Different coordination modes of the polyfunctional ylide Ph 3P=C(H)C(O)CH2C(O)OEt: C- vs. O,O′-boading in PdII, PtII and AuI complexes

Article abstract of DOI:10.1002/ejic.200300801

Treatment of the polyfunctional ylide Ph₃P=C(H)C(O)CH ₂-COOEt (1) with the solvated complexes [M(C∧X)(THF) ₂]ClO₄ gave the O,O′ derivatives [M(C∧X)(Ph ₃PCH₂C(O)=C(H)-C(= O)OEt-κ-O,O′]ClO ₄ [M(C∧X) = Pd(C₆H₄CH₂NMe ₂) (2), Pd(CH₂C₉H₆N) (3), Pd(NC ₅H₄-2-C₆H₄) (4), Pd(NC ₁3H₈) (5), Pd[(S)-C₆H₄C(H)MeNMe ₂] (6), Pt[o-CH₂C₆H₄P(o-tol) ₂] (7), Pd[o-CH₂C₆H₄P(o-tol) ₂] (8), and Pd(C₆F₅)(SC₄H ₈) (9)]. During the reaction, one proton of the methylene unit is transferred to the ylidic carbon, which is transformed into a phosphonium group generating the zwitterion [Ph₃PCH₂C(O)= C(H)-C(=O)OEt], which coordinates to the metal center as an O,O′-chelating ligand. Treatment of 1 with [AuCl(SC₄H₈)] or [Au(PPh ₃)(OCMe₂)]ClO₄ gave [AuCl{C(H)(PPh ₃)C(O)-CH₂COOEt}] (10) or [Au{C(H)(PPh₃)C(O) CH₂COOEt}-(PPh₃)]ClO₄ (11), in which the ylide is C-bonded. The X-ray crystal structures of complexes 2a, 9 and 10 have been determined. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300801

FULL PAPER
Different Coordination Modes of the Polyfunctional Ylide Ph3P؍
C(H)C(O)CH2C(O)OEt: C- vs. O,OЈ-Bonding in PdII, PtII and AuI Complexes
[a]
[a]
[a]
[a]
´
Marta Carbo, Larry R. Falvello, Rafael Navarro,* Tatiana Soler, and
Esteban P. Urriolabeitia*[a]
Keywords: Palladium / Platinum / Gold / Ylides / Structure elucidation
Treatment of the polyfunctional ylide Ph3P=C(H)C(O)CH2-
COOEt (1) with the solvated complexes [M(C∧X)(THF)2]ClO4
gave the O,OЈ derivatives [M(C∧X)(Ph3PCH2C(O)=C(H)−C(=
C(H)−C(=O)OEt], which coordinates to the metal center as
an O,OЈ-chelating ligand. Treatment of 1 with [AuCl(SC4H8)]
or [Au(PPh3)(OCMe2)]ClO4 gave [AuCl{C(H)(PPh3)C(O)-
CH2COOEt}] (10) or [Au{C(H)(PPh3)C(O)CH2COOEt}-
(PPh3)]ClO4 (11), in which the ylide is C-bonded. The X-ray
crystal structures of complexes 2a, 9 and 10 have been deter-
mined.
O)OEt-κ-O,OЈ]ClO4 [M(C∧X)
= Pd(C6H4CH2NMe2) (2),
Pd(CH2C9H6N) (3), Pd(NC5H4-2-C6H4) (4), Pd(NC13H8) (5),
Pd[(S)−C6H4C(H)MeNMe2] (6), Pt[o-CH2C6H4P(o-tol)2] (7),
Pd[o-CH2C6H4P(o-tol)2] (8), and Pd(C6F5)(SC4H8) (9)]. During
the reaction, one proton of the methylene unit is transferred
to the ylidic carbon, which is transformed into a phosphon-
ium group generating the zwitterion [Ph3PCH2C(O)=
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
ligand (using combinations of the four possible donor
atoms). The synthesis of 1 was reported four decades ago[2]
but, with the exception of applications in purely synthetic
organic processes,[3] its bonding properties have remained
unexplored. We have found quite different patterns of reac-
tivity of this ylide as a function of the metallic precursor:
C-bonding in AuI complexes (leaving the β-keto ester func-
tionality unchanged) and O,OЈ-coordination in PdII and
PtII derivatives (which generates a phosphonium func-
tionality). This paper describes the results obtained, and
synthetic possibilities are also discussed.
We have recently shown that the keto-stabilized ylides
[Ph3PϭC(H)C(O)R] (R ϭ Me, OMe, Ph) can behave as am-
bidentate ligands towards PdII complexes, since they can
coordinate either through the soft ylidic Cα atom or
through the hard carbonyl oxygen depending on the vacant
coordination site at the palladium precursor. This coordi-
nation occurs with notable selectivity, which has been ex-
plained in terms of the anti-symbiotic effect and the nature
of the donor atoms bonded to the PdII center.[1] In all cases
studied, the ylide bonds to the metal center using only one
donor atom. Further introduction of new functional groups
at the molecular skeleton of the ylide should result in an
expansion of its bonding abilities and in the transformation
of the aforementioned ambidenticity to polydenticity. We
are currently pursuing the study of the coordinating proper-
ties of polydentate ylides, and how the presence of new
functionalities alters the bonding patterns observed in am-
bidentate ylides.
Results and Discussion
1. Palladium(II) and Platinum(II) Complexes
The ylide 1 was prepared following the method described
[2b]
´
by Serratosa and Sole,
and has been characterized
through its analytical and spectroscopic data. Here we also
report the 1H and 13C{1H} NMR spectroscopic parameters,
since they were not provided in the original[2] or subsequent
works[3f] (see Exp. Sect.). In order to check the chelating
ability of 1, its reactivity towards the bis(solvated) deriva-
tives [M(C∧X)(THF)2]ClO4 was examined (see Scheme 1).
These bis(solvate) complexes were prepared by treatment
of the corresponding dinuclear µ-halide complexes
[M(C∧X)(µ-Cl)]2 with AgClO4 (1:2 molar ratio) in THF,
followed by removal of AgCl by filtration. The freshly pre-
pared solutions of [M(C∧X)(THF)2]ClO4 were treated with
the stoichiometric amount of 1. After the initial dissolution
of 1, complexes 2Ϫ9 precipitated as yellow solids from the
Here we describe the complete characterization of ethyl
3-oxo-4-(triphenylphosphoranylidene)butanoate
[Ph3Pϭ
C(H)C(O)CH2COOEt] (1) and its reactivity towards com-
plexes of PdII, PtII and AuI, in order to determine its coord-
inating ability. The ylide 1 could behave, at first sight, as a
C-donor ligand (through the Cα atom), as an O-donor li-
gand (through three different O atoms) or as a polydentate
[a]
´
´
Departamento de Quımica Inorganica, Instituto de Ciencia de
´
Materiales de Aragon, Universidad de Zaragoza-CSIC,
50009 Zaragoza, Spain
E-mail: esteban@unizar.es
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DOI: 10.1002/ejic.200300801
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Different Coordination Modes of a Polyfunctional Ylide
FULL PAPER
respective reaction solutions. The process is represented in observed; (iii) instead, two singlets appear at
δ ϭ
Scheme 1. 4.5Ϫ5 ppm (δ ϭ 4.81 ppm, major isomer; 4.86 ppm, minor
isomer) and two doublets at about 4.15 ppm (δ ϭ 4.13 ppm,
JPH ϭ 13.8 Hz, major isomer, 4.16 ppm, JPH ϭ 13.8 Hz,
minor isomer), with a relative intensity ratio singlet/doub-
let ϭ 1:2. These observations strongly suggest that the
methylene-ylide skeleton [ϪCH2ϪC(O)ϪC(H)ϭP] in 1 has
been transformed into the phosphonium-enolate func-
tionality [ϪC(H)ϭC(O)ϪCH2P] in 2, by the transfer of one
H atom from the methylene group to the ylidic carbon Cα
(see Scheme 2). The signals in the range 4.5Ϫ5 ppm can
then be attributed to the ϭC(H)Ϫ proton (shifted slightly
to high-field with respect to the usual position in β-diketon-
ate ligands)[4] and the signals at about 4.15 ppm can be as-
signed to the CH2P protons.[5] The resultant structure of
the coordinated ligand in 2 is shown in Scheme 1.
Scheme 1
Scheme 2. Proton transfer in 1 and resonance forms of the zwit-
terion [Ph3PCH2ϪC(O)ϭC(H)C(ϭO)OEt]
Complexes 2Ϫ9 gave elemental analyses in good agree-
ment with the stoichiometries depicted in Scheme 1, and the
mass spectra in all cases show the presence of the cationic
The structures depicted in Scheme 1 also account for the
molecular peak [M Ϫ ClO4]ϩ with the correct isotopic dis- observation, in the 31P{1H} NMR spectrum of 2, of two
tribution. The IR spectra of 2Ϫ9 clearly show two strong resonances at approximately 22 ppm, typical for phos-
absorptions in the 1500Ϫ1630 cmϪ1 region: one at approxi- phonium groups.[5] In addition, the 13C{1H} NMR spec-
mately 1614Ϫ1628 cmϪ1 (attributed to the νCOO stretch) trum (acquired as APT) of 2 also shows signals character-
and the other one at around 1502Ϫ1525 cmϪ1, assigned to istic of the generated phosphonium-enolate moiety: (i) two
the νCO stretch of the carbonyl group adjacent to the ylide doublets at about 36 ppm (1JP,C ഠ 53 Hz) with negative
unit. A comparison of these values with those obtained for phase can be attributed to the CH2P carbon atoms, and (ii)
the free ylide 1 (1717 and 1546 cmϪ1, respectively)[2b] shows two doublets at about 90 ppm (3JP,C ഠ 7 Hz) with positive
that both absorptions have been shifted to lower energies. phase can be assigned to the ϭC(H) carbon atoms. Finally,
This fact strongly suggests that both carbonyl groups are the question of whether structure (a) or (b) in Scheme 1
bonded to the metal center, since it has been well estab- corresponds to the major isomer must be addressed. The
lished that C-coordination of the keto-stabilized ylides pro- assignment of structure (a) to the major isomer can easily
1
duces a high energy shift of the νCO stretch (with respect to be inferred from the H NMR spectrum in which the sig-
the free ylide)[1] and, thus, a shift of the absorption at 1546 nals assigned to the protons of the metallated C6H4 group,
cmϪ1 to higher wavenumbers should be observed for C- for the major isomer, appear well spread in the range δ ϭ
bonding of 1.
7.0Ϫ5.8 ppm, with the signal due to the H6 proton (ortho
The NMR spectra of complex 2 provide valuable struc- to the metallated position) at δ ϭ 5.89 ppm. This signal is
tural information. Firstly, all NMR spectra (1H, 13C{1H} clearly shifted to high field with respect to its position in the
and 31P{1H}) display two identical sets of signals (ratio starting dinuclear derivative [Pd(µ-Cl)(C6H4CH2NMe2)]2 (
4.5:1), showing the presence of two isomers (a) and (b) in δ ഠ 7.0 ppm), and this high-field shift must be due to the
solution. Due to the asymmetric nature of 1 and its O,OЈ- anisotropic shielding[6] produced by a phenyl ring of the
bonding mode, two geometric isomers can be envisaged. In PPh3 group. This fact implies a cis arrangement of the C6H4
1
addition, the H NMR spectrum of 2 shows three notable fragment of the metallated ligand and the PPh3 unit of the
features: (i) the signals due to the CH2N and NMe2 protons phosphonium-enolate ligand, which occurs in structure (a).
appear as singlets, indicating that the molecular plane is Moreover, this anisotropic shielding should not be pro-
a symmetry plane; (ii) signals which could result from the duced in the other isomer (which possesses an OEt group
methylene protons or the ylidic proton PϭCα(H) were not in a position remote from the H6 proton) and, in fact, the
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´
M. Carbo, L. R. Falvello, R. Navarro, T. Soler, E. P. Urriolabeitia
FULL PAPER
aromatic resonances of the metallated C6H4 ring in the getically more stable, since it minimizes intramolecular
minor isomer all appear around 7.0 ppm. We can thus con- steric repulsions.
clude, on the basis of the NMR spectroscopic data, that the
In the case of complex 9 we have also observed the for-
major isomer is that represented in Scheme 1 by structure mation of a single isomer, although we do not have direct
(a) and the minor isomer by structure (b).
spectroscopic evidence in favor of a given structure for this
complex. Throughout the description of the structures of
2Ϫ8 it is possible to detect a repetitive arrangement of the
ligands, which places the carbonyl oxygen of the C(O)OEt
unit trans to the metallated carbon atom, and the oxygen
of the enolate group trans to the heteroatom. Since we also
have a metallated carbon atom (C6F5 ligand) and a neutral
heteroatom (the S atom of the SC4H8 ligand) in 9, we pro-
pose a similar stereochemistry for 9 and, thus, the structure
(a) as depicted in Scheme 1. This hypothesis has been cor-
roborated through the determination of the X-ray structure
(see below).
The IR data of complexes 2Ϫ9, and their comparison
with those for the free ylide 1 show that, in all cases, the
bonding mode of the ylide to the metal center should be the
same (O,OЈ-chelate), since the same shifts of the carbonyl
absorptions were observed.
Moreover, the NMR spectroscopic data of complexes
2Ϫ9 show two relevant facts: (i) in all cases the coordinated
ylide has undergone a proton transfer and, hence, the actual
O,OЈ-bonded ligand is the zwitterionic tautomer of 1
[Ph3(Pϩ)ϪCH2ϪC(OϪ)ϭC(H)C(O)OEt] (Scheme 2); (ii)
complexes 3, 7, 8, and 9 were obtained as single isomers,
within the limit of detection of the technique, while com-
plexes 2, 4, 5 and 6 were obtained as a mixture of the geo-
metric isomers (a) and (b) depicted in Scheme 1.
In summary, the interaction of the ylide 1 with PdII and
PtII complexes promotes the generation of the phos-
phonium-enolate [Ph3(Pϩ)ϪCH2ϪC(OϪ)ϭC(H)C(O)OEt]
ligand in all cases. It is remarkable to observe the presence
of a free phosphonium unit in a ligand strongly anchored
to the metal center. This phosphonium moiety could be the
clue for further functionalization of the ligand, since its de-
protonation would generate a new ylide unit, which could
be involved in a variety of new processes (e.g. synthesis of
polynuclear complexes, Wittig reactions, etc.) which are not
possible starting from the free ligand 1.
For complexes 4, 5, and 6, the assignment of structure
(a) to the major isomers can be inferred, as for complex 2,
from their 1H NMR spectra. In the case of 4, the resonance
assigned to the H6Ј proton (ortho to the metallated position)
in the major isomer appears shifted to high field (δ ϭ
6.07 ppm), and the same shift was observed in complex 5
(δ ϭ6.05 ppm). In complex 6, the signal due to the H6 pro-
ton appears at δ ϭ 5.88 ppm, virtually the same chemical
shift as that observed for 2. Thus, we can assign structure
(a) for the major isomers of 4, 5 and 6.
2. Gold(
I) Complexes
As we have seen in the preceding discussion, the reactiv-
The assignment of structure (a) to complex 3 rests on the ity of 1 towards cationic bis(solvate) complexes of PdII and
similarity of the chemical shifts of the carbonyl C atoms in PtII does not result in the expected C-coordination. In an
the 13C{1H} NMR spectrum with those in 2a and 4aϪ6a. attempt to involve the ylidic Cα atom in bonding to a tran-
These chemical shifts appear in a very narrow range of fre- sition metal, we have focused our attention to gold() com-
quencies [δCO ϭ 173.44 (3), 173.67 (2a), 173.89 (4a), 173.90 pounds, taking into account the exceptional stability of AuI
(5a), 173.78 (6a) ppm; δCOO ϭ 171.33 (3), 171.21 (2a), complexes with C-bonded α-stabilized P-ylides,[7] and also
171.57 (4a), 171.51 (5a), 171.21 (6a) ppm], suggesting quite that the O-coordination of keto-stabilized P-ylides to AuI
similar chemical environments and a very similar structural remains unknown.
arrangement. In comparison, the corresponding resonances
Treatment of [AuCl(SC4H8)] with 1 (1:1 molar ratio) in
of the minor isomers (b) appear, systematically, at lower CH2Cl2 at room temperature occurs with displacement of
field. Moreover, the resemblance of the ancillary C,N-cyclo- the labile ligand SC4H8 and C-bonding of the ylide, giving
metallated ligands in 3 with those in 2, 4, 5 or 6 (they do the
neutral
derivative
[AuCl{C(H)(PPh3)C(O)-
not show notable structural differences and similar behavior CH2C(O)OEt}] (10). In addition, treatment of the solvated
should be expected) also supports this assignment. These complex [Au(OCMe2)(PPh3)]ClO4 (obtained by treatment
extrapolations cannot be performed for complexes 7 and 8. of [AuCl(PPh3)] with AgClO4 in acetone, see details in Exp.
Here, changes in the donor atom (N replaced by P) induce Sect.) with 1 (1:1 molar ratio) results in the formation of
a change in the electronic requirements at the trans posi- [Au{C(H)(PPh3)COCH2COOEt}(PPh3)]ClO4 (11), which
tion, and the substituents at the donor atom also change also contains the C-coordinated ylide. These two processes
(the P atom contains two bulky ortho-tolyl groups) so that are presented in Scheme 3.
the steric requirements at the cis position are different.
Both complexes gave elemental analyses and mass spectra
However, the assignment of structure (a) for 7 and 8 can be in good agreement with the proposed structures. The C-
inferred from the 13C{1H} NMR spectra, since the signal bonding of the ylide 1 in compounds 10 and 11 can be
of the methylene carbon CH2P appears as a doublet of dou- inferred from the IR spectra, since the absorptions assigned
blets through coupling with the adjacent phosphonium P to the CϭO stretch appear at 1731 cmϪ1 (νCOO) and 1666
atom and with the trans P atom of the cyclometallated li- cmϪ1 (νCO) in 10, and at 1724 and 1657 cmϪ1 for the re-
gand [4JP,C ϭ 5.9 Hz for 7 and 4JP,C ϭ 5.1 Hz for 8]. More- spective absorptions in 11. A comparison of these values
over, the remote trans location of the two bulkiest fragments with those reported for the free ylide (1717 and 1546
of the molecule, ϪCH2PPh3 and P(o-tol)2, should be ener- cmϪ1 [2b]
)
shows that the absorption of the carboxylate
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Eur. J. Inorg. Chem. 2004, 2338Ϫ2347

Different Coordination Modes of a Polyfunctional Ylide
FULL PAPER
that observed in 1 (108.3 Hz), and shifted to high field with
respect to the corresponding signal in 1. All these changes
are in good agreement with the presence of a C-bonded yl-
ide.[1]
As expected, the chemical behavior in this case is quite
different from that observed in PdII and PtII complexes. The
C-bonding of the ylide 1 blocks further reactivity at the Cα
atom, but leaves the β-keto ester moiety unchanged. It
seems likely then, that any further reactivity of the gold
complexes could be directed selectively to the methylene
group. This is not possible in the free ligand 1, in which
most of its reactivity occurs at the Cα center after depro-
tonation of the CH2 unit.
Scheme 3
group undergoes very small shifts, suggesting that it does
not interact with the metal center, whereas that due to the
carbonyl adjacent to the ylide group appears shifted to high
energy by up to 120 cmϪ1. This latter shift implies a higher
participation of the keto-form in the description of the
Crystal Structure of [Pd(C6H4CH2NMe2)(Ph3PCH2C(O)؍
C(H)C(؍O)OEt-κ-O,OЈ)]ClO4 (2a)
A solution of a mixture of 2a/2b in CH2Cl2 was slowly
bonded ylide, and it is a clear indicator of the presence of evaporated to dryness at room temperature. During this
a C-coordinated ylide.[1]
process very regular yellow crystals were formed, which
Additional evidence for the C-coordination of the ylide, should be a mixture of the complexes 2a and 2b in the same
and for the concomitant hybridization change (sp2 Ǟ sp3), molar ratio as that of the crude complex, and from this
comes from the analysis of the NMR spectroscopic data. mixture of crystals, a yellow block was selected. The struc-
Key features of the NMR spectra of 10 and 11 are: (i) the ture corresponds to that of complex 2a, already established
ylidic proton PCα(H) appears at about 4.8 ppm as a singlet by spectroscopic methods.
in 10 or as a doublet in 11, with a small coupling constant
A drawing of the cationic organometallic fragment is
2JPH (9 Hz); (ii) the methylene protons appear dia- shown in Figure 1. The parameters concerning the data col-
stereotopic, showing the absence of a symmetry plane; (iii) lection and refinement are given in Table 1, and selected
the P atom PCα(H) appears in the 31P{1H} NMR spectrum bond lengths and angles are collected in Table 2. The Pd
as a singlet (10) or as a doublet (11), shifted to low field atom is located in a slightly distorted square-planar en-
(24.84 ppm for 10, 26.15 ppm for 11) with respect to the vironment, surrounded by the ortho-metallated carbon
free ylide (δ ϭ15.50 ppm); (iv) the ylidic carbon atom atom C(25), the aminic N atom N(1), and the two oxygen
PCα(H) appears in the 13C{1H} NMR spectrum (acquired atoms, O(1) and O(2), of the phosphonium-enolate
as APT) as a doublet with positive phase, with a 1JP,C coup- [Ph3PCH2C(O)ϭCHϪC(O)OEt] ligand, which coordinates
ling constant (55.7 Hz for 10, 58.6 Hz for 11) smaller than as an O,OЈ-chelate. The structural parameters of the ortho-
Table 1: Crystal data and structure refinement for complexes 2a, 9 and 10
2a
9
10
Empirical formula
Mol mass
C33H35ClNO7PPd
730.44
C34H31ClF5O7PPdS
851.47
C24H23AuClO3P
622.81
monoclinic
P21/n
12.2186(11)
14.5885(13)
12.9320(12)
Crystal system
Space group
triclinic
triclinic
¯
¯
P1
P1
˚
a (A)
11.3130(6)
12.2269(6)
14.2943(7)
94.123(1)
112.790(1)
116.409(1)
1559.61(14)
2
11.7925(8)
11.8733(8)
13.2719(9)
77.936(1)
87.107(1)
79.959(1)
1789.2(2)
2
˚
b (A)
˚
c (A)
α (°)
β (°)
γ (°)
96.1960(10)
3
˚
V (A )
2291.7(4)
4
1.805
Z
Dcalcd. (Mg·mϪ3
)
1.555
0.782
1.580
0.769
µ (mmϪ1
)
6.628
Reflections collected
Unique reflections
Data/restraints/parameters
R1 [I Ͼ 2σ(I)]
9964
9962
13973
6729, Rint ϭ 0.0103
6729/0/400
0.0220
0.0556
1.087
100(2)
0.71073
6237, Rint ϭ 0.0183
6237/0/452
0.0590
0.1450
1.045
291(2)
0.71073
5157, Rint ϭ 0.0264
5157/0/272
0.0248
0.0620
1.041
100(2)
0.71073
wR2 [I Ͼ 2σ(I)]
Goodness of fit
T/K
˚
λ(Mo-Kα)/A
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M. Carbo, L. R. Falvello, R. Navarro, T. Soler, E. P. Urriolabeitia
FULL PAPER
length is only slightly shorter than those found in other O-
[8b]
˚
bonded α-stabilized keto-ylides [2.154(2) A].
These facts
are in good agreement with a higher keto character for the
C(22)ϪO(2) bond and a higher enolic character for the
C(20)ϪO(1) bond. Moreover, the CϪC bond lengths in the
chelate ring are also quite different. The C(21)ϪC(22) bond
˚
length [1.426(2) A] shows a small double bond component,
since it is intermediate between a single σ(CϪC) bond and
a double CϭC bond,[10] while the C(20)ϪC(21) bond length
˚
[1.372(2) A] clearly shows double bond character. Outside
˚
the ring, the C(19)ϪC(20) bond length [1.521(2) A] implies
a single σ(CϪC) bond, and all PϪC bond lengths are also
in the range found for single bonds.[10]
The geometry around the carbon atoms C(20) and C(22)
is strictly planar [sum of the bond angles ϭ 359.99(15)° in
both cases] and the bond angle C(20)ϪC(21)ϪC(22)
[124.69(15)°] also reflects its sp2 character. The environ-
ments around the atoms C(19) and P(1) are tetrahedral.
Furthermore, the intramolecular distance P(1)ϪO(1)
Figure 1. Thermal ellipsoid plot of the cationic fragment of 2a.
Non-hydrogen atoms are drawn at the 50% probability level
˚
[3.001(2) A] is shorter than the sum of the van der Waals
[11]
˚
radii (3.32 A),
suggesting an intramolecular interaction
˚
Table 2. Selected bond lengths (A) and angles (°) for 2a
between the positively charged phosphonium atom P(1) and
the formally anionic atom O(1). This type of 1,4-interaction
has recently been described by us for keto-stabilized P-yl-
ides.[12] However, this intramolecular interaction should be
weaker than those described in P-ylides, as can be deduced
from the value of the torsion angle P(1)ϪC(19)ϪC(20)Ϫ
O(1) (51.2°), which is considerably different from the value
obtained in the more stable cisoid forms of the ylides
(nearly 0°).[12] Finally, the H atom H(26) [bonded to C(26)]
points to the phenyl ring C(7)ϪC(12), the distance between
H(26) and the best least-squares plane defined by the C
Pd(1)ϪC(25)
Pd(1)ϪN(1)
P(1)ϪC(7)
1.9619(16) Pd(1)ϪO(1)
2.0511(14) Pd(1)ϪO(2)
1.7840(16) P(1)ϪC(1)
1.7941(16) P(1)ϪC(19)
2.0390(11)
2.1265(11)
1.7930(17)
1.8129(16)
1.2876(19)
1.426(2)
P(1)ϪC(13)
C(19)ϪC(20)
C(20)ϪC(21)
C(22)ϪO(2)
1.521(2)
1.372(2)
1.240(2)
C(20)ϪO(1)
C(21)ϪC(22)
C(22)ϪO(3)
1.3376(19)
1.504(2)
O(3)ϪC(23)
1.4546(19) C(23)ϪC(24)
C(25)ϪC(26)
C(26)ϪC(27)
C(28)ϪC(29)
C(31)ϪN(1)
1.394(2)
1.396(2)
1.390(3)
1.497(2)
1.487(2)
93.73(6)
175.490(5)
90.91(4)
111.86(8)
112.50(8)
107.54(7)
C(25)ϪC(30)
C(27)ϪC(28)
C(30)ϪC(31)
N(1)ϪC(33)
1.398(2)
1.385(3)
1.498(2)
1.481(2)
˚
atoms of the Ph ring being 2.74 A. It is reasonable to as-
N(1)ϪC(32)
sume that this short intramolecular distance could explain
the strong anisotropic shielding exhibited by this proton in
C(25)ϪPd(1)ϪO(1)
O(1)ϪPd(1)ϪN(1)
O(1)ϪPd(1)ϪO(2)
C(7)ϪP(1)ϪC(1)
C(1)ϪP(1)ϪC(13)
C(1)ϪP(1)ϪC(19)
C(20)ϪC(19)ϪP(1) 111.41(11)
O(1)ϪC(20)ϪC(19) 113.40(13)
C(20)ϪC(21)ϪC(22) 124.69(15)
O(3)ϪC(22)ϪC(21) 112.75(14)
C(25)ϪPd(1) ϪN(1) 82.39(6)
C(25)ϪPd(1)ϪO(2) 174.25(6)
N(1)ϪPd(1)ϪO(2)
C(7)ϪP(1)ϪC(13)
C(7)ϪP(1)ϪC(19)
C(13)ϪP(1)ϪC(19) 106.85(7)
O(1)ϪC(20)ϪC(21) 129.57(15)
C(21)ϪC(20)ϪC(19) 117.02(14)
1
the H NMR spectrum of 2a.
93.11(5)
105.77(7)
112.28(8)
Crystal Structure of [Pd(C6F5)(SC4H8)(Ph3PCH2C(O)؍
C(H)C(؍O)OEt-κ-O,OЈ)]ClO4 (9)
A solution of 9 in CH2Cl2 was very slowly evaporated to
dryness at room temperature. During this process yellow
crystals were formed. A drawing of the cationic organomet-
allic fragment is shown in Figure 2. The parameters con-
cerning the data collection and refinement are summarized
O(2)ϪC(22)ϪO(3)
127.33(15)
metallated C6H4CH2NMe2 ligand are similar to those re- in Table 1, and selected bond lengths and angles are given
ported in related complexes and they do not show special in Table 3. The Pd atom is located in a distorted square-
features.[8] The two PdϪO bond lengths are different planar environment, surrounded by the ipso carbon atom
˚
˚
[Pd(1)ϪO(1) ϭ 2.0390(11) A; Pd(1)ϪO(2) ϭ 2.1265(11) A] C(1) of the C6F5 ligand, the S(1) atom of the tht ligand, and
probably due to two concurrent facts, namely (i) the differ- the two oxygen atoms, O(1) and O(2), of the phosphonium-
ent nature of the two oxygen atoms involved, since the enolate [Ph3PCH2C(O)ϭCHϪC(O)OEt] ligand. The struc-
C(22)ϪO(2) bond shows a higher double bond character tural arrangement confirms that the enolate oxygen O(2) is
˚
˚
[1.240(2) A] than the C(20)ϪO(1) bond [1.2876(19) A] (see trans to the sulfur atom S(1) and, hence, that the carbonylic
Scheme 2), and (ii) the different trans influences of the C- oxygen O(1) is trans to the ipso carbon atom C(1) of the
and N-donor atoms of the C6H4CH2NMe2 ligand. A com- C6F5 group, as we proposed previously. The Pd(1)ϪC(1)
˚
parison of these distances with those of related complexes bond length [1.987(5) A] is typical for C6F5 groups trans to
shows that the Pd(1)ϪO(1) bond length falls in the range O-donor ligands,[4b] and the Pd(1)ϪS(1) bond length
˚
usually reported for O,OЈ-acetylacetonate derivatives of [2.2772(17) A] also falls in the usual range of distances
PdII (range 2.007Ϫ2.073 A), while the Pd(1)ϪO(2) bond found in the literature for this type of bond.[9] The two
[9]
˚
2342
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Eur. J. Inorg. Chem. 2004, 2338Ϫ2347

Different Coordination Modes of a Polyfunctional Ylide
FULL PAPER
Crystal Structure of [AuCl{C(H)(PPh3)C(O)CH2C-
(O)OEt}] (10)
Crystals of complex 10 were grown by slow vapor dif-
fusion of Et2O into a CH2Cl2 solution of the crude complex
at room temperature. A drawing of the molecular structure
of 10 is shown in Figure 3. The parameters concerning the
data collection and refinement are presented in Table 1, and
selected bond lengths and angles are collected in Table 4.
Complex 10 crystallizes in the monoclinic space group P21/
c. Since this space group is centrosymmetric, and although
the complex is chiral, the crystal as a whole is racemic. The
structure shown in Figure 3 corresponds to an absolute
configuration (S) for the ylidic carbon Cα, following the
system of priorities of Cahn, Ingold and Prelog.[13] The
gold atom lies in a nearly linear environment, since the
bond angle C(19)ϪAu(1)ϪCl(1) is 176.48(9)°. The bond
˚
lengths Au(1)ϪC(19) [2.079(3) A] and Au(1)ϪCl(1)
˚
[2.2928(9) A] are similar to those found in the literature for
Figure 2. Thermal ellipsoid plot of the cationic fragment of 9. Non-
related structural arrangements.[14] The bond lengths
hydrogen atoms are drawn at the 50% probability level
˚
˚
C(20)ϪO(1) [1.214(4) A] and C(22)ϪO(3) [1.199(4) A] are
typical[8,9] for carbonyl groups which are not delocalized
through adjacent functional groups (e.g. the ylide function),
while the bond length C(19)ϪC(20) is identical (within ex-
˚
Table 3. Selected bond lengths (A) and angles (°) for 9
Pd(1)ϪC(1)
Pd(1)ϪS(1)
P(1)ϪC(25)
P(1)ϪC(13)
1.987(5)
2.2772(17) Pd(1)ϪO(2)
Pd(1)ϪO(1)
2.066(4)
2.028(3)
1.797(5)
1.804(5)
1.283(6)
1.453(7)
1.351(7)
1.473(9)
1.794(6)
1.799(5)
1.250(6)
1.324(6)
1.523(7)
1.414(7)
86.94(18)
91.57(14)
P(1)ϪC(19)
P(1)ϪC(7)
O(2)ϪC(8)
O(3)ϪC(11)
C(8)ϪC(9)
C(11)ϪC(12)
C(1)ϪPd(1)ϪO(1) 178.47(18)
C(1)ϪPd(1)ϪS(1)
O(1)ϪPd(1)ϪS(1)
C(25)ϪP(1)ϪC(13) 111.2(2)
C(25)ϪP(1)ϪC(7) 111.9(3)
C(13)ϪP(1)ϪC(7) 110.5(3)
C(8)ϪO(2)ϪPd(1) 122.9(3)
C(8)ϪC(7)ϪP(1)
O(2)ϪC(8)ϪC(7)
C(8)ϪC(9)ϪC(10) 125.3(5)
O(1)ϪC(10)ϪC(9) 127.1(5)
O(3)ϪC(11)ϪC(12) 108.0(5)
O(1)ϪC(10)
O(3)ϪC(10)
C(7)ϪC(8)
C(9)ϪC(10)
C(1)ϪPd(1)ϪO(2)
O(2)ϪPd(1)ϪO(1)
O(2)ϪPd(1)ϪS(1) 173.97(11)
C(25)ϪP(1)ϪC(19) 107.1(3)
C(19)ϪP(1)ϪC(13) 110.9(3)
C(19)ϪP(1)ϪC(7) 105.0(2)
C(10)ϪO(1)ϪPd(1) 123.7(3)
C(10)ϪO(3)ϪC(11) 118.4(4)
87.76(15)
93.74(11)
114.6(4)
113.6(4)
O(2)ϪC(8)ϪC(9)
C(9)ϪC(8)ϪC(7)
O(1)ϪC(10)ϪO(3) 118.9(5)
O(3)ϪC(10)ϪC(9) 114.0(5)
129.2(5)
117.1(5)
Figure 3. Thermal ellipsoid plot of 10. Non-hydrogen atoms are
drawn at the 50% probability level
˚
Table 4. Selected bond lengths (A) and angles (°) for 10
PdϪO bond lengths are different [Pd(1)ϪO(1) ϭ 2.066(4)
A and Pd(1)ϪO(2) ϭ 2.028(3) A], as we have described for
2a, reflecting the different trans influences of the trans do-
Au(1)ϪC(19)
P(1)ϪC(19)
P(1)ϪC(13)
C(19)ϪC(20)
2.079(3) Au(1)ϪC1(1)
1.780(3) P(1)ϪC(7)
1.800(3) P(1)ϪC(1)
1.487(5) C(20)ϪO(1)
1.529(4) C(21)ϪC(22)
1.199(4) C(22)ϪO(2)
1.501(6)
2.2928(9)
1.799(3)
1.801(3)
1.214(4)
1.499(5)
1.330(4)
˚
˚
nor atoms, although in 9 the differences between them are
˚
less pronounced than in 2a [2.1265(11) A and 2.0390(11) C(20)ϪC(21)
˚
C(22)ϪO(3)
C(23)ϪC(24)
A]. The internal bond lengths and angles of the phos-
phonium-enolate ligand are identical, within experimental
error, to those described for complex 2a, and thus the same
structural conclusions can be derived here. Finally, the simi-
larity between the structures of complexes 2a and 9 is also
reflected in the presence of short intramolecular P···O con-
C(19)ϪP(1)ϪC(13) 114.20(16) C(7)ϪP(1)ϪC(13) 107.48(15)
C(19)ϪP(1)ϪC(1)
C(13)ϪP(1)ϪC(1)
C(20)ϪC(19)ϪAu(1) 104.9(2)
O(1)ϪC(20)ϪC(19) 125.2(3)
C(19)ϪC(20)ϪC(21) 114.3(3)
O(3)ϪC(22)ϪC(21) 125.2(3)
O(2)ϪC(22)ϪC(21) 110.2(3)
109.98(15) C(7)ϪP(1)ϪC(1)
110.00(15) C(20)ϪC(19)ϪP(1) 115.1(2)
107.40(16)
P(1)ϪC(19)ϪAu(1) 113.53(17)
O(1)ϪC(20)ϪC(21) 120.4(3)
C(3)ϪC(22)ϪO(2) 124.5(3)
C(19)ϪAu(1)ϪCl(1) 176.48(9)
C(19)ϪP(1)ϪC(7) 107.50(16)
tacts[12] [P(1)ϪO(2) ϭ 2.950(7) A], although in this case the
˚
value of the torsion angle P(1)ϪC(7)ϪC(8)ϪO(2) (35.5°) is
clearly narrower than that reported for 2a.
Eur. J. Inorg. Chem. 2004, 2338Ϫ2347
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2343

´
M. Carbo, L. R. Falvello, R. Navarro, T. Soler, E. P. Urriolabeitia
FULL PAPER
[Ph3P؍C(H)؊C(O)؊CH2؊COOEt] (1): The ylide 1 was prepared
perimental error) to that found in other C-bonded keto-
stabilized ylides.[8a] The P(1)ϪC(19) bond length [1.780(3)
A] is slightly shorter than the other PϪC(Ph) bond lengths
[2b]
´
following the method reported by F. Serratosa and E. Sole. The
analytical and IR data were in good agreement with those pre-
viously published. Here we present the MS and NMR spectro-
scopic data for 1, which have not been reported previously. MS
˚
and, in turn, is similar to those found in other C-coordi-
nated stabilized ylides.[8a] Typical single bond σ(CϪC) dis-
1
(FABϩ): m/z (%) ϭ 391 (100) [Mϩ]. H NMR (CD2Cl2): δ ϭ 1.26
˚
tances are found for C(20)ϪC(21) [1.529(4) A] and
3
4
(t, JH,H ϭ 7.2 Hz, 3 H, CH3), 3.29 (d, JPH ϭ 1.5 Hz, 2 H, CH2),
˚
C(21)ϪC(22) [1.499(5) A]. Finally, the environments
2
3.77 (d, JPH ϭ 24.9 Hz, 1 H, PϭCH), 4.16 (q, 2 H, OCH2),
7.46Ϫ7.70 (m, 15 H, PPh3) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ
around P(1) and C(19) are tetrahedral, while those around
the carbonyl atoms C(20) and C(22) are strictly planar.
3
1
14.53 (CH3), 48.63 (d, CH2, JP,C ϭ 15.5 Hz), 52.18 (d, JP,C
ϭ
1
108.3 Hz, PϭCα), 60.81 (OCH2), 127.13 (d, JP,C ϭ 90.8 Hz, Cipso
,
PPh3), 129.28 (d, 2JP,C ϭ 12.2 Hz, Cortho, PPh3), 132.66 (d, 4 JP,C ϭ
3
2.8 Hz, Cpara, PPh3), 133.50 (d, JP,C ϭ 10.2 Hz, Cmeta, PPh3),
Conclusion
170.79 (s, COO), 184.22 (d, JP,C ϭ 2.9 Hz, CϭO) ppm. 31P{1H}
2
NMR (CD2Cl2): δ ϭ 15.50 ppm.
The
polyfunctional
ylide
[Ph3PϭC(H)C(O)CH2-
C(O)OEt] (1) shows versatile reactivity towards different
transition metals, giving very different structural motifs as
a function of the metal center. Towards cationic PdII and
PtII complexes with two available coordination sites, 1 un-
dergoes a proton transfer giving the zwitterionic phos-
phonium-enolate [Ph3(Pϩ)CH2C(OϪ)ϭCHϪC(O)OEt] li-
gand, which coordinates as an O,OЈ-chelate. The presence
of a phosphonium group, which can be easily deprotonated,
could open new pathways of reactivity towards polynuclear
complexes with a great variety of structural arrangements.
On the other hand, the reactivity of 1 towards AuI deriva-
tives gives complexes with the ylide C-bonded, leaving the
β-keto ester unit ϪC(O)CH2C(O)OEt unchanged. This fact
also opens new pathways of reactivity. This rich coordi-
nation chemistry is unprecedented for α-stabilized ylide li-
gands and the fine tuning of the reactivity allows us to sug-
gest that new and more interesting results may await dis-
covery.
Complex 2: To
a suspension of [Pd(µ-Cl)(C6H4CH2NMe2)]2
(0.0755 g, 0.137 mmol) in THF (20 mL) under argon, was added
AgClO4 (0.0567 g, 0.273 mmol). 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(solv-
ate) was treated with 1 (0.107 g, 0.273 mmol) giving a yellow solu-
tion, which was stirred for an additional 30 min. During this time,
2 precipitated as a yellow solid, which was filtered, washed with
Et2O (10 mL) and air dried. Yield: 0.100 g (50%). Complex 2 was
characterized by NMR spectroscopy as a mixture of the isomers
2a/2b in molar ratio 2a/2b ϭ 4.5:1. C33H35ClNO7PPd (730.47):
calcd. C 54.26, H 4.83, N 1.92; found C 54.26, H 4.83, N 1.93. MS
(FABϩ): m/z (%) ϭ 630 (100) [M Ϫ ClO4]ϩ. IR: ν˜ ϭ 1628 (νCOO),
1525 (νCO) cmϪ1. 1H NMR (CD2Cl2): δ ϭ 1.23 (t, JH,H ϭ 7.2 Hz,
CH3, 2a), 1.27 (t, JH,H ϭ 6.9 Hz, CH3, 2b), 2.24 (s, NMe2, 2b),
2.75 (s, NMe2, 2a), 3.76 (s, CH2N, 2b), 3.86 (s, CH2N, 2a), 4.06 (q,
OCH2, 2a), 4.13 (d, JPH ϭ 13.8 Hz, CH2P, 2a), 4.16 (d, JPH
3
3
2
2
ϭ
4
13.8 Hz, CH2P, 2b), 4.18 (q, OCH2, 2b), 4.81 (d, JPH ϭ 0.6 Hz, ϭ
3
6
5
CH, 2a), 4.86 (s, ϭCH, 2b), 5.89 (dd, JH H
ϭ
4
8.1,
4
4
3
3
JH H ϭ 0.9 Hz, H6, C6H4, 2a), 6.43 (td, JH H
ϭ JH H ϭ 8.1,
6
4
5
6
5
JH H ϭ 2.4 Hz, H5, C6H4, 2a), 6.83Ϫ7.01 [m, H3 ϩ H4 (2a) ϩ
5
3
C6H4 (2b)], 7.66Ϫ7.87 (m, PPh3, 2a ϩ 2b) ppm. 13C{1H} NMR
1
(CD2Cl2): δ ϭ 14.49 (Me, 2a ϩ 2b), 36.36 (d, JP,C ϭ 52.5 Hz,
CH2P, 2a), 36.47 (d, JP,C ϭ 54.2 Hz, CH2P, 2b), 52.36 (NMe2, 2a
Experimental Section
1
ϩ 2b), 61.26 (OCH2, 2a), 61.75 (OCH2, 2b), 73.20 (CH2N, 2a),
CAUTION: Perchlorate salts of metal complexes with organic li-
gands are potentially explosive. Only small amounts of these mate-
rials should be prepared and handled with great caution.[15]
3
73.78 (CH2N, 2b), 88.91 (d, JP,C ϭ 7.4 Hz, ϭCH, 2b), 90.43 (d,
1
3JP,C ϭ 7.0 Hz, ϭCH, 2a), 118.50 (d, JP,C ϭ 87.8 Hz, Cipso, PPh3,
1
2a), 118.88 (d, Cipso, PPh3, 2b, JP,C ϭ 88.1 Hz), 121.67 (2 C),
124.74 (2 C), 143.33 (C2), 147.53 (C1) (C6H4, 2a), 124.98 (2 C),
125.09 (2 C), 144.23 (C2), 147.75 (C1), (C6H4, 2b), 130.72 (d,
2JP,C ϭ 12.7 Hz, Cortho, 2a ϩ 2b), 134.11(Cpara, 2b), 134.34 (d,
3JP,C ϭ 10.0 Hz, Cmeta, 2a ϩ 2b), 135.64 (Cpara, 2a, PPh3), 171.21
General Methods: Solvents were dried and distilled under argon
using standard procedures. Elemental analyses were carried out
with a PerkinϪElmer 2400-B machine. Infrared spectra (4000Ϫ200
cmϪ1) were recorded with a PerkinϪElmer 883 infrared spec-
trometer from nujol mulls between polyethylene sheets. Mass spec-
tra (positive ion FAB) were recorded from CH2Cl2 solutions with
2
(CO2, 2a), 172.48 (CO2, 2b), 173.67 (d, JP,C ϭ 7.2 Hz, CO, 2a),
2
175.18 (d, JP,C ϭ 7.1 Hz, CO, 2b) ppm. 31P{1H} NMR (CD2Cl2):
a
V. G. Autospec spectrometer. 1H (300.13 MHz), 13C{1H}
δ ϭ 22.11 (2b), 22.71 (2a) ppm.
(75.47 MHz), 19F (282.40 MHz), and 31P{1H} (121.49 MHz) NMR
spectra were recorded in CDCl3 or CD2Cl2 solutions at room tem-
perature with a Bruker ARX-300 spectrometer. The 1H and
Complex 3: Complex 3 was prepared following a synthetic pro-
cedure similar to that reported for 2. Thus, [Pd(µ-Cl)(CH2C9H6N)]2
13C{1H} NMR spectra were referenced using the residual solvent (0.192 g, 0.338 mmol) reacted, in THF (20 mL), with AgClO4
signal as the internal standard, whereas the 31P{1H} NMR spectra
were referenced to external H3PO4 (85%). The 19F NMR spectra
were referenced to CFCl3. The starting compounds were prepared
(0.140 g, 0.676 mmol) and 1 (0.264 g, 0.676 mmol) to give 3 as a
yellow solid. Yield: 0.344 g (69%). C34H31ClNO7PPd (738.45):
calcd. C 55.30, H 4.23, N 1.89; found C 55.38, H 4.37, N 1.83. MS
following published methods: 1,[2b] [Pd(µ-Cl){(C6H4CH2NMe2- (FABϩ): m/z (%) ϭ 638 (100) [M Ϫ ClO4]ϩ. IR: ν˜ ϭ 1624 (νCOO),
3
(C2,N)}]2,[16] [Pd(µ-Cl){(S)-C6H4C(H)MeNMe2(C2,N)}]2,[16] [Pd(µ-
1521 (νCO) cmϪ1. 1H NMR (CD2Cl2): δ ϭ 1.31 (t, JH,H ϭ 7.2 Hz,
2
Cl){NC13H8(C8,N)}]2,[17]
[Pd(µ-Cl){CH2NC9H6(C8,N)}]2,[6,18] 3 H, CH3), 3.02 (s, 2 H, CH2Pd), 4.19 (d, JPH ϭ 13.5 Hz, 2 H,
[Pd(µ-Cl){NC5H4-2-C6H4(C2,N)}]2,[19] [Pd(µ-Cl)(tht)(C6F5)]2,[20] CH2P), 4.22 (q, 2 H, OCH2), 4.92 (s, 1 H, ϭCH), 7.40Ϫ7.52 (m, 2
[M(µ-Cl){o-CH2C6H4P(o-tol2)(C,P)}]2 (M
ϭ
Pd,[21] Pt[22]), H, C9H6N), 7.62Ϫ7.76 (m, 15 H, PPh3), 7.82Ϫ7.87 (m, 2 H,
4
4
[AuCl(tht)],[23] and [AuCl(PPh3)].[23]
C9H6N), 8.31 (dd, 3JH H ϭ 8.4, JH H ϭ 1.5 Hz, 1 H, H , C9H6N),
4
3
4
2
2344
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2338Ϫ2347

Different Coordination Modes of a Polyfunctional Ylide
FULL PAPER
3
4
8.58 (dd, JH H ϭ 5.1, JH H ϭ 1.5 Hz, 1 H, H2, C9H6N) ppm. C13H8N, 5b), 7.39 (t, 3JH,H ϭ 7.5 Hz, C13H8N, 5b), 7.47 (d, 3JH,H ϭ
2
3
2
4
13C{1H} NMR (CD2Cl2): δ ϭ 14.54 (CH3), 22.48 (CH2Pd), 37.08 7.5 Hz, C13H8N, 5a), 7.51 (d, JH,H ϭ 8.7 Hz, C13H8N, 5a), 7.55
(d, JP,C ϭ 57.6 Hz, CH2P), 61.15 (OCH2), 89.32 (d, JP,C
7.9 Hz, ϭCH), 119.34 (d, JP,C ϭ 88.4 Hz, Cipso, PPh3), 121.93,
3
1
3
ϭ
(dd, 3JH,H ϭ 7.5, 4JH,H ϭ 0.6 Hz, C13H8N, 5b), 7.85Ϫ7.63 (m, PPh3
1
3
4
ϩ C13H8N, 5a ϩ 5b), 8.16 (dd, JH,H ϭ 8.1, JH,H ϭ 1.2 Hz,
3
4
124.23, 128.65, 128.81, 129.47, 138.37, 147.85, 148.33, 153.61
C13H8N, 5a), 8.20 (dd, JH,H ϭ 8.1, JH,H ϭ 1.2 Hz, C13H8N, 5b),
2
3
4
(C9H6N), 130.52 (d, JP,C ϭ 13 Hz, Cortho), 134.25 (d, JP,C
ϭ
8.31 (dd, 3JH,H ϭ 5.1, JH,H ϭ 1.2 Hz, C13H8N, 5a) ppm. 13C{1H}
4
10.3 Hz, Cmeta), 135.38 (d, JP,C ϭ 3 Hz, Cpara) (PPh3), 171.33
NMR (CD2Cl2): δ (signals due to 5b in the low field region were
2
1
(COO), 173.44 (d, JP,C ϭ 7.2 Hz, CO) ppm. 31P{1H} NMR not observed) ϭ 14.50 (CH3, 5a ϩ 5b), 36.26 (d, JP,C ϭ 52.3 Hz
(CD2Cl2): δ ؍ 23.15 ppm.
CH2P, 5a ϩ 5b), 61.63 (OCH2, 5a), 62.12 (OCH2, 5b), 88.92 (d,
3
3JP,C ϭ 5.9 Hz, ϭCH, 5b), 91.12 (d, JP,C ϭ 6.7 Hz, ϭCH, 5a),
1
1
Complex 4: Complex 4 was prepared following a synthetic pro-
cedure similar to that reported for 2. Thus, [Pd(µ-Cl)(NC5H4-2-
C6H4)]2 (0.118 g, 0.20 mmol) reacted, in THF (20 mL), with
AgClO4 (0.083 g, 0.40 mmol) and 1 (0.156 g, 0.40 mmol) to give 4
as a yellow solid. Yield: 0.227 g (75.8%). Complex 4 was charac-
terized by NMR as a mixture of the isomers 4a/4b in molar ratio
4a/4b ϭ 3.2:1. C35H31ClNO7PPd (750.46): calcd. C 56.02, H 4.16,
N 1.87; found C 55.69, H 4.49, N 1.67. MS (FABϩ): m/z (%) ϭ
118.47 (d, JP,C ϭ 87.8 Hz, Cipso, PPh3, 5a), 118.63 (d, JP,C
ϭ
87.8 Hz, Cipso, PPh3, 5b), 121.66, 122.92, 123.65, 128.37, 128.74,
129.15, 133.44, 137.55, 141.03, 147.26, 148.43, 154.83 (C13H8N, 5a,
one of the quaternary carbon atoms was not observed), 130.76 (d,
2
3
PPh3, JP,C ϭ 12.8 Hz, Cortho), 134.40 (d, JP,C ϭ 9.4 Hz, Cmeta
,
2
PPh3), 135.63 (Cpara, PPh3), 171.51 (COO, 5a), 173.90 (d, JP,C
ϭ
6.9 Hz, CO, 5a) ppm. 31P{1H} NMR (CD2Cl2): δ ؍ 23.08 (5a),
22.74 (5b) ppm.
650 (100) [M Ϫ ClO4]ϩ. IR: ν˜ ϭ 1620 (νCOO), 1515 (νCO) cmϪ1
.
1H NMR (CD2Cl2): δ ϭ 1.28 (t, JH,H ϭ 7.2 Hz, CH3, 4a), 1.30 (t,
Complex 6: Complex 6 was prepared following a synthetic pro-
cedure similar to that reported for 2. Thus, [Pd(µ-Cl){(S)-
3
3JH,H ϭ 7.2 Hz, CH3, 4b), 4.16 (q, OCH2, 4a), 4.18 (d, JPH
ϭ
2
2
14 Hz, CH2P, 4b), 4.20 (d, JPH ϭ 16 Hz, CH2P, 4a), 4.24 (q, C6H4C(H)MeNMe2}]2 (0.105 g, 0.181 mmol) reacted, in THF
4
OCH2, 4b), 4.87 (d, JPH ϭ 1 Hz, ϭCH, 4a), 4.90 (s, ϭCH, 4b), (20 mL), with AgClO4 (0.075 g, 0.362 mmol) and 1 (0.142 g,
3
4
6.07 (dd, JH,H ϭ 7.8, JH,H ϭ 1.2 Hz, NC5H4-2-C6H4, 4a), 6.58
0.36 mmol) to give 6 as a yellow solid. Yield: 0.2627 g (97.5%).
Complex 6 was characterized by NMR spectroscopy as a mixture
3
4
(td, JH,H ϭ 7.9, JH,H ϭ 1.2 Hz, NC5H4-2-C6H4, 4a), 6.68 (td,
3JH,H ϭ 7.2, 4JH,H ϭ 1.2 Hz, NC5H4-2-C6H4, 4b), 7.01 (td, 3JH,H ϭ of the isomers 6a/6b in molar ratio 6a/6b
ϭ
4.3:1.
4
7.5, JH,H ϭ 1 Hz, NC5H4-2-C6H4, 4a), 7.16 (m, NC5H4-2-C6H4, C34H37ClNO7PPd (744.50): calcd. C 54.85, H 5.01, N 1.88;
3
4
4a), 7.33 (dd, JH,H ϭ 7.9, JH,H ϭ 1.2 Hz, NC5H4-2-C6H4, 4a), found: C 55.19, H 4.73, N 1.89. MS (FABϩ): m/z (%) ϭ 644 (65)
7.88Ϫ7.57 (m, PPh3 ϩ NC5H4-2-C6H4), 8.35 (dd, JH,H ϭ 5.7, [M Ϫ ClO4]ϩ. IR: ν˜ ϭ 1622 (νCOO), 1505 (νCO) cmϪ1
.
1H NMR
3
4JH,H ϭ 1 Hz, NC5H4-2-C6H4, 4a) ppm. The assignment of reson-
ances for the NC5H4-2-C6H4 ligand could be performed unequivo-
cally only for the major isomer 4a, due to extensive overlapping of
the signals of the minor isomer 4b with those of the major isomer
(CD2Cl2): δ ؍ 1.23 (t, JH,H ϭ 7.2 Hz, CH3, 6a), 1.26 (t, JH,H
ϭ
3
3
3
7.2 Hz, CH3, 6b), 1.35 [d, JH,H ϭ 6.9 Hz, CH(Me), 6b], 1.48 [d,
3JH,H ϭ 6.6 Hz, CH(Me), 6a], 2.03 (s, NMe2, 6b), 2.31 (s, NMe2,
6b), 2.55 (s, NMe2, 6a), 2.81 (s, NMe2, 6a), 3.86 [q, CH(Me), 6a],
4.06 (q, OCH2, 6a), 4.12Ϫ4.25 [m, OCH2 (6b) ϩ CH(Me) (6b) ϩ
and with the PPh3 group. 13C{1H} NMR (CD2Cl2): δ ϭ 14.43
1
(CH3, 4a ϩ 4b), 36.23 (d, JP,C ϭ 52.1 Hz, CH2P, 4a ϩ 4b), 61.56 CH2P (6a) ϩ CH2P (6b)], 4.83 (s, ϭCH, 6a), 4.88 (s, ϭCH, 6b),
(OCH2, 4a), 62.03 (OCH2, 4b), 89.89 (d, 3JP,C ϭ 7.3 Hz, ϭCH, 4b),
5.88 (dd, JH,H ϭ 7.5, JH,H ϭ 1.2 Hz, H6, C6H4, 6a), 6.42 (td,
3
4
3
1
91.07 (d, JP,C ϭ 6.7 Hz, ϭCH, 4a), 118.37 (d, JP,C ϭ 87.7 Hz, 3JH,H ϭ 7.5, 4JH,H ϭ 1.5 Hz, H5, C6H4, 6a), 6.77 (d, 3JH,H ϭ 7 Hz,
3
4
C
ipso, PPh3, 4a), 118.58 (d, 1JP,C ϭ 86.0 Hz, Cipso, PPh3, 4b), 119.15, C6H4, 6a), 6.90 (td, JH,H ϭ 7.5, JH,H ϭ 1.2 Hz, C6H4, 6a), 6.92
3
4
122.79, 123.49, 125.18, 129.16, 131.30, 139.57, 145.24, 148.45,
151.47, 165.51 (NC5H4-2-C6H4, 4a), 119.20, 122.58, 123.49, 125.48,
(td, JH,H ϭ 4.0, JH,H ϭ 1.2 Hz, C6H4, 6b), 6.97Ϫ7.02 (m, C6H4,
6b), 7.65Ϫ7.84 (m, PPh3, 6a ϩ 6b) ppm. 13C{1H} NMR (CD2Cl2):
δ ϭ 14.51 (CH3, 6a), 17.38 (CH3, 6b), 18.28 (CHMe), 6a), 30.53
129.41, 131.31, 139.58, 145.32, 148.41, 152.67, 165.91 (NC5H4-2-
2
C6H4, 4b), 130.76 (d, JP,C ϭ 12.4 Hz, Cortho, PPh3), 134.35 (d, (CHMe), 6b), 36.30 (d, 1JP,C ϭ 52.8 Hz, CH2P, 6a), 36.51 (d, CH2P,
3JP,C ϭ 9.1 Hz, Cmeta, PPh3), 135.69 (s, Cpara, PPh3, both isomers),
6b, JP,C ϭ 54.2 Hz), 46.12 (NMe2, 6b), 46.34 (NMe2, 6a), 51.58
1
2
171.57 (COO, 4a), 172.69 (COO, 4b), 173.89 (d, JP,C ϭ 7.3 Hz, (NMe2, 6b), 51.87 (NMe2, 6a), 61.23 (OCH2, 6a), 61.67 (OCH2,
2
3
CO, 4a), 175.23 (d, JP,C ϭ 6.6 Hz, CO, 4b) ppm. 31P{1H} NMR 6b), 75.30 [CH(Me), 6a], 75.72 [CH(Me), 6b], 88.88 (d, JP,C
ϭ
3
(CD2Cl2): δ ϭ 22.57 (4b), 22.84 (4a) ppm.
6.6 Hz, ϭCH, 6b), 90.30 (d, JP,C ϭ 6.8 Hz, ϭCH, 6a), 118.59 (d,
1
1JP,C ϭ 87.8 Hz, Cipso, PPh3, 6a), 118.94 (d, JP,C ϭ 88.1 Hz, Cipso
,
Complex 5: Complex 5 was prepared following a synthetic pro-
cedure similar to that reported for 2. Thus, [Pd(µ-Cl)(C13H8N)]2
(0.101 g, 0.158 mmol) reacted, in THF (20 mL), with AgClO4
(0.065 g, 0.32 mmol) and 1 (0.123 g, 0.316 mmol) to give 5 as a
yellow solid. Yield: 0.0622 g (25.5%). Complex 5 was characterized
by NMR as a mixture of the isomers 5a/5b in molar ratio 5a/5b ϭ
3.6:1. C37H31ClNO7PPd (774.48): calcd. C 57.38, H 4.03, N 1.81;
found C 56.90, H 4.05, N 1.79. MS (FABϩ): m/z (%) ϭ 674 (100)
PPh3, 6b), 122.16 (2 C, C6H4, 6a), 124.71 (2 C, C6H4, 6a), 122.32,
2
124.98, 125.08, 125.21 (C6H4, 6b), 130.69 (d, JP,C ϭ 11.5 Hz,
3
Cortho, PPh3, 6a ϩ 6b), 134.35 (d, JP,C ϭ 10.0 Hz, Cmeta, PPh3, 6a
ϩ 6b), 135.60 (Cpara, PPh3, 6a ϩ 6b), 143.87 (C6H4, 6a), 144.91
(C6H4, 6b), 152.77 (C6H4, 6b), 152.80 (C6H4, 6a), 171.21 (COO,
2
6a), 172.48 (COO, 6b), 173.78 (d, CO, 6a, JP,C ϭ 7.2 Hz), 175.26
2
(d, JP,C ϭ 6.9 Hz, CO, 6b) ppm. 31P{1H} NMR (CD2Cl2): δ ϭ
22.74 (6a), 22.10 (6b) ppm.
[M Ϫ ClO4]ϩ. IR: ν˜ ϭ 1616 (νCOO), 1512 (νCO) cmϪ1
.
1H NMR
3
3
(CD2Cl2): δ ϭ 1.33 (t, JH,H ϭ 7.2 Hz, CH3, 5a), 1.35 (t, JH,H
ϭ
Complex 7: Complex 7 was prepared following a synthetic pro-
2
6.3 Hz, CH3, 5b), 4.21 (q, OCH2, 5a), 4.21 (d, JPH ϭ 13.8 Hz, cedure similar to that reported for 2. Thus, [Pt(µ-Cl){o-
CH2P, 5b), 4.28 (d, 2JPH ϭ 13.8 Hz, CH2P, 5a), 4.30 (q, OCH2, 5b),
CH2C6H4P(o-tol)2}]2 (0.135 g, 0.126 mmol) reacted, in THF
4.93 (s, ϭCH, 5b), 4.94 (s, ϭCH, 5a), 6.05 (dd, 3JH,H ϭ 7.5, 4JH,H ϭ (20 mL), with AgClO4 (0.052 g, 0.25 mmol) and
1 (0.103 g,
3
0.6 Hz, C13H8N, 5a), 6.94 (t, JH,H ϭ 7.5 Hz, C13H8N, 5a), 6.97 0.264 mmol) to give 7 as a pale yellow solid. Yield: 0.222 g (88.6%).
(dd, JH,H ϭ 8.1, JH,H ϭ 5.1 Hz, C13H8N, 5b), 7.18 (dd, JH,H
5.1, JH,H ϭ 1.2 Hz, C13H8N, 5b), 7.30 (dd, JH,H ϭ 8.1, JH,H
3
3
3
ϭ
C45H43ClO7P2Pt (988.32): calcd. C 54.69, H 4.38; found C 54.52,
4
3
3
ϭ
H 4.08. MS (FABϩ): m/z (%) ϭ 888 (45) [M Ϫ ClO4]ϩ. IR: ν˜ ϭ
3
4
5.1 Hz, C13H8N, 5a), 7.30 (dd, JH,H ϭ 6.0, JH,H ϭ 0.9 Hz, 1614 (νCOO), 1520 (νCO) cmϪ1 1H NMR (CD2Cl2): δ ϭ 1.18 (t,
.
Eur. J. Inorg. Chem. 2004, 2338Ϫ2347
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2345

´
M. Carbo, L. R. Falvello, R. Navarro, T. Soler, E. P. Urriolabeitia
FULL PAPER
3JH,H ϭ 7.2 Hz, 3 H, CH3), 2.40 (s, 3 H, Me tolyl), 2.64 (s, 3 H,
Complex 10: To a solution of 1 (0.110 g, 0.281 mmol) in CH2Cl2
Me tolyl), 2.98 (s broad, 2 H, CH2Pt), 3.61 (q, 2 H, OCH2), 4.27 (15 mL) was added [AuCl(tht)] (0.090 g, 0.28 mmol) at room tem-
2
(d, JPH ϭ 13.5 Hz, 2 H, CH2P), 5.08 (s, 1 H, ϭCH), 6.78Ϫ7.74 perature, and the resultant solution was stirred for 30 min. The
(m, 27 H, PPh3 ϩ C6H4) ppm. 13C{1H} NMR (CDCl3): δ ؍ 7.77
solvent was then evaporated to dryness and the white residue
(PtCH2), 13.98 (CH3), 22.19 (CH3 tolyl), 30.31 (CH3 tolyl), 36.21 treated with Et2O (30 mL), giving 10 as a white solid, which was
1
4
(dd, JP,C ϭ 55.4, JP,C ϭ 5.9 Hz, CH2P), 60.97 (OCH2), 90.41 (d, filtered, washed with additional Et2O (10 mL) and air dried. Yield:
1
3JP,C ϭ 7.5 Hz, ϭCH), 118.86 (d, JP,C ϭ 88.02 Hz, Cipso, PPh3),
0.170 g (96.9%). C24H23AuClO3P (622.84): calcd. C 46.28, H 3.72;
125.66 (d, JP,C ϭ 9.1 Hz, C6H4, tolyl), 127.09 (d, JP,C ϭ 15.9 Hz, found C 46.21, H 3.71. MS (FABϩ): m/z (%) ϭ 623 (9) [M ϩ H]ϩ,
2
C6H4, tolyl), 130.07 (d, JP,C
ϭ
13.0 Hz, Cortho
,
PPh3),
587 (15) [M Ϫ Cl]ϩ. IR: ν˜ ϭ 1731 (νCOO), 1666 (νCO) cmϪ1
.
1H
3
3
130.40Ϫ132.62 (m, C6H4, tolyl), 133.90 (d, JP,C ϭ 10.3 Hz, Cmeta
,
,
NMR (CD2Cl2): δ ϭ 1.24 (t, JH,H ϭ 7.2 Hz, 3 H, CH3), 3.48 (dd,
PPh3), 134.61 (C1, C6H4, tolyl), 134.80 (d, JP,C ϭ 2.5 Hz, Cpara
2JH,H ϭ 15.3, JPH ϭ 2.7 Hz, 1 H, CH2), 3.93 (dd, JH,H ϭ 15.3,
4
4
2
PPh3), 158.51 (d, JP,C ϭ 24.7 Hz, C2, C6H4, tolyl), 169.26 (s, 4JPH ϭ 1.5 Hz, 1 H, CH2), 4.15 (q, 2 H, OCH2), 4.73 (s, 1 H,
2
COO), 172.22 (d, JP,C ϭ 7.3 Hz, CO) ppm. 31P{1H} NMR AuCHP), 7.53Ϫ7.83 (m, 15 H, PPh3) ppm. 13C{1H} NMR
2
(CDCl3): δ ϭ 23.27 (s, PPh3), 10.72 [s, JPt,P ϭ 4739 Hz, Pt(C∧P)]
(CD2Cl2): δ ؍ 14.34 (CH3), 38.08 (d, JP,C ϭ 55.7 Hz, AuCHP),
1
1
3
1
ppm.
49.17 (d, JP,C ϭ 10.3 Hz, CH2), 61.82 (OCH2), 123.89 (d, JP,C ϭ
2
88.17 Hz, Cipso, PPh3), 129.84 (d, JP,C ϭ 12.5 Hz, Cortho, PPh3),
4
3
134.07 (d, JP,C ϭ 2.7 Hz, Cpara), 134.24 (d, JP,C ϭ 10 Hz, Cmeta),
196.28 (d, 2JP,C ϭ 4.5 Hz, CO) ppm. 31P{1H} NMR (CD2Cl2): δ ؍
24.84 ppm.
Complex 8: Complex 8 was prepared following a synthetic pro-
cedure similar to that reported for (2). Thus, [Pd(µ-Cl){o-
CH2C6H4P(o-tol)2}]2 (0.129 g, 0.145 mmol) reacted, in THF
(20 mL), with AgClO4 (0.060 g, 0.29 mmol) and
1 (0.113 g,
Complex 11: To a solution of [Au(Cl)PPh3] (0.104 g, 0.210 mmol) in
acetone (30 mL), was added AgClO4 (0.0436 g, 0.210 mmol). The
resultant suspension was stirred in the dark for 30 min at room
temperature and then filtered through a Celite pad. To the freshly
prepared solution of [Au(OCMe2)PPh3]ClO4 (0.210 mmol) was ad-
ded the ylide 1 (0.0821 g, 0.210 mmol), and the resultant solution
stirred for 15 min. The solvent was evaporated to dryness, and the
oily residue treated with Et2O (25 mL), giving complex 11 as a
white solid. Yield: 0.131 g (65.6%). C42H38AuClO7P2 (949.13):
calcd. C 53.15, H 4.04; found C 53.28, H 4.15. MS (FABϩ): m/z
0.290 mmol) to give 8 as a pale yellow solid. Yield: 0.190 g (72.8%).
C45H43ClO7P2Pd (899.63): calcd. C 60.08, H 4.82; found C 60.25,
H 4.46. MS (FABϩ): m/z (%) ϭ 799 (100) [M Ϫ ClO4]ϩ. IR: ν˜ ϭ
1619 (νCOO), 1512 (νCO) cmϪ1 1H NMR (CD2Cl2): δ ؍ 1.18 (t,
.
3JH,H ϭ 6.9 Hz, 3 H, CH3), 2.40 (s, 3 H, CH3 tolyl), 2.52 (d,
2JH,H ϭ 11.0 Hz, 1 H, CH2Pd), 2.63 (s, 3 H, CH3 tolyl), 2.91 (d, 1
2
H, CH2Pd), 3.56 (q, 2 H, OCH2), 4.24 (d, JPH ϭ 13.2 Hz, 2 H,
CH2P), 4.92 (s, 1 H, ϭCH), 6.67Ϫ7.74 (m, 27 H, C6H4 ϩ PPh3)
ppm. 13C{1H} NMR (CDCl3): δ ϭ 14.34 (CH3), 22.73 (d, JP,C
ϭ
3
(%) ϭ 849 (15) [M Ϫ ClO4]ϩ. IR: ν˜ ϭ 1724 (νCOO), 1657 (νCO
)
9.8 Hz, CH3 tolyl), 28.72 (PdCH2), 30.51 (CH3 tolyl), 37.53 (dd,
1JP,C ϭ 56, 4JP,C ϭ 5.1 Hz, CH2P), 60.72 (OCH2), 88.68 (d, 3JP,C ϭ
cmϪ1. 1H NMR (CD2Cl2): δ ؍ 1.18 (t, 3JH,H ϭ 7.2 Hz, 3 H, CH3),
1
3.65 (dd, 2JH,H ϭ 15.3, 4JPH ϭ 2.4 Hz, 1 H, CH2), 3.93 (dd, 2JH,H ϭ
7.1 Hz, ϭCH), 119.45 (d, JP,C ϭ 88.2 Hz, Cipso, PPh3), 125.83
4
(C6H4, tolyl), 126.58 (d, JP,C ϭ 8.2 Hz, C6H4, tolyl), 127.51 (d,
JP,C ϭ 10.5 Hz, C6H4, tolyl), 127.88 (C6H4, tolyl), 130.47 (d,
2JP,C ϭ 12.8 Hz, Cortho, PPh3), 131.43Ϫ133.66 (m, C6H4, tolyl),
15.3, JPH ϭ 1.8 Hz, 1 H, CH2), 4.10 (q, 2 H, OCH2), 4.83 (d,
2JPH ϭ 9 Hz, 1 H, AuCHP), 7.18Ϫ7.76 (m, 30 H, PPh3) ppm.
3
13C{1H} NMR (CDCl3): δ ؍ 14.09 (CH3), 49.33 (d, JP,C
ϭ
3
1
2
134.28 (d, JP,C ϭ 9.9 Hz, Cmeta, PPh3), 135.35 (s, Cpara, PPh3),
10.4 Hz, CH2), 50.83 (dd, JP,C ϭ 58.6, JP,C ϭ 54.6 Hz, AuCHP),
2
1
142.44 (d, JP,C ϭ 13.0 Hz, C2, C6H4, tolyl), 156.82 (d, JP,C
ϭ
61.35 (OCH2), 123.02 (d, 1JP,C ϭ 88.6 Hz, Cipso, CPPh3), 127.90 (d,
29.1 Hz, C1, C6H4, tolyl), 171.26 (s, COO), 173.78 (d, JP,C
ϭ
2
1JP,C ϭ 58.6 Hz, Cipso, AuPPh3), 129.55 (d, JP,C ϭ 11.8 Hz, Cortho
,
2
7.1 Hz, CO) ppm. 31P{1H} NMR (CD2Cl2): δ ϭ 34.83 [s, Pd(C∧P)],
2
CPPh3), 129.78 (d, JP,C ϭ 12.7 Hz, Cortho, AuPPh3), 132.27 (d,
4JP,C ϭ 2.2 Hz, Cpara, AuPPh3), 133.64 (d, JP,C ϭ 10.1 Hz, Cmeta
,
,
3
23.43 (s, PPh3) ppm.
3
AuPPh3), 133.83 (d, JP,C ϭ 9.6 Hz, Cmeta, CPPh3), 134.01 (Cpara
CPPh3), 167.94 (COO), 196.69 (t, 2JP,C ഠ 3JP,C ϭ 4.9 Hz, CO) ppm.
Complex 9: Complex 9 was prepared following a synthetic pro-
cedure similar to that reported for 2. Thus, [Pd(µ-Cl)(C6F5)(tht)]2
(0.1164 g, 0.146 mmol) reacted, in THF (20 mL), with AgClO4
(0.061 g, 0.29 mmol) and 1 (0.115 g, 0.292 mmol) to give 9 as a
deep yellow solid. Yield: 0.189 g (75.7%). C34H31ClF5O7PPdS
31P{1H} NMR (CD2Cl2): δ ؍ 39.89 (d, JP,P ϭ 11.2 Hz, AuPPh3),
3
26.15 (d, CHPPh3) ppm.
Crystallography
(851.50): calcd. C 47.96, H 3.67; found C 47.89, H 3.36. MS Data Collection: Crystals of complexes 2a and 9 of adequate qual-
(FABϩ): m/z (%) ϭ 752 (47) [M Ϫ ClO4]ϩ. IR: ν˜ ϭ 1603 (νCOO),
ity for X-ray purposes were obtained by slow evaporation of solu-
1
1502 (νCO), 1283 (tht), 959, 798 (C6F5) cmϪ1. H NMR (CD2Cl2): tions of either the crude mixture of complexes 2a/2b, or the crude
δ ϭ 1.26 (t, 3JH,H ϭ 7.2 Hz, 3 H, CH3), 2.06 (s, 4 H, Hβ, tht), 2.64 complex 9 in CH2Cl2. In contrast, crystals of 10 were grown by
3
(s, 2 H, Hα, tht), 3.12 (s, 2 H, Hα, tht), 4.07 (q, JH,H ϭ 7.2 Hz, 2 slow vapor diffusion of Et2O into a CH2Cl2 solution of the crude
H, OCH2), 4.23 (d, 2JPH ϭ 13.5 Hz, 2 H, ϪCH2P), 5.07 (s, 1 H, ϭ
complex at room temperature. A crystal of dimensions 0.36 ϫ 0.34
CH), 7.43Ϫ7.81 (m, 15 H, PPh3) ppm. 13C{1H} NMR (CD2Cl2): ϫ 0.22 mm (2a), 0.39 ϫ 0.25 ϫ 0.043 mm (9) or 0.49 ϫ 0.30 ϫ
1
δ ϭ 14.40 (CH3), 30.39 (Cβ, SC4H8), 35.49 (d, JP,C ϭ 57.2 Hz, 0.19 mm (10) was mounted onto a quartz fiber in a random orien-
3
CH2P), 37.01 (Cα, SC4H8), 62.20 (OCH2), 89.39 (d, JP,C
ϭ
tation and covered with epoxy. Data collection was performed at
1
8.1 Hz, ϭCH), 118.88 (d, JP,C ϭ 88.7 Hz, Cipso, PPh3), 130.33 (d, 100 K (2a, 10) or at room temperature (9) with a Bruker Smart
2JP,C ϭ 12.7 Hz, Cortho, PPh3), 133.80 (d, JP,C ϭ 10.0 Hz, Cmeta
,
Apex CCD diffractometer using graphite-monochromated Mo-Kα
3
˚
PPh3), 135.21 (Cpara, PPh3), 137.13 (m, C6F5), 140.12 (m, C6F5),
radiation (λ ϭ 0.71073 A). In all cases, a hemisphere of data was
4
146.29 (m, C6F5), 149.36 (m, C6F5), 171.84 (d, JP,C ϭ 1.3 Hz,
collected based on three ω-scan runs. For each of these runs, frames
2
COO), 174.26 (d, JP,C ϭ 7.1 Hz, CO) ppm. 19F NMR (CD2Cl2): (606, 435, and 230, respectively) were collected at 0.3° intervals and
3
3
δ ϭ Ϫ120.89 (d, JF,F ϭ 22 Hz, 2 F, Fortho), Ϫ159.33 (t, JF,F
22 Hz, 1 F, Fpara), Ϫ162.41 (t, 2 F, Fmeta) ppm. 31P{1H} NMR using the program SAINT[24] and the integrated intensities were
(CD2Cl2): δ ϭ 22.61 ppm.
corrected for systematic errors with SADABS.[25]
ϭ
10 s per frame. In all cases, the diffraction frames were integrated
2346
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2338Ϫ2347

Different Coordination Modes of a Polyfunctional Ylide
FULL PAPER
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cated in a local slant Ϫ Fourier calculation and then refined as
riding atoms with the torsion angles about the OϪC(methyl) or
NϪC(methyl) bonds treated as variables. Each hydrogen atom was
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3
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retrieving.html [or from the Cambridge Crystallographic Data
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Funding by the Direccion General de Investigacion Cientıfica y
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BQU2002Ϫ00554) is gratefully acknowledged. T. S. thanks the
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Early View Article
Published Online April 7, 2004
[4] [4a]
´
´
J. Fornies, F. Martınez, R. Navarro, E. P. Urriolabeitia, J.
Eur. J. Inorg. Chem. 2004, 2338Ϫ2347
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2347