined extracts were dried with anhydrous MgSO4
(15 min stirring at room temp.) and filtered. The clear solution was
concentrated to dryness, and the white residue was treated with
Et2O (20 mL) and stirred. Compound 2 was obtained as a white
solid, which was collected by filtration, washed with additional
Conclusions
Four different coordination modes have been charac-
terized for bis(ylide) [Ph3PC(H)COC(H)SR1R2] (R1 = R2 =
Et O, and dried in vacuo. Yield: 0.186 g (75.3%). IR: ν = 1555
˜
2
Et; R1
= = Ph), ylide–sulfide [Ph3PC(H)-
Me, R2
(νCO) cm–1. H NMR (CDCl3): δ = 1.37 (br., 6 H, CH3, Et), 3.64–
1
COCH2SR] (R = Et, Ph), and ylide–methanide [Ph3PC(H)-
COC(H)SPh]– species when bonded to a PdII center. The
bis(ylides) [Ph3PC(H)COC(H)SR2] coordinate as κ2C,C-
3.75 (2 m, 4 H, CH2, Et), 4.22 (d, 2JP,H = 21.8 Hz, 1 H, CHP), 4.77
(s, 2 H, CH2S), 7.43 (m, 6 H, Hm, Ph3P), 7.50–7.58 (m, 9 H, Hp,
Ho, Ph3P) ppm. 31P{1H} NMR (CDCl3): δ = 15.10 ppm. 13C{1H}
chelates and show full diastereoselectivity (meso form), NMR (CDCl3): δ = 9.96 (s, CH3, SEt2), 33.94 (s, CH2, SEt2), 48.71
Eur. J. Inorg. Chem. 2013, 2129–2138
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3
(d, 3JP,C = 20.7 Hz, CH2S), 56.89 (d, 1JP,C = 107.4 Hz, CHP), 125.0
Ph3P), 7.47 (dd, JP,H = 12.4 Hz, 6 H, Ho, Ph3P), 7.52 (t, 3 H, Hp,
1
3
3
(d, JP,C = 91.5 Hz, Ci), 120.20 (d, JP,C = 12.5 Hz, Cm, Ph3P),
132.85 (d, 4JP,C = 2.3 Hz, Cp, Ph3P), 133.01 (d, 2JP,C = 10.4 Hz, Co,
Ph3P), 176.71 (br. s, CO) ppm. MS (FAB+): m/z (%) = 407 (100)
[M – Br]+. C25H28BrOPS (487.46): calcd. C 61.60, H 6.09, S 6.92;
found C 61.39, H 5.89, S 6.91.
Ph3P), 7.48 (t, JH,H = 7.8 Hz, 2 H, Hm, PhS), 7.64 (t, 1 H, Hp,
PhS), 7.98 (d, 2 H, Ho, PhS) ppm. 31P{1H} NMR (CDCl3): δ =
15.02 ppm. 13C{1H} NMR (CDCl3): δ = 26.71 (s, CH3S), 56.66 (d,
3JP,C = 20.6 Hz, CH2), 56.76 (d, 1JP,C = 107.1 Hz, CHP), 124.00 (s,
1
3
Ci, PhS), 124.77 (d, JP,C = 91.5 Hz, Ci, Ph3P), 129.21 (d, JP,C
=
12.5 Hz, Cm, Ph3P), 130.87 (s, Cm, PhS), 130.97 (s, Co, PhS), 132.83
(d, 4JP,C = 2.7 Hz, Cp, Ph3P), 132.97 (d, 2JP,C = 10.5 Hz, Co, Ph3P),
134.25 (s, Cp, PhS), 175.54 (s, CO) ppm. C28H26ClO5PS (541.002):
calcd. C 62.16, H 4.84, S 5.93; found C 61.83, H 5.00, S 5.96.
[Ph3PCH2COCH2SEt]Br (3): Compound 3 was obtained according
to the same experimental procedure as that described for 2. There-
fore, Ph3PC(H)COCH2Br (0.502 g, 1.26 mmol) reacted with SEt2
(5.50 mL, 50.5 mmol) in THF (15 mL) at reflux to give 3 as a
[PdCl2{Ph3PC(H)COC(H)SEt2-κC,C}] (6): To
a solution of
brown solid. Yield: 0.38 g (66.2%). IR: ν = 1709 (νCO) cm–1. 1H
˜
[Ph3PCHC(O)CH2SEt2]Br (2) (0.115 g, 0.239 mmol) in MeOH
(15 mL), NEt3 (33.0 μL, 0.239 mmol) was added. No apparent
change was observed. To this solution PdCl2(NCMe)2 (0.062 g,
0.239 mmol) was added, which dissolved in a few seconds. Almost
instantaneously after the formation of this initial solution, an
orange solid precipitated. After a few minutes of stirring at room
temp., the solid was collected by filtration, washed with MeOH
(10 mL) and Et2O (25 mL), air-dried, and identified as 6. Yield:
3
NMR (CDCl3): δ = 0.99 (t, JH,H = 7.1 Hz, 3 H, CH3, SEt), 2.07
4
(q, 2 H, CH2, SEt), 3.69 (d, JP,H = 2.5 Hz, 2 H, CH2S), 6.04 (d,
2JP,H = 11.4 Hz, 2 H, CH2P), 7.58 (m, 6 H, Hm, Ph3P), 7.69 (t,
3JH,H = 8.0 Hz, 3 H, Hp, Ph3P), 7.79 (m, 6 H, Ho, Ph3P) ppm.
31P{1H} NMR (CDCl3): δ = 20.61 ppm. 13C{1H} NMR (CDCl3):
1
δ = 13.95 (s, CH3, SEt), 25.94 (s, CH2, SEt), 37.84 (d, JP,C
62.46 Hz, CH2P), 44.83 (d, JP,C = 7.7 Hz, CH2S), 118.65 (d, JP,C
=
3
1
3
= 93.6 Hz, Ci), 130.17 (d, JP,C = 13.7 Hz, Cm, Ph3P), 133.86 (d,
0.100 g (72.6%). IR: ν = 1583 (νCO) cm–1. Complex 6 is insoluble
˜
2JP,C = 10.7 Hz, Co, Ph3P), 134.82 (s, Cp, Ph3P), 196.34 (d, JP,C
=
2
in the usual NMR solvents, which precluded its characterization
7.4 Hz, CO) ppm. MS (FAB+): m/z (%) = 379 (100) [M – Br]+.
C23H24BrOPS (459.41): calcd. C 60.14, H 5.26, S 6.98; found C
60.38, H 4.94, S 6.91.
by this technique. MS (MALDI+): m/z (%)
= 548.8 (10)
[M – Cl]+. C25H27Cl2OPPdS (583.87): calcd. C 51.43, H 4.66, S
5.50; found C 51.28, H 4.40, S 5.28.
[Ph3PC(H)COCH2SPh] (4): The synthesis of 4 was carried out ac-
cording to previously reported procedures.[12] To a solution of
PhSH (0.130 mL, 1.26 mmol) in MeOH (10 mL), KOH (0.070 g,
1.26 mmol) was added, and the resulting solution was stirred at
25 °C for 1 h. To this solution the ylide Ph3PC(H)COCH2Br (1)
(0.502 g, 1.26 mmol) was added, and stirring was maintained for
15 h. After this time, the solvent was evaporated to dryness, and
the residue was extracted with CH2Cl2 (2ϫ 15 mL). The combined
extracts were dried with anhydrous MgSO4 and filtered, and the
resulting solution was concentrated to a small volume (ca. 2 mL).
After the addition of Et2O (30 mL) and stirring, compound 4 was
obtained as a white solid, which was collected by filtration, washed
[PdCl2{Ph3PC(H)COC(H)SMePh-κC,C}] (7): Complex 7 was pre-
pared according to a synthetic method identical to that described
for 6. Thus, [Ph3PC(H)COCH2SMePh]ClO4 (5) (0.120 g,
0.221 mmol) was treated with NEt3 (31.0 μL, 0.221 mmol) and
PdCl2(NCMe)2 (0.057 g, 0.221 mmol) in MeOH (20 mL) to give 7
as a yellow solid. Yield: 0.092 g (67%). IR: ν = 1546 (νCO) cm–1.
˜
NMR: Complex 7 was insoluble in the usual NMR solvents, which
precluded its characterization by this technique. C28H25Cl2OPPdS
(617.86): calcd. C 54.43, H 4.57, S 5.19; found C 54.64, H 4.39, S
5.14. MS (MALDI+): m/z (%) = 583.0 (85.3) [M – Cl]+.
[Pd(acac-O,OЈ){Ph3PC(H)COC(H)SEt2-κC,C}]ClO4 (8): To a sus-
pension of 6 (0.047 g, 0.081 mmol) in a CH2Cl2/Me2CO (9:1,
20 mL) mixture, AgClO4 (0.017 g, 0.081 mmol) was added, and the
resulting grey suspension was stirred in the dark for 30 min. After
this time, Tl(acac) (0.025 g, 0.081 mmol) was added, and stirring
was continued for an additional 30 min. The grey suspension was
carefully filtered through a Celite pad, and the resulting pale yellow
solution was concentrated to dryness. The oily residue was treated
with Et2O (20 mL) to give 8 as a yellow solid. Yield: 0.020 g (35%).
with Et2O (30 mL), and dried in vacuo. Yield: 0.453 g (84.4%). IR:
1
ν = 1547 (νCO) cm–1. H NMR (CDCl3): δ = 3.62 (s, 2 H, CH2S),
˜
2
3
4.15 (d, JP,H = 23.3 Hz, 1 H, CHP), 7.06 (t, JH,H = 7.5 Hz, 1 H,
Hp, PhS), 7.17 (t, JH,H = 7.5 Hz, 2 H, Hm, PhS), 7.31–7.38 (m, 8
3
H, Hm, Ph3P, Ho, PhS), 7.45–7.53 (m, 9 H, Ho, Hp, Ph3P) ppm.
31P{1H} NMR (CDCl3): δ = 15.96 ppm. 13C{1H} NMR (CDCl3):
δ = 41.78 (d, 3JP,C = 15.9 Hz, CH2S), 51.74 CHP (1JP,C = 107.8 Hz,
1
CHP), 125.10 (s, Cp, SPh), 126.53 (d, JP,C = 92.9 Hz, Ci, Ph3P),
IR: ν = 1611 (νCO), 1563, 1518 (νCO-acac), 1085, 622 (νClO4) cm–1.
˜
3
128.00 (s, Cm, SPh), 128.65 (s, Co, SPh), 128.88 (d, JP,C = 12.3 Hz,
3
1H NMR (CDCl3): δ = 1.38 (t, JH,H = 7.8 Hz, 3 H, CH3, SEt2),
4
2
Cm, Ph3P), 132.18 (d, JP,C = 1.2 Hz, Cp, Ph3P), 133.13 (d, JP,C
=
3
1.40 (t, JH,H = 7.4 Hz, 3 H, CH3, SEt2), 1.41 (s, 3 H, CH3, acac),
10.3 Hz, Co, Ph3P), 187.23 (s, CO) ppm; the signal due to Ci–SPh
was not observed. MS (MALDI+): m/z (%) = 426.8 (100) [M]+.
C27H23OPS (426.54): calcd. C 76.03, H 5.43, S 7.52; found C 76.09,
H 5.07, S 7.56.
1.80 (s, 3 H, CH3, acac), 3.23–3.56 (m, 4 H, CH2, SEt2), 3.68 (d,
2JP,H = 5.1 Hz, 1 H, CHP), 4.30 (s, 1 H, CHS), 5.11 (s, 1 H, CH,
3
4
acac), 7.49 (td, JH,H = 7.8, JP,H = 3.2 Hz, 6 H, Hm, Ph3P), 7.47
(td, 5JP,H = 1.6 Hz, 3 H, Hp, Ph3P), 7.70 (dd, JP,H = 13.0 Hz, 6 H,
3
Ho, Ph3P) ppm. 31P{1H} NMR (CDCl3): δ = 24.87 ppm. 13C{1H}
NMR (CDCl3): δ = 9.47 (s, CH3, SEt2), 9.75 (s, CH3, SEt2), 26.03
[Ph3PC(H)COCH2SMePh]ClO4 (5): To a solution of Ph3PC(H)-
COCH2Br (1) (0.150 g, 0.378 mmol) in Me2CO/CH2Cl2 (1:1,
40 mL), thioanisol (PhSMe, 1.80 mL, 15.1 mmol) and TlClO4
(0.114 g, 0.378 mmol) were added, and the resulting suspension was
stirred at room temp. for 24 h. After this time, the precipitated TlCl
was removed by filtration through Celite, and the resulting clear
solution was concentrated to dryness. To the oily residue Et2O
(40 mL) was added. Further stirring gave 5 as a pale brown solid,
which was filtered, washed with additional Et2O (2ϫ 15 mL), and
1
(s, CH3, acac), 26.69 (s, CH3, acac), 27.10 (d, JP,C = 49.5 Hz,
PCH), 32.91 (s, CH2, SEt2), 35.37 (s, CH2, SEt2), 39.42 (d, JP,C
3
=
1
15.2 Hz, CHS), 99.59 (s, CH, acac), 121.58 (d, JP,C = 90 Hz, Ci,
Ph3P), 129.32 (d, 3JP,C = 13 Hz, Cm, Ph3P), 132.66 (d, 4JP,C = 3 Hz,
2
2
Cp, Ph3P), 132.90 (d, JP,C = 11 Hz, Co, Ph3P), 173.91 (d, JP,C
=
2 Hz, C=O), 185.78 (s, CO, acac), 186.07 (s, CO, acac) ppm. MS
(MALDI+): m/z (%) = 612.0 (100) [M – ClO4]+. C30H34ClO7PPdS
(711.53): calcd. C 50.64, H 4.82, S 4.50; found C 50.50, H 4.64, S
4.37.
dried in vacuo. Yield: 0.151 g (74%). IR: ν = 1546 (νCO), 1080, 622
˜
1
(νClO4) cm–1. H NMR (CDCl3): δ = 3.16 (s, 3 H, MeS), 4.21 (d,
2JP,H = 21.1 Hz, 1 H, CHP), 4.71 (d, 2JH,H = 14.3 Hz, 1 H, CH2S),
4.95 (d, 1 H, CH2S), 7.39 (td, 3JH,H = 7.5, 4JP,H = 3.1 Hz, 6 H, Hm,
[Pd(acac-O,OЈ){Ph3PC(H)COC(H)SMePh-κC,C}]ClO4 (9): Com-
pound 9 was obtained according to the same procedure as that
Eur. J. Inorg. Chem. 2013, 2129–2138
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FULL PAPER
described for 8. Therefore, 7 (0.08 g, 0.129 mmol) was treated with
NMR (CDCl3): δ = 13.04 (s, CH3-Et), 13.14 (s, CH3-EtЈ), 25.32 (s,
AgClO4 (0.027 g, 0.129 mmol) and Tl(acac) (0.039 g, 0.129 mmol) 2 CH3, acac), 26.99 (s, 2 CH3, acacЈ), 31.25 (s, CH2-Et), 33.90 (d,
1
1
in CH2Cl2/Me2CO (9:1, 20 mL) to give 9 as a yellow solid. Com-
plex 9 was characterized by NMR spectroscopy as a mixture of
two diastereomers in a 10:1 molar ratio. Yield: 0.068 g (68.0%). IR:
CHPPh3, JP,C = 55.1), 34.57 (d, CHPPh3, JP,C = 54.9), 35.04 (s,
CH2-EtЈ), 36.83 (d, 3JP,C = 9.8 Hz, SCH2), 37.82 (d, 3JP,C = 9.1 Hz,
3
SCH2), 99.62 (s, CH, acac), 100.03 (s, CH, acacЈ), 129.12 (d, JP,C
ν = 1616 (νCO), 1574, 1514 (νCO-acac), 1082, 621 (νClO4) cm–1. 1H = 12.8 Hz, Cm, Ph3P), 129.16 (d, JP,C = 12.7 Hz, Cm, Ph3PЈ),
3
˜
4
4
NMR (CD2Cl2): δ = 1.40 (s, CH3, acac, minor), 1.43 (s, CH3, acac,
133.39 (d, JP,C = 2.9 Hz, Cp, Ph3P), 133.25 (d, JP,C = 2.9 Hz, Cp,
2
2
major), 1.60 (s, CH3, acac, minor), 1.83 (s, CH3, acac, major), 3.17
Ph3PЈ), 133.82 (d, JP,C = 10.0 Hz, Co, Ph3P), 133.86 (d, JP,C
=
(s, CH3, MeS, minor), 3.19 (s, CH3, MeS, major), 3.58 (dd, 2JP,H
4.8, JH,H = 0.9 Hz, CHP, minor), 3.60 (dd, JP,H = 4.7, JH,H
=
=
10.1 Hz, Co, Ph3PЈ), 183.36 (s, CO, acac), 183.61 (s, CO, acacЈ),
4
2
4
2
2
193.99 (d, JP,C = 2.1 Hz, C=O), 194.90 (d, JP,C = 2.1 Hz, C=OЈ)
ppm; the signals of Ci were not observed. MS (MALDI+): m/z (%)
= 583.0 (100) [M – ClO4]+. C28H30ClO7PPdS (683.48): calcd. C
49.20, H 4.42, S 4.69; found C 49.45, H 4.26, S 4.51.
0.9 Hz, CHP, major), 4.34 (s, CHS, minor), 4.42 (s, CHS, major),
5.09 (s, CH, acac, minor), 5.19 (s, CH, acac, major), 7.48 (m, Hm,
Ph3P, major, minor), 7.51–7.55 (m, Hm, PhS, major, minor), 7.58–
7.67 (m, Ho, Hp Ph3P, major, minor, Hp, PhS, major, minor), 7.86
[PdCl2{Ph3PC(H)COCH2SPh-κC,S}] (12): Complex 12 was pre-
pared according to a synthetic method identical to that described
for 10. Therefore, [Ph3PC(H)COCH2SPh] (4) (0.100 g, 0.234 mmol)
was treated with PdCl2(NCMe)2 (0.061 g, 0.148 mmol) in MeOH
(20 mL) to give 12 as a yellow-orange solid. Complex 12 was char-
acterized by NMR spectroscopy as a mixture of two diastereomers
3
3
(d, JH,H = 8.1 Hz, Ho, PhS, major), 7.92 (d, JH,H = 8.1 Hz, Ho,
PhS, minor) ppm. 31P{1H} NMR (CD2Cl2): δ = 24.61 (minor),
24.80 (major) ppm. 13C{1H} NMR (CD2Cl2): δ = 25.41 (d, JP,C
=
1
62.7 Hz, CHP, minor), 25.72 (s, CH3, acac, major), 25.81 (s, CH3,
acac, minor), 26.14 (d, 1JP,C = 57.7 Hz, CHP, major), 26.59 (s, MeS,
CH3, acac, major), 26.78 (s, MeS, CH3, acac, minor), 42.14 (d, 3JP,C
in a 6.7:1 molar ratio. Yield: 0.102 g (72.0%). IR: ν = 1660 (ν
)
=
˜
CO
3
= 15.7 Hz, CHS, minor), 44.02 (d, JP,C = 14.9 Hz, CHS, major),
cm–1. 1H NMR (CD2Cl2): δ = 2.75 (dd, JH,H = 12.8, JP,H
2
4
98.69 (s, CH, acac, minor), 98.86 (s, CH, acac, major), 120.66 (d,
7.0 Hz, CH2S, major), 3.04 (dd, 2JH,H = 13.2, 4JP,H = 5.0 Hz, CH2S,
minor), 4.32 (d, CH2S, minor), 4.38 (d, CH2S, major), 5.46 (br. s,
CHP, minor), 5.87 (br. s, CHP, major), 7.36 (t, Hm, Ph, major,
minor), 7.3–7.44 (m, Hm, Ph3P, major, minor), 7.50–7.56 (m, Hp,
Ph3P, major, Hp, Ph, major, minor), 7.61 (t, Hp, Ph3P, minor), 7.81
(dd, 3JP,H = 12.5, 3JH,H = 8.0 Hz, Ho, Ph3P, major, minor), 8.05 (d,
3JHH = 7.2 Hz, Ho, Ph, major, minor) ppm. 31P{1H} NMR
(CD2Cl2): δ = 24.90 (minor), 27.31 (major) ppm. 13C{1H} NMR
3
1JP,C = 89.4 Hz, Ci, Ph3P), 127.28 (s, Ci, PhS), 128.56 (d, JP,C
=
12.8 Hz, Cm, Ph3P, major, minor), 128.70 (s, Co, Ph, major), 129.55
(s, Cm, Ph, minor), 129.92 (s, Cm, Ph, major), 130.22 (s, Co, Ph,
minor), 132.80 (s, Cp, Ph, major), 132.89 (s, Cp, Ph, minor), 133.05–
133.14 (m, Cp, Co, Ph3P, major, minor), 172.68 (s, broad, CO, ylide,
major), 185.34 (s, CO, acac, major), 185.40 (s, CO, acac, minor),
185.80 (s, CO, acac, major), 185.87 (s, CO, acac, minor) ppm; the
signals of Ci and C=O for the minor isomer were not observed
owing to their low intensity. MS (MALDI+): m/z = 645.1 [M –
ClO4]+. C33H32ClO7PPdS (745.55): calcd. C 53.16, H 4.19, S 4.17;
found C 52.96, H 4.47, S 4.02.
1
(CD2Cl2): δ = 34.59 (d, JP,C = 54.8 Hz, CHP, minor), 34.67 (d,
1JP,C = 57.2 Hz, CHP, major), 42.97 (d, JP,C = 13.0 Hz CH2S,
3
minor), 43.53 (d, 3JP,C = 10.0 Hz, CH2S, major), 129.13 (d, JP,C
=
3
3
12.7 Hz, Cm, Ph3P, major), 129.53 (d, JP,C = 12.4 Hz, Cm, Ph3P,
minor), 129.99 (s, Cm, PhS, major), 130.31(s, Cm, PhS, minor),
130.99 (s, Cp, PhS, major), 132.71 (s, Cp, Ph3P, minor), 133.20 (d,
4JP,C = 2.4 Hz, Cp, Ph3P, major), 133.78 (s, Cp, PhS, major), 133.97
[PdCl2{Ph3PC(H)COCH2SEt-κC,S}] (10): To a solution of the
phosphonium–sulfide salt [Ph3PCH2C(O)CH2SEt]Br (3) (0.101 g,
0.218 mmol) in MeOH (10 mL), NEt3 (30.4 μL, 0.218 mmol) and
then PdCl2(NCMe)2 (0.056 g, 0.218 mmol) were added. A deep yel-
low solid precipitated after a few seconds. This suspension was
stirred at room temp. for 20 min, and then the solid 10 was col-
lected by filtration, washed with cold MeOH (15 mL) and Et2O
2
(s, Cp, PhS, minor), 134.44 (d, JP,C = 9.8 Hz, Co, Ph3P, major),
2
134.63 (d, JP,C = 9.9 Hz, Co, Ph3P, minor) ppm; the signals of Ci
and C=O were not observed. MS (MALDI+): m/z (%) = 533.1
(35.4) [M – 2 Cl + H]+. C27H23Cl2OPPdS (603.86): calcd. C 53.70,
H 3.84, S 5.31; found C 53.63, H 3.62, S 5.00.
(2ϫ 10 mL), and dried in vacuo. Yield: 0.082 g (68%). IR: ν =
˜
1650 (νCO) cm–1. Complex 10 was insoluble in the usual NMR
solvents, which precluded its characterization by this technique. MS
(ESI+): m/z (%) = 520.8 (44) [M – Cl]+. C23H23Cl2OPPdS (555.81):
calcd. C 49.70, H 4.17, S 5.77; found C 49.84, H 4.04, S 5.62.
[PdCl{Ph3PC(H)COC(H)Ph-μ-S:κC,C,S}]2 (13): To a solution of
Ph3PCHCOCH2SPh (4) (0.101 g, 0.234 mmol) in MeOH (15 mL),
NEt3 (32.7 μL, 0.234 mmol) was added. To this solution
PdCl2(NCMe)2 (0.061 g, 0.234 mmol) was added, and in a few sec-
onds a yellow solution formed. This solution was stirred at room
temp. for 3 h. During this time, complex 13 precipitated as a yellow
solid. After this time, 13 was collected by filtration, washed with
[Pd(acac-O,OЈ){Ph3PC(H)COCH2SEt-κC,S}]ClO4 (11): Com-
pound 11 was obtained according to the same procedure as that
described for 8. Therefore, 10 (0.06 g, 0.108 mmol) was treated with
AgClO4 (0.022 g, 0.108 mmol) and Tl(acac) (0.033 g, 0.11 mmol) cold MeOH (5 mL) and Et2O (20 mL), and dried in vacuo. Yield:
in CH2Cl2/Me2CO (9:1, 20 mL) to give 11 as a deep yellow solid.
Compound 11 was characterized as a mixture of two diastereomers
0.078 g (58.2%). IR: ν = 1595 (νCO) cm–1. 1H NMR (CD2Cl2): δ =
˜
4
2
4.09 (d, JP,H = 5.2 Hz, 1 H, CHS), 4.45 (d, JP,H = 5.8 Hz, 1 H,
in a 1:1 molar ratio. Yield: 0.045 g (61%). IR: ν = 1673 (νCO), 1557,
CHP), 7.20–7.26 (m, 3 H, Hp, Hm, PhS), 7.49 (td, 3JH,H = 7.6, 4JP,H
˜
1514 (νCO-acac), 1082, 622 (νClO4) cm–1. 1H NMR (CDCl3): δ = 0.97 = 2.8 Hz, 6 H, Hm, Ph3P), 7.61 (t, JH,H = 7.5 Hz, 3 H, Hp, Ph3P),
3
3
3
(s, CH3, acac), 0.98 (s, CH3Ј, acac), 1.41 (t, JH,H = 7.4 Hz, CH3,
7.70 (d, 2 H, Ho, PhS), 7.82 (dd, JP,H = 11.5 Hz, 6 H, Ho, Ph3P)
3
Et), 1.42 (t, JH,H = 7.4 Hz, CH3Ј, Et), 1.86 (s, CH3, acac), 1.87 (s, ppm. 31P{1H} NMR (CD2Cl2): δ = 25.64 ppm. 13C{1H} NMR
2
4
1
3
CH3Ј, acac), 2.54 (dd, JH,H = 13.9, JP,H = 6.9 Hz, CH2S), 2.74–
(CD2Cl2): δ = 35.24 (d, JP,C = 69.0 Hz, CHP), 54.00 (d, JP,C =
2
4
2.86 (m, CH2-Et, CH2SЈ), 3.20 (dd, JH,H = 13.2, JP,H = 7.4 Hz,
10.1 Hz, CHS), 128.30 (s, Cp, Ph), 129.27 (s, Cm, Ph), 129.48 (d,
CH2-Et), 3.48 (dd, 2JH,H = 13.1, JP,H = 7.2 Hz, CH2-EtЈ), 4.17 (d, 3JP,C = 12.7 Hz, Cm, Ph3P), 129.50 (s, Co, Ph), 133.78 (d, JP,C
=
4
4
2JH,H = 12.9 Hz, CH2SЈ), 4.33 (d, CH2S), 5.06 (s, CH, acac), 5.08
2.4 Hz, Cp, Ph3P), 134.55 (d, JP,C = 10.2 Hz, Co, Ph3P), 138.90 (s,
2
2
2
(s, CHЈ, acac), 5.62 (d, JP,H = 2.0 Hz, CHP), 5.88 (d, JP,H
=
Ci, Ph), 178.98 (s, CO) ppm; the signal of Ci–Ph3P was not ob-
2.6 Hz, CHPЈ), 7.53 (m, Hm, Ph3P), 7.63 (m, Hp, Ph3P), 7.76 (dd,
served. MS (MALDI+): m/z (%) = 1099.20 (18) [M – Cl]+.
3
3JP,H = 12.6, JH,H = 7.8 Hz, Ho, Ph3P) ppm. 31P{1H} NMR C54H44Cl2O2P2Pd2S2 (1134.8): calcd. C 57.15, H 3.91, S 5.65; found
(CDCl3): δ = 25.88 (Ph3PCH), 26.17 (Ph3PЈCH) ppm. 13C{1H} C 57.47, H 3.75, S 5.51.
Eur. J. Inorg. Chem. 2013, 2129–2138
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Selected examples of complexes with C-bonded ylides: a) M.
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G. Nardin, M. Mari, J. Chem. Soc., Dalton Trans. 1987, 1381.
Selected examples of complexes with O- or N-bonded ylides:
a) L. R. Falvello, J. C. Ginés, J. J. Carbó, A. Lledós, R. Nav-
arro, T. Soler, E. P. Urriolabeitia, Inorg. Chem. 2006, 45, 6803;
b) L. R. Falvello, S. Fernández, R. Navarro, E. P. Urriolabeitia,
Inorg. Chem. 1997, 36, 1136; c) D. Soulivong, C. Wieser, M.
Marcellin, D. Matt, A. Harriman, L. Toupet, J. Chem. Soc.,
Dalton Trans. 1997, 2257; d) L. R. Falvello, S. Fernández, R.
Navarro, I. Pascual, E. P. Urriolabeitia, J. Chem. Soc., Dalton
Trans. 1997, 763; e) U. Belluco, R. A. Michelin, R. Bertani,
G. Facchin, G. Pace, L. Zanotto, M. Mozzon, M. Furlan, E.
Zangrando, Inorg. Chim. Acta 1996, 252, 355; f) L. R. Falvello,
S. Fernández, R. Navarro, E. P. Urriolabeitia, Inorg. Chem.
1996, 35, 3064.
C,X-Chelating ylides: a) R. Zurawinski, C. Lepetit, Y. Canac,
M. Mikolajczyk, R. Chauvin, Inorg. Chem. 2009, 48, 2147; b)
Y. Canac, C. Lepetit, M. Abdalilah, C. Duhayon, R. Chauvin,
J. Am. Chem. Soc. 2008, 130, 8406; c) J. Vignolle, H. Gor-
nitzka, L. Maron, W. W. Schoeller, D. Bourissou, G. Bertrand,
J. Am. Chem. Soc. 2007, 129, 978; d) J. Vignolle, B. Donnadieu,
D. Bourissou, M. Soleilhavoup, G. Bertrand, J. Am. Chem. Soc.
2006, 128, 14810; e) L. R. Falvello, S. Fernández, R. Navarro,
E. P. Urriolabeitia, New J. Chem. 1997, 21, 909; f) J. Vicente,
M. T. Chicote, M. C. Lagunas, Inorg. Chem. 1993, 32, 3748.
Chiral C,X-chelating ylides: g) R. Zurawinski, B. Donnadieu,
M. Mikolajczyk, R. Chauvin, Organometallics 2003, 22, 4810;
h) L. Viau, C. Lepetit, G. Commenges, R. Chauvin, Organome-
tallics 2001, 20, 808.
[PdCl{Ph3PC(H)COC(H)SPh-κC,C}PPh3] (14): To a suspension of
13 (0.061 g, 0.053 mmol) in CH2Cl2 (25 mL), PPh3 (0.028 g,
0.108 mmol) was added. The initial yellow suspension was stirred
at room temp., and the solid gradually dissolved; a clear solution
was obtained after 10 min. Stirring was maintained for an ad-
ditional 5 h. After this time, the solution was concentrated to dry-
ness, and the residue was treated with Et2O (15 mL) to give 14 as
a yellow solid. Yield: 0.071 g (78.1%). IR: ν = 1605 (νCO) cm–1. 1H
˜
3
4
NMR (CDCl3): δ = 3.32 (t, JP,H and JP,H = 6.8 Hz, 1 H, CHS),
4.80 (t, JP,H and JP,H = 9.6 Hz, 1 H, CHP), 7.06 (m, 1 H, Hp,
2
3
PhS), 7.18 (m, 4 H, Ho, Hm, PhS), 7.28–7.40 (m, 9 H, Hp, Hm,
3
4
Ph3P), 7.52 (td, JH,H = 7.6, JP,H = 2.8 Hz, 6 H, Hm, Ph3P), 7.63
[3]
(t, Hp, Ph3P), 7.70 (dd, 3JP,H = 11.2, 3JH,H = 7.2 Hz, 6 H, Ho, Ph3P),
7.89 (dd, JP,H = 12.8 Hz, 6 H, Ho, Ph3P) ppm. 31P{1H} NMR
3
(CDCl3): δ = 24.69 (s, 1 P, Ph3PCH), 26.32 (s, 1 P, Ph3PPd) ppm.
1
2
13C{1H} NMR (CDCl3): δ = 41.41 (dd, JP,C = 75.8, JP,C
=
=
3
1
58.6 Hz, PCH), 51.80 (d, JP,C = 11.1 Hz, SCH), 123.72 (d, JP,C
89.5 Hz, Ci, Ph3P), 124.49 (s, Cp, PhS), 126.37 (s, Cm, PhS), 128.15
3
3
(d, JP,C = 10.1 Hz, Cm, Ph3P), 128.54 (s, Co, PhS), 128.92 (d, JP,C
4
= 13.1 Hz, Cm, Ph3P), 130.20 (d, JP,C = 3.0 Hz, Cp, Ph3P), 131.78
1
4
(d, JP,C = 45.5 Hz, Ci, Ph3P), 132.79 (d, JP,C = 3.0 Hz, Cp, Ph3P),
2
2
134.21 (d, JP,C = 10.1 Hz, Co, Ph3P), 134.64 (d, JP,C = 12.1 Hz,
Co, Ph3P), 142.15 (d, JP,C = 4.0 Hz, Ci, PhS), 178.79 (d, JP,C
4
2
=
4.0 Hz, C=O) ppm. MS (MALDI+): m/z (%) = 794.0 (44.8) [M –
Cl]+. C45H37ClOP2PdS (829.72): calcd. C 62.14, H 4.59, S 3.86;
found C 61.83, H 4.40, S 3.86.
[4]
X-ray Crystallography: Crystals of 8 and 9 of suitable quality for
X-ray diffraction measurements were grown by vapor diffusion of
Et2O into CH2Cl2 solutions of the crude products at 25 °C. In each
case, a single crystal was mounted at the end of a quartz fiber in a
random orientation, covered with perfluorinated oil, and placed
under a cold stream of N2 gas. The data collections were performed
with Bruker Smart Apex CCD or Oxford Diffraction Xcalibur2
diffractometers with graphite-monochromated Mo-Kα radiation (λ
= 0.71073 Å). In all cases, a hemisphere of data was collected based
on ω- and φ-scan runs. The diffraction frames were integrated by
using the programs SAINT[17] or CrysAlis RED,[18] and the inte-
grated intensities were corrected for absorption with SADABS.[19]
The structures were solved and developed by Fourier methods.[20]
All non-hydrogen atoms were refined with anisotropic displace-
ment parameters. The H atoms were placed at idealized positions
and treated as riding atoms. Each H atom was assigned an isotropic
displacement 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.[21] CCDC-913538 (for 8) and -913539 (for 9) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[5]
Supporting Information (see footnote on the first page of this arti-
cle): NMR spectra of organometallic compounds 8–14.
[6]
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Acknowledgments
Financial support from the Spanish Ministerio de Economía y
Competitividad (MINECO) under project CTQ2011-22589 and the
Regional Government of Aragón under project E-97 is gratefully
acknowledged.
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FULL PAPER
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Received: December 4, 2012
Published Online: February 12, 2013
Eur. J. Inorg. Chem. 2013, 2129–2138
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