P,N-Heterodifunctional ligands by selective Staüdinger reaction of β-substituted vinylazides with (Z)-1,2-bis(diphenylphosphanyl)ethene and formation of cyclometalled complexes of palladium(II) of these ligands - crystal and molecular structure of a new chiral cyclometallaphosphoraniminophosphane of palladium(II)

Article abstract of DOI:10.1016/S0022-328X(99)00731-7

Staüdinger reactions of the β-aryl-, heteroaryl- and ferrocenylvinylazides (2) with (Z)-1,2-bis(diphenylphosphanyl)ethene afford the P,N-ligands (3) in good yields. Reaction of 3 with dichlorobis(benzonitrile)palladium(II) leads to the Pd(II) metallacycle derivatives 5. The molecular structure of 5e has been determined by X-ray crystallography. The electrochemical behavior of this compound is also reported.

Full text of DOI:10.1016/S0022-328X(99)00731-7

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 598 (2000) 329–338
P,N-Heterodifunctional ligands by selective Stau¨dinger reaction of
b-substituted vinylazides with (Z)-1,2-bis(diphenylphosphanyl)-
ethene and formation of cyclometalled complexes of palladium(II)
of these ligands — crystal and molecular structure of a new chiral
cyclometallaphosphoraniminophosphane of palladium(II)
Antonio Arques* a,1, Pedro Molina* a,2, David Aun˜o´n a, Mar´ıa Jesu´s Vilaplana a,
M. Desamparados Velasco a, Francisco Mart´ınez b, Delia Bautista c,
Fernando J. Lahoz d
a Departamento de Qu´ımica Orga´nica, Facultad de Qu´ımica, Uni6ersidad de Murcia, Campus de Espinardo, E-30071 Murcia, Spain
b Departamento de Qu´ımica F´ısica, Facultad de Qu´ımica, Uni6ersidad de Murcia, Campus de Espinardo, E-30071 Murcia, Spain
c Ser6icio de Apoyo a las Ciencias Experimentales (SACE), Uni6ersidad de Murcia, Campus de Espinardo, E-30071 Murcia, Spain
d Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de los Materiales de Arago´n, Facultad de Ciencias, Uni6ersidad de Zaragoza,
E-50009 Zaragoza, Spain
Received 20 September 1999; accepted 24 November 1999
Abstract
Stau¨dinger reactions of the b-aryl-, heteroaryl- and ferrocenylvinylazides (2) with (Z)-1,2-bis(diphenylphosphanyl)ethene afford
the P,N-ligands (3) in good yields. Reaction of 3 with dichlorobis(benzonitrile)palladium(II) leads to the Pd(II) metallacycle
derivatives 5. The molecular structure of 5e has been determined by X-ray crystallography. The electrochemical behavior of this
compound is also reported. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: b-Arylvinyl azides; b-Ferrocenylvinylazide; (Z)-1,2-bis(Diphenylphosphanyl)ethene; P,N-Difunctional ligands; Cyclometalled com-
plexes; Palladium; X-ray structure analysis
1. Introduction
means of the Stau¨dinger imination [4] of trivalent phos-
phorus compounds with azides to produce an
iminophosphorane function after nitrogen evolution.
This method, which allows the selective oxidation of
diphosphanes using the b-ferrocenylvinyl azide [5], is
also applicable to diphosphanes of various chain
lengths, and even to tri- and tetraphosphanes. The
resulting asymmetrically substituted (iminophospho-
rane)phosphane ligands are good complexing agents,
utilizing the phosphane and iminophosphorane nitro-
gen centers, and the Pd(II) complex derived from the
1,2-bis(diphenylphosphanyl)methane catalyzed aryl am-
ination reactions [3a]. In this context, it has been de-
scribed [6] the selective azide mono-oxidation of the
(Z)-1,2-bis(diphenylphosphanyl)ethene using aryl, ben-
zyl and heterosubstituted azides. It has been postulated
that the failure to induce reaction at the second phos-
The design of difunctional ligands which can form
heterodinuclear transition-metal complexes, with well-
defined geometries, is of considerable interest consider-
ing the rapidly evolving area of bimetallic catalysis [1].
In this context, heterodifunctional ligands that incorpo-
rate both a trivalent phosphorus atom and a ferrocene
moiety have proven to be suitable for the construction
of heterobimetallic systems with well-defined geometry,
in which the two metals remain sufficiently close to
allow a multisite activation of organic substrates [2].
We have recently reported [3] an efficient preparation
of P,N-heterodifunctional ferrocene-based ligands by
1 *Corresponding author. E-mail: arques@fcu.um.es
2 *Corresponding author. E-mail: pmolina@fcu.um.es
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00731-7

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A. Arques et al. / Journal of Organometallic Chemistry 598 (2000) 329–338
phane center is a direct result of steric crowding created
by the rigid Z configuration of the phosphorus centers,
which inhibits the formation of the intermediate
phosphazide.
showed change only slightly for the P(III) atom (+2
ppm) compared with the much larger chemical shift
change experienced by the P(V) center (−26.5 ppm).
3
The JPP coupling constants in 3e and 4 are similar in
We now wish to report the preparation of P,N-het-
erodifunctional ligands derived from (Z)-1,2-bis-
(diphenylphosphanyl)ethene and b-aryl-, heteroaryl-
and ferrocenylvinylazides and subsequent formation of
Pd(II)-metallacycle derivatives.
magnitude, with the trans coupling in 4 being slightly
longer (by approximately 7 Hz) than in the cis.
With the new ligands 3 in hand, we investigated their
suitability for complexation to transition metals. Repre-
sentative palladium complexes were prepared by reac-
tion of 3 with dichlorobis(benzonitrile)palladium(II) in
dichloromethane at room temperature to form the cor-
responding complexes 5 in yields higher than 60%
(Scheme 2). In this reaction the iminophosphorane unit
acts as an N-donating side arm with a pendent ferro-
cenylvinyl group arm. Compounds 5 show a limited
solubility in polar solvent and are insoluble in nonpolar
solvent, but 5e was readily recrystallized from chloro-
form. The best method for the isolation of pure samples
of 5 was simply to use precise stoichiometry with
careful control of reaction conditions and, upon com-
pletion of the reaction, to remove the solvent under
reduced pressure. This method produced an amorphous
powder of 5 of sufficient purity for subsequent struc-
tural characterization. Analytical samples were purified
by column chromatography using the appropriate
eluent.
2. Results and discussion
Reaction of (Z)-1,2-bis(diphenylphosphanyl)ethene
(1) with b-(4-methylphenyl)vinyl azide [7] 2a (1:1 molar
ratio) in dry dichloromethane at room temperature
provides the monoiminophosphorane 3a in 94% yield.
The reaction of 1 with several others vinylazides [5,7,8]
2b–2g also proceeded smoothly in a similar straightfor-
ward fashion to give the corresponding iminophospho-
ranes 3b–3g in yields ranging from 55 to 85% after
purification by column chromatography (Scheme 1).
1
The H- and 13C{1H}-NMR data of compounds 3a–3d
and 3f–3g are in good agreement with the proposed
structures. The 31P{1H}-NMR spectrum of 3 features
two doublets in the regions l −5.75 to −0.1 and l
−25.49 to −23.14 (3JPP=11.8–13.2 Hz) attributable
to the pentavalent and trivalent phosphorus atoms,
respectively. Comparison of the 31P{1H}-NMR spectra
of 3e and the isomeric monoiminophosphorane [3b] 4
Evidence for the stability of the ligands 3 and their
complexes 5 comes from their lack of the aza Wittig
reaction with isocyanates up to reflux temperature in
dichloromethane even for an extended reaction time.
Scheme 1.

A. Arques et al. / Journal of Organometallic Chemistry 598 (2000) 329–338
331
Scheme 2.
This fact is in contrast to the observed behavior of the
iminophosphoranes derived from azides and
ligand 3e, only three resonances were observed for the
substituted Cp ring (l 83.25 (q), 69.7 and 67.87) and
only one resonance for the unsubstituted Cp ring (l
68.9). In contrast, the complex 5e clearly showed five
separated resonances for the substituted Cp ring (l
78.29 (q), 71.62, 70.52, 70.33 and 69.44) and one reso-
nance for the unsubstituted Cp ring (l 68.92). This
structural information suggested that the complex 5e
might exist as atropoisomers due to the restricted rota-
tion about the C–N bond.
The fact that the anisochrony of the methylene pro-
tons in the aromatic analogs 5a–5d and heteroaromatic
5f–5g was not observed could be due to the ferrocene
subunit, which sterically represents a quite bulky group
with unique spatial requirements due to its cylindrical
geometry and its fixed interannular spacing. In retro-
spect, the typical cone volume of the ferrocenyl unit is
2
triphenylphosphane, which led to the expected carbodi-
imides by reaction with isocyanates [7] under the same
reaction conditions. We think that the failure to induce
the aza Wittig reaction, which needs the initial forma-
tion of a cyclic intermediate, could be due either to the
steric crowding created by the cis configuration of the
diphenylphosphino group, which inhibits the reaction
mechanism, or to the conjugation of the nitrogen lone
pair with the CꢀC double bond of the phosphine
backbone.
It is well known that coordination of a P,N-ligand to
palladium causes shifts of the 31P resonance of the
complex ligand to higher frequency [9]. The magnitude
of the coordination chemical shift (Dl 31P coordinated–
l 31P free ligand) in complexes 5a–5d and 5f–5g for the
P(III) (DP(III)=29.0–32.5) is higher than for the P(V)
(DP(V)=13.2–18.6). However, in the complex 5e these
values for the two phosphorus atoms (DP(III)=25.7
and DP(V)=21.5) are quite close. An interesting fea-
,
about 17 A [10]. The pendent ferrocenylvinyl arm is not
chiral, but is prochiral in the sense that chirality is
produced upon coordination and adoption of a particu-
lar conformation.
3
ture of complexes 5 is the variability of the JPP cou-
pling constant, which increases significantly from
11.8–13.2 to 37.7–51.7 Hz upon complexation to palla-
dium, the smallest observed value in the complex 5e
being from 13.2 to 37.0 Hz.
3. Crystal structure of the complex 5e
In order to get a better knowledge of the relative
spatial distribution of the different groups conforming
the 5e molecule, a single crystal X-ray analysis was
carried out (Fig. 1). This analysis revealed the confor-
mation of the six-membered heteroatom ring and the
effect of coordination upon the iminophosphorane
bond. Compound 5e crystallizes in a centrosymmetric
space group with the palladium atom exhibiting a
slightly distorted square-planar coordination. The metal
environment is formed by the P,N-chelate iminophos-
phorane ligand and two cis-disposed chloride atoms.
Distortions from ideal square-planar metal coordina-
tion concern fundamentally the cis-angles (range
84.35(3)–95.80(8)°) and minor deviations out of the
calculated least-square plane (maximum deviation for
1
The H-, 13C{1H}-NMR and MS in FAB mode of
the complexes 5a–5d and 5f–5g are in accord with the
proposed structure. However, a rather astonishing as-
1
pect of the H-NMR spectrum of the heterobimetallic
complex 5e was the appearance of the OꢁCH2ꢁCH3
protons as an ABX3 system (JAX=JBX=7.0 Hz, JAB
=
−9.8 Hz), the diastereotopicity and anisochrony of the
methylene protons reflecting the chiral nature of com-
pound 5e (racemic). This spectrum also showed two
broad singlets for two protons of the substituted Cp
ring, whereas the signals for the two remaining protons
are overlapped with the signal corresponding to the
unsubstituted Cp rings. The olefinic resonances of the
bridging ethylene backbone are apparently embedded
in the broad aromatic region and hence cannot be seen.
Further evidence for the ordered conformation in 5e
was obtained from the 13C{1H}-NMR data for the Cp
carbon atoms. In the 13C{1H}-NMR spectrum of the
,
P(1), 0.032(1) A).
The two PdꢁCl bond distances are significantly dif-
ferent, 2.3615(9) and 2.3016(8), but both are within the
usual range of terminal PdꢁCl bond separations (mean

332
A. Arques et al. / Journal of Organometallic Chemistry 598 (2000) 329–338
,
Cremer and Pople parameters (Q=0.643(2) A, ƒ2=
69.2(2)°, q2=59.5(2)°) [12] characterize this het-
eroatomic ring, PdꢁNꢁP(2)ꢁC(13)ꢁC(14)ꢁP(1), as
having an envelope conformation E2 — with the nitro-
gen out-of-plane — slightly distorted toward a half-
chair conformation [13].
Another interesting feature determined by the struc-
tural analysis concerns the modifications of the
iminophosphorane ligand upon coordination to the
metal. Thus, the P(2)ꢁNꢁC(12) bond angle has been
seriously reduced from 131.6(2)° in a related free ligand
[3b] to a value of 121.0(2)° in 5e. Additionally, both
P(2)ꢁN and NꢁC(12) bonds have been lengthened from
,
,
1.566(2) and 1.384(3) A to 1.605(3) and 1.426(4) A,
respectively. These data compare well with those ob-
served in related iminophosphorane metal complexes
[14] and support that coordination of iminophospho-
rane to the metal significantly reduces the double-bond
character of the PꢁN bond [6,15]. The directional dona-
tion of the lone pair of the sp2 nitrogen atom upon
formation of complex 5e restores the trigonal planar
geometry at the nitrogen. The PdꢁP bond length
Fig. 1. ORTEP plot of compound 5e. 50% probability ellipsoids.
,
Selected bond lengths (A) and angles (°): PdꢁN 2.077(2), PdꢁP(1)
2.2287(9), PdꢁCl(2) 2.3016(8), PdꢁCl(1) 2.3615(9), P(1)ꢁC(14),
1.804(3), C(14)ꢁC(13) 1.326(4), C(13)ꢁP(2) 1.800(3), P(2)ꢁN 1.605(3),
Nꢁ(12) 1.426(4) NꢁPdꢁP(1) 95.80(8), NꢁPdꢁCl(1) 90.33(8),
Cl(1)ꢁPdꢁCl(2) 89.56(3), Cl(2)ꢁPdꢁP(1) 84.35(3), PdꢁP(1)ꢁC(14)
114.35(11), P(1)ꢁC(14)ꢁC(13) 125.4(3), C(14)ꢁC(13)ꢁP(2) 128.2(3),
C(13)ꢁP(2)ꢁN 107.7(2), P(2)ꢁNꢁPd 115.00(14), P(2)ꢁNꢁC(12)
121.0(2).
,
2.2287(9) is shorter than the single bond 2.41 A, sug-
gesting a p-bonding interaction [16], which is similar to
the other found earlier [17].
,
value 2.321(6) A) [11]. They clearly reflect the different
trans-influences of the iminophosphorane donor atoms:
the longest PdꢁCl(1) distance is located trans to the
stronger p-acceptor P(1), meanwhile the shorter one,
PdꢁCl(2), is opposite to the imino nitrogen atom. The
dihedral angle between the main plane of the
PdꢁNꢁP(2)ꢁC(13)ꢁC(14)ꢁP(1) and the palladium coor-
dination plane is 20.65(2)°.
Considering the best idealized coordinating plane of
the palladium, it is instructive to analyze the position of
the different parts of the molecule with respect to this
plane (Fig. 2). Observing that (a) the ferrocene subunit
lies below this plane and (b) completing the ring by
joining the phosphorus and nitrogen atoms with the
palladium atom, one arrives at a propeller-type position
of the four P-phenyl groups, two pseudoaxial and two
pseudoequatorial. The pseudoaxial PhꢁP(1) and pseu-
doequatorial PhꢁP(2) are edge-on exposed, whereas the
pseudoequatorial PhꢁP(1) and pseudoaxial PhꢁP(2) are
face-on exposed [18]. (c) The structure 5e presents a
chiral axis, the helical sense of which is maintained
through hindered rotation around the NꢁC(12) single
bond. Thus, anti-clockwise rotation around this bond is
hindered by the chlorine atom that lies on the
PdꢁNꢁP(2) plane, whereas clockwise rotation is hin-
dered by the pseudoequatorial PhꢁP(2).
The analysis of the molecular structure of 5e has also
shown the puckering of the six-membered metallacycle.
4. Electrochemistry
Compounds 3e and 5e were further characterized by
cyclic voltammetry. All potentials are referenced to the
SCE. E1/2=(Epa+Epc)/2 for reversible electron transfer
processes and oxidation peak potentials (Epa) for irre-
versible processes are given.
The complex 5e exhibits an uncomplicated reversible
electron-transfer pattern involving the ferrocenyl sub-
unit. The cyclic voltammogram of 5e in dimethylfor-
Fig. 2. View of 5e along the coordination plane showing the confor-
mation of the metallacycle as well as the disposition of the substituent
on the ring, with hydrogen atoms and ethoxycarbonyl group omitted
for clarity.
mamide solution displayed
a
simple reversible

A. Arques et al. / Journal of Organometallic Chemistry 598 (2000) 329–338
333
Fig. 3. Cyclic voltammograms of: (a) 5e in DMF solution; (b) 3e in DMF solution; (c) 3d in DMF solution, (d) 3e in acetonitrile solution.
Experimental conditions: 1×10−3 M, Pt disk working electrode, SCE reference electrode, 0.1 M [n-Bu4N][ClO4], scan rate: 200 mV s−1
.
one-electron transfer process at E1/2=0.517 V versus
SCE, (DEp=116 mV) less anodic than that displayed
by the free ligand 3e, Epa=0.782 V versus SCE. No
peaks corresponding to the oxidation process of the
Pd(II)/Pd(III) couple were observed [19] (Fig. 3(a)). It
has been reported [20] that in heterobimetallic fer-
rocene–palladium complexes the potential of the
Fe(II)/Fe(III) couple is shifted to a high-potential re-
respect to the free ligand 3e (Epa=0.782 V), we con-
clude that there is only, if any, bonding interaction
between the Fe and Pd atoms in complex 5e.
In striking contrast with the electrochemical behavior
observed in the complex 5e, the redox pattern for the
free ligand 3e is much more complicated under identical
experimental conditions. The cyclic voltammogram of
3e shows two oxidation peaks at 0.337 and 0.780 V
versus SCE at a scan rate of 200 mV s−1 and a very
low response in the cathodic scan (Fig. 3(b)). Taking
into account that in the cyclic voltammogram of the
aromatic analog 3d (Fig. 3(c)), in which the ferrocene
group has been replaced by an aromatic ring, only an
oxidation peak at 0.610 V appears due to the irre-
gion. This fact is probably due to
a
dative
ironꢁpalladium bond, which decreases the electron den-
sity on the iron atom. As the potential oxidation value
in the complex 5e (E1/2=0.517 V) is quite similar to
that of the ferrocene itself (E1/2=0.485 V, DEp=80
mV) and it is shifted to a lower-potential region with

334
A. Arques et al. / Journal of Organometallic Chemistry 598 (2000) 329–338
versible oxidation of the iminophosphorane group [21],
it would be reasonable to assign the first oxidation peak
to the iminophosphorane oxidation. Fig. 3(d) also
shows that the diphenylphosphino group does not un-
dergoes electrochemical oxidation under these
conditions.
rected. Electrochemistry: Quiceltron potentiostat/gal-
vanostat controlled by a personal computer and driven
by dedicated software. Experiments were carried out in
a three-electrode cell. Electrochemical experiments were
performed on 1 mM dimethylformamide or acetonitrile
solutions containing 0.1 M [n-Bu4N][ClO4] as support-
ing electrolyte. Deoxygenation of the solutions was
achieved by bubbling nitrogen for at least 10 min. All
of the potential values are referred to SCE. Cyclo-
voltammetric tests were performed at scan rates from
The second electron transfer concerns the iron center
[Fe(II)/Fe(III)] which gives an irreversible wave. This
observation, coupled with the above-mentioned absence
of any chemical complication when both diphenylphos-
phino and iminophosphorane groups are coordinated
by palladium, would lead to the conclusion that the
ferrocene–ferrocinium electron transfer in the free lig-
and 3e might be complicated by chemical reactions.
The observed lack of a coupled cathodic peak after
the last oxidation is probably due to the fast disappear-
ance of the ferricinium cation. This behavior has also
been found in several ferrocenylphosphanes in which
the diphenylphosphino group is directly linked to the
ferrocene ring, and it has been attributed to an oxida-
tion of the phosphorus atom via a ferrocinium cation
by a fast intramolecular electron transfer with regenera-
tion of Fe(II) [22]. However, in the free ligand 3e, the
diphenylphosphino group is not directly linked to the
ferrocene ring, so that the absence of the cathodic peak
is not likely to be due to this type of interaction. This
idea was supported by changing the solvent. Thus, the
cyclic voltammogram of 3e in acetonitrile solution dis-
played a first irreversible electron process (Epa=0.275
vs. SCE) corresponding to the iminophosphorane
group oxidation, and a second quasi-reversible electron
process (E1/2=0.634 V vs. SCE) due to the oxidation
Fe(II) to Fe(III). This observation could suggest cou-
pled reactions between the resulting product of the
initial iminophosphorane group oxidation with the fer-
rocene ring, and the loss of the cathodic peak observed
in DMF solution could be due to low stability of the
ferrocinium cation in this solvent. The quantitative
electrochemical studies of 3e and others types of ferro-
cenylimino–phosphorane compounds are under active
investigation.
50 to 500 mV s−1
.
5.2. Preparation of azides 2b–c and 2g — general
procedure
To a well-stirred solution containing sodium (0.76 g,
33 mmol) in dry ethanol (10 ml), a solution of ethyl
azidoacetate (4.3 g, 33 mmol) in dry ethanol (3 ml) and
the appropriate aldehyde (15 mmol) were added drop-
wise at −15°C under nitrogen. The reaction mixture
was stirred at this temperature for 7 h. After this it was
poured into aqueous 30% ammonium chloride (30 ml)
and was extracted with diethyl ether (3×30 ml). The
combined extracts were washed with water (3×10 ml),
dried (Na2SO4) and evaporated under reduced pressure
at 30°C. The residual material was chromatographed
on a silica gel column using ethylacetate–n-hexane
(2:1).
2b: (78%), yellow prisms, m.p. 57–58°C, Rf=0.50.
IR (Nujol): w=2122, 1700, 1605, 1515, 1334, 1313,
1266, 1218, 1180, 1124, 1085, 1033, 900, 840, 762, 728
3
cm−1.1H-NMR (CDCl3): l=7.29 (d, 2H, J=8.7 Hz),
3
6.90 (d, 2H, J=8.7 Hz), 6.88 (s, 1H, CHꢀC), 4.35 (q,
3
2H, J=7.2 Hz, CH2), 3.83 (s, 3H, CH3O), 1.39 (t, 3H,
3J=6.9 Hz, CH2CH3). 13C-NMR (CDCl3): l=163.16
(CO), 160.42 (C-4), 132.34 (C-2), 127.73 (C-1), 126.02
(CHꢀC), 125.37 (CHꢀC), 113.88 (C-3), 62.03 (CH2),
55.28 (CH3O), 14.21 (CH2CH3). MS (EI, 70 eV); m/z
(%): 219 (45) [M+−N2], 174 (20), 173 (100), 158 (16),
146 (33), 145 (34). C12H13N3O3 (247.25): Anal. Calc. C,
58.29; H, 5.30; N, 16.99; found C, 58.20; H, 5.35; N,
16.85%.
2c: (69%), yellow prisms, m.p. 46–48°C, Rf=0.54.
IR (Nujol): w=2124, 2104, 1714, 1624, 1581, 1305,
1285, 1260, 1237, 1163, 1108, 1098, 1049, 1030, 943,
5. Experimental
1
914, 888, 862, 787, 762 cm−1. H-NMR (CDCl3): l=
5.1. General
7.42 (m, 1H, 2-H), 7.37–7.22 (m, 2H), 6.93–6.85 (m,
1H), 6.87 (s, 1H, CHꢀC), 4.36 (q, 2H, 3J=7.1 Hz,
CH2), 3.83 (s, 3H, CH3O), 1.39 (t, 3H, 3J=7.1 Hz,
CH2CH3). 13C-NMR (CDCl3): l=163.45 (CO), 159.41
(C-3), 134.38 (C-1), 129.32 (C-5), 125.74 (CHꢀC),
125.09 (CHꢀC), 123.34 (C-6), 115.42 (C-2)*, 115.24
(C-4)*, 62.25 (CH2), 55.25 (CH3O), 14.16 (CH2CH3).
MS (EI, 70 eV); m/z (%): 219 (60) [M+−N2], 174 (29),
173 (100), 158 (29), 147 (53), 146 (39). C12H13N3O3
(247.25): Anal. Calc. C, 58.29; H, 5.30; N, 16.99; found
C, 58.40; H, 5.38; N, 16.75%. *Interchangeable.
All experiments were carried out with the exclusion
of air and moisture under nitrogen. Solvents were
predried over molecular sieves and freshly distilled from
appropriate drying agents. Compounds 2a and 2d–g
were prepared according to the literature procedure
[5,7,8]. NMR: Bruker AC200 or Varian Unity 300. MS:
Fisons Autospec 5000 VG. IR: Nicolet Impact 400.
Elemental analyses: Perkin–Elmer 240c. Melting points
were determined on a Kofler hot-plate and are uncor-

A. Arques et al. / Journal of Organometallic Chemistry 598 (2000) 329–338
335
2g: (5%), brown viscous oil, Rf=0.10. IR (Nujol):
w=2129, 1723, 1618, 1595, 1343, 1273, 1250, 1201,
1121, 1098, 1076, 1022, 999, 906, 892, 874, 823, 765,
3b: (86%), yellow prisms, m.p. 121–122°C, Rf=0.18.
IR (Nujol): w=1743, 1690, 1599, 1556, 1310, 1198,
1
1177, 1113, 1033, 856, 824, 728, 701 cm−1. H-NMR
1
3
726 cm−1. H-NMR (CDCl3): l=8.62 (m, 2H; 2-H/6-
(CDCl3): l=8.19 (d, 2H, J=8.8 Hz, 3-H/5-H), 7.83–
3
H), 7.63 (m, 2H; 3-H/5-H), 6.76 (s, 1H; CHꢀC), 4.39 (q,
2H, 3J=7.2 Hz, CH2), 1.41 (t, 3H, 3J=7.2 Hz,
CH2CH3). 13C-NMR (CDCl3): l=162.65 (CO), 150.06
(C-2/C-6), 140.14 (C-4), 129.92 (CHꢀC), 123.89 (C-3/C-
5), 121.31 (CHꢀC), 62.73 (CH2), 14.09 (CH2CH3). MS
(EI, 70 eV); m/z (%): 218 (9) [M+], 190 (55) [M+−N2],
145 (22), 144 (100), 116 (19). C10H10N4O2 (218.21):
Anal. Calc. C, 55.04; H, 4.62; N, 25.67; found C, 55.12;
H, 4.60; N, 25.80%.
7.68 (m, 4H), 7.52–7.11 (m, 18H), 6.85 (d, 2H, J=8.8
4
Hz, 2-H/4-H), 6.85 (d, 1H, J=8.2 Hz, CHꢀCꢁCO),
3
3.93 (q, 2H, J=7.0 Hz, CH2), 3.82 (s, 3H, CH3O),
1.10 (t, 3H, 3J=7.0 Hz, CH2CH3). 13C{1H}-NMR
3
(CDCl3): l=168.39 (d, J=8.7 Hz, CO), 157.63 (C-4),
1
2
148.02 (dd, J=23.0, J=2.2 Hz, CHꢁP(III)), 139.79
(dd, 1J=85.1, 2J=23.7 Hz, CHꢁP(V)), 138.65 (dd,
4
1
1J=12.3, J=1.1 Hz, C-1%%), 135.32 (d, J=110.7 Hz,
C-1%), 134.30 (dd, 2J=8.1, 5J=1.1 Hz, ꢀCꢁCO), 132.78
(d, J=19.3 Hz, C-2%%), 131.54 (d, J=0.9 Hz, C-1),
2
4
2
5
131.18 (dd, J=9.4, J=1.4 Hz, C-2%), 130.84 (C-2),
4
5.3. Preparation of monoiminophosphoranes 3 —
general procedure
130.40 (d, J=2.8 Hz, C-4%), 128.25 (C-4%%), 128.19 (d,
3J=6.3 Hz, C-3%%), 128.13 (d, 3J=11.9 Hz, C-3%),
116.14 (d, 3J=21.1 Hz, CHꢀCꢁCO), 113.10 (C-3),
60.76 (CH2), 55.21 (CH3O), 14.18 (CH2CH3). 31P-NMR
(CDCl3): l= −3.20 (d, P(V)), −23.88 (d, P(III)),
3JPP=11.8 Hz. HR-MS (EI, 70 eV); m/z (%): 615. 2118
To a solution of the appropriate b-substituted viny-
lazide 2 (1.53 mmol) in 10 ml of dry CH2Cl2, an
equimolecular amount of (Z)-1,2-bis(diphenylphospho-
ranyl)ethene 1 in 10 ml of dry CH2Cl2 was added at
room temperature. The reaction mixture was stirred for
24 h. The solvent was then removed in vacuo and the
remaining residue was chromatographed on a silica gel
column using ethyl acetate–n-hexane (1:5) as eluent for
3a–3e and ethyl acetate–n-hexane (2:1) for 3f–3g.
3a: (94%), yellow prisms, m.p. 42–43°C, Rf=0.26.
IR (Nujol): w=1684, 1588, 1561, 1326, 1236, 1198,
(31) [M+, Anal. Calc. for C138H3145N16O331P2 615.2092],
12
558.1755 (9), 539.1743 (19), 538.1708 (53), 431.1594
(27), 430.1558 (100), 429.1487 (42), 396.1192 (14),
335.0750 (31). MS (EI, 70 eV); m/z (%): 616 (14)
[M++1], 615 (31) [M+], 558 (9), 539 (19), 538 (53), 431
(27), 430 (100), 429 (42), 396 (14), 335 (31).
3c: (86%), yellow prisms, m.p. 45–47°C, Rf=0.24.
IR (Nujol): w=1693, 1591, 1476, 1465, 1299, 1265,
1243, 1220, 1190, 1160, 1115, 1044, 999, 957, 882, 848,
1
1113, 1038, 851, 824, 744, 717, 696 cm−1. H-NMR
3
1
(CDCl3): l=8.13 (d, 2H, J=8.4 Hz), 7.79 (ddd, 4H,
788, 739, 694 cm−1. H-NMR (CDCl3): l=8.23 (dd,
3
4
4
4
3
3JP=12.0, J=7.8, J=1.5), 7.58 (ddd, 1H, JP=29.1,
1H, J=2.0, J=1.5 Hz, 2-H), 7.76 (ddd, 4H, JP=
3
3
4
JP=22.5, Jcis=13.8 Hz), 7.46–7.09 (m, 19H), 6.67 (d,
12.3, J=8.1, J=1.5 Hz), 7.55–7.10 (m, 20H), 6.71
(dd, 1H, J=8.4, J=2.0 Hz, 4-H), 6.66 (d, 1H J=
4
3
3
4
4
1H, J=8.1 Hz, CHꢀCꢁCO), 3.92 (q, 2H, J=7.2 Hz,
3
3
CH2); 2.35 (s, 3H, CH3Ar), 1.10 (t, 3H, J=7.2 Hz,
8.1 Hz, CHꢀCꢁCO), 3.94 (q, 2H, J=7.5 Hz, CH2),
CH2CH3). 13C{1H}-NMR (CDCl3): l=168.34 (d, J=
3.58 (s, 3H, CH3O), 1.11 (t, 3H, J=7.5 Hz, CH2CH3).
3
3
8.7 Hz, CO), 148.08 (dd, 1J=23.0, 2J=2.3 Hz,
CHꢁP(III)), 138.80 (dd, 1J=84.2, 2J=23.6 Hz,
CHꢁP(V)), 138.63 (dd, 1J=12.0, 4J=1.1 Hz, C-1%%),
135.74 (C-4), 135.28 (dd, 2J=8.1, 5J=1.1 Hz,
13C{1H}-NMR (CDCl3): l=168.29 (d, 3J=9.2 Hz,
1
2
CO), 159.23 (C-3), 148.40 (dd, J=23.6, J=2.0 Hz,
CHꢁP(III)), 139.98 (C-1), 138.60 (dd, 1J=12.0, 4J=1.1
Hz, C-1%%), 138.60 (dd, 1J=84.2, 2J=22.2 Hz,
CHꢁP(V)), 136.33 (dd, 2J=8.0, 5J=1.1 Hz, =C–CO),
135.18 (d, J=110.7 Hz, C-1%), 132.79 (d, J=19.5 Hz,
C-2%%), 131.18 (dd, J=9.2, J=1.7 Hz, C-2%), 130.48
1
ꢀCꢁCO), 135.26 (d, J=110.1 Hz, C-1%), 135.18 (C-1),
132.79 (d, 2J=19.5 Hz, C-2%%), 131.19 (dd, 2J=9.2,
5J=1.2 Hz, C-2%), 130.42 (d, 4J=2.1 Hz, C-4%), 129.50*
(C-2), 128.24 (C-4%%), 128.20 (d, 3J=6.4 Hz, C3%%),
1
2
2
5
4
(d, J=2.9 Hz, C-4%), 128.33 (C-4%%+C-5), 128.26 (d,
3
128.14 (d, J=12.0 Hz, C-3%), 128.03* (C-3), 116.25 (d,
3J=6.3 Hz, C-3%%), 128.18 (d, 3J=12.0 Hz; C-3%),
3J=20.7 Hz, CHꢀCꢁCO), 60.83 (CH2), 21.36
(CH3ꢁAr), 14.15 (CH2CH3). 31P-NMR (CDCl3): l= −
3.28 (d, P(V)), −23.93 (d, P(III)), 3JPP=12.3 Hz.
HR-MS (EI, 70 eV); m/z (%): 599.2128 (15) [M+, Anal.
122.57 (C-6), 115.91 (d, J=21.3; CHꢀCꢁCO), 113.21
3
(C-2), 112.90 (C-4), 60.94 (CH2), 55.12 (CH3O), 14.14
(CH2CH3). 31P-NMR (CDCl3): l= −1.93 (d, P(V)),
−24.00 (d, P(III)), 3JPP=11.8 Hz. MS (EI, 70 eV); m/z
(%): 615 (11) [M+], 586 (5), 558 (14), 538 (47), 431 (30),
430 (100), 396 (14), 335 (22), 201 (44), 185 (38), 183
(63). C38H35NO3P2 (615.65): Anal. Calc. C, 74.14; H,
5.73; N, 2.28; found C, 74.28; H, 5.70; N, 2.31.
3d: (85%), yellow prisms, m.p. 47–49°C, Rf=0.22.
IR (Nujol): w=1738, 1684, 1599, 1567, 1310, 1241,
1113, 1033, 750, 696 cm−1. 1H-NMR (CDCl3): l=9.22
12
Calc. for C138H1354N16O231P2 599.2143], 570.1803 (4),
543.1836 (4), 542.1804 (11), 523.1793 (18), 522.1757
(49), 415.1642 (29), 414.1609 (100), 396.1158 (10),
335.0731 (21). MS (EI, 70 eV); m/z (%): 600 (6) [M++
1], 599 (15) [M+], 570 (4), 543 (4), 542 (11), 523 (18),
522 (49), 415 (29), 414 (100), 396 (10), 335 (21).
*Interchangeable.

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A. Arques et al. / Journal of Organometallic Chemistry 598 (2000) 329–338
3
4
3
6
(dd, 1H, JH5=7.5, JH4=1.8 Hz, 6-H), 7.82–7.75 (m,
13C{1H}-NMR (CDCl3): l=167.57 (dd, J=9.1, J=
3
1
2
4H), 7.70–7.09 (m, 20H), 6.97 (t, 1H, J=8.1 Hz), 6.85
0.7 Hz, CO), 150.41 (C-6), 148.61 (dd, J=23.2, J=
(d, 1H, 3J=7.5 Hz, 3-H), 3.94 (q, 2H, 3J=7.2 Hz,
CH2), 3.84 (s, 3H, CH3O), 1.09 (t, 3H, 3J=7.2 Hz,
2.3 Hz, CHꢁP(III)), 145.66 (C-2), 138.32 (dd, J=11.9,
1
4J=1.1 Hz, C-1%%), 138.24 (dd, J=8.1, J=1.2 Hz,
2
5
CH2CH3). 13C{1H}-NMR (CDCl3): l=168.42 (d, J=
ꢀCꢁCO), 138.00 (dd, 1J=85.4, 2J=23.5 Hz,
3
1
2
1
8.9 Hz, CO), 156.28 (C-2), 147.99 (dd, J=23.3, J=
CHꢁP(V)), 135.57 (C-4), 134.67 (d, J=111.3 Hz, C-
1
2
4
2
2.3 Hz, CHꢁP(III)), 138.82 (dd, J=84.7, J=23.5 Hz,
1%), 134.62 (d, J=0.9 Hz, C-3), 132.64 (d, J=19.5
CHꢁP(V)), 138.55 (dd, 1J=12.3, 4J=1.6 Hz, C-1%%),
Hz, C-2%%), 130.99 (dd, 2J=9.5, 5J=1.4 Hz, C-2%),
2
1
4
3
135.91 (d, J=6.9 Hz, ꢀCꢁCO), 135.29 (d, J=111.0
130.61 (d, J=2.7 Hz, C-4%), 128.24 (d, J=11.8 Hz,
C-3%), 128.21 (d, 3J=6.6 Hz, C-3%%), 128.36 (C-4%%),
122.72 (C-5), 111.52 (d, 3J=21.3 Hz, CHꢀCꢁCO),
61.10 (CH2), 14.10 (CH2CH3). 31P-NMR (CDCl3): l=
2
Hz, C-1%), 132.73 (d, J=19.2 Hz, C-2%%), 131.19 (dd,
2J=9.9, 5J=1.3 Hz, C-2%), 130.72 (C-6), 130.34 (d,
4J=2.6 Hz, C-4%), 128.23 (C-4%%), 128.17 (d, 3J=6.3 Hz,
C-3%%), 128.06 (d, 3J=12.0 Hz, C-3%), 127.42 (C-1),
126.41 (C-4), 119.92 (C-5), 109.59 (C-3), 108.78 (d,
3J=20.6 Hz, CHꢀCꢁCO), 60.84 (CH2), 55.47 (CH3O),
14.16 (CH2CH3). 31P-NMR (CDCl3): l= −3.59 (d,
3
−1.00 (d, P(V)), −23.50 (d, P(III)), JPP=11.8 Hz.
MS (EI, 70 eV); m/z (%): 587 (32) [M++1], 586 (36)
[M+], 557 (21), 529 (22), 509 (71), 402 (54), 401 (100),
335 (55), 201 (62), 185 (44), 183 (63). C36H32N2O2P2
(586.61): Anal. Calc. C, 73.71; H, 5.50; N, 4.78; found
C, 73.80; H, 5.55; N, 4.82.
3
P(V)), −25.84 (d, P(III)), JPP=12.3 Hz. MS (EI, 70
eV); m/z (%): 615 (14) [M+], 558 (15), 538 (46), 431
(43), 430 (100), 396 (18), 356 (48), 335 (31), 201 (56),
185 (59), 183 (91), 108 (38), 107 (21). C38H35NO3P2
(615.65): Anal. Calc. C, 74.14; H, 5.73; N, 2.28; found
C, 74.08; H, 5.67; N, 2.32.
3g: (62%), yellow prisms, m.p. 58–60°C, Rf=0.18.
IR (CH2Cl2): w=1735, 1699, 1584, 1526, 1329, 1240,
1196, 1113, 1036, 990, 854, 817, 738, 697 cm−1. H-
1
3
NMR (CDCl3): l=8.43 (d, 2H, J=6.1 Hz, 2-H/6-H),
3e: (41%), red prisms, m.p. 48–51°C, Rf=0.22. IR
7.99 (d, 2H, 3J=6.1 Hz, 3-H/5-H), 7.75 (ddd, 4H,
(Nujol): w=1685, 1590, 1412, 1213, 1108, 807 cm−1
.
3JP=12.1, J=7.4, J=1.5 Hz, 2%-H), 7.54–7.09 (m,
3
4
1H-NMR (CDCl3): l=7.89 (ddd, 4H, JP=12.0, J=
18H), 6.45 (d, 1H, JP=8.2 Hz, CHꢀCꢁNꢀP(V)), 3.96
3
3
4
4
7.5, J=1.8 Hz; 2%-H), 7.68 (ddd, 1H, JP=30.3 Hz,
JP=21.6, Jcis=13.5 Hz; ꢀCHꢁP(V)), 7.46–7.33 (m,
6H, 3%-H, 4%-H), 7.26–7.13 (m, 11H, 2%%-H, 3%%-H, 4%%-H,
ꢀCHꢁP(III)), 6.50 (d, 1H, JP=8.4 Hz, CHꢀC), 5.02
(pt, 2H, J=1.8 Hz, 2-H/5-H), 4.25 (pt, 2H, J=1.8 Hz,
(q, 2H, 3J=7.0 Hz, CH2), 1.29 (t, 3H, 3J=7.0 Hz,
CH2CH3). 13C{1H}-NMR (CDCl3): l=167.24 (d, J=
3
3
9.8 Hz, CO), 149.23 (d, 1J=23.0 Hz, CHꢁP(III)),
4
1
148.56 (C-2/C-6), 146.25 (C-4), 141.04 (d, J=8.1 Hz,
C-1%%), 138.18 (d, 2J=11.5 Hz, ꢀCꢁCO), 137.31 (dd,
3
3-H/4-H), 4.07 (s, 5H, Cp), 3.98 (q, 2H, J=7.2 Hz,
1J=85.3, 2J=23.1 Hz, CHꢁP(V)), 134.22 (d, 1J=
CH2), 1.16 (t, 3H, 3J=7.2 Hz, CH2CH3). 13C{1H}-
110.7 Hz, C-1%), 132.69 (d, J=19.6 Hz, C-2%%), 131.06
2
3
NMR (CDCl3): l=168.97 (d, J=8.5 Hz, CO), 146.97
(d, 2J=9.2 Hz, C-2%), 130.84 (d, 4J=2.3 Hz, C-4%),
(d, 1J=22.0 Hz, ꢀCHꢁP(III)), 140.17 (dd, 1J=84.6,
128.26 (C-4%%), 128.35 (d, J=12.6 Hz, C-3%), 128.39 (d,
3
2J=24.5 Hz, ꢀCHꢁP(V)), 138.62 (d, J=11.5 Hz, C-
3J=6.9 Hz, C-3%), 123.25 (C-3/C-5), 111.68 (d, J=
1
3
1
2
1%%), 135.65 (d, J=109.6 Hz, C-1%), 133.92 (d, J=8.0
20.7 Hz, CHꢀCꢁCO), 61.35 (CH2), 14.07 (CH2CH3).
Hz, ꢀCꢁCO), 132.68 (d, 2J=19.0 Hz, C-2%%), 131.21
31P-NMR (CDCl3): l= −0.10 (d, P(V)), 23.14 (d,
2
5
4
3
(dd, J=9.0, J=1.5 Hz, C-2%), 130.33 (d, J=2.4 Hz,
C-4%), 128.27 (C-4%%), 128.23 (d, 3J=6.0 Hz, C-3%%),
P(III)), JPP=11.8 Hz. MS (EI, 70 eV); m/z (%): 587
(5) [M++1], 586 (10) [M+], 557 (14), 529 (14), 509
(72), 402 (29), 401 (100), 335 (67), 201 (81), 185 (40),
183 (74). C36H32N2O2P2 (586.61): Anal. Calc. C, 73.71;
H, 5.50; N, 4.78; found C, 73.68; H, 5.42; N, 4.73.
3
3
128.11 (d, J=11.5 Hz, C-3%), 115.86 (d, J=22.5 Hz,
CHꢀCꢁCO), 83.25 (C-1), 69.70 (C-2/C-5), 68.92 (Cp),
67.87 (C-3/C-4), 60.62 (CH2), 14.24 (CH2CH3). 31P-
NMR (CDCl3): l= −5.72 (d, P(V)), −25.49 (d,
3
P(III)), JPP=13.2 Hz. MS (EI, 70 eV); m/z (%): 693
5.4. Synthesis of complexes 5 — general procedure
(100) [M+], 616 (12), 224 (23). C41H37NO2P2Fe
(693.55): Anal. Calc. C, 71.00; H, 5.38; N, 2.02; found
C, 70.90; H, 5.41; N, 1.97.
To a solution of the appropriate monoiminophos-
phorane 3 (0.367 mmol) in 15 ml of dry dichloro-
methane, a suspension of dichlorobis(benzonitrile)-
palladium(II) (0.14 g, 0.367 mmol) in 10 ml of the same
solvent was added dropwise. The resulting mixture was
stirred at room temperature for 4 h. The precipitated
solid was collected by filtration and chromatographed
on a silica gel column using 1:9 methanol–dichloro-
methane as eluent.
3f: (78%), yellow prisms, m.p. 55–57°C, Rf=0.50.
IR (CH2Cl2): w=1694, 1592, 1560, 1430, 1332, 1268,
1220, 1119, 1043, 899, 737, 713 cm−1
.
1H-NMR
4
(CDCl3): l=9.00 (d, 1H, J=1.8 Hz, 2-H), 8.85 (dt,
1H, J=8.1, JH4=4JH2=1.8 Hz, 6-H), 8.32 (dd, 1H,
3
4
3JH5=4.8, JH2=1.8 Hz, 4-H), 7.75 (ddd, 4H, JP=
4
3
3
4
12.0, J=7.5, J=1.2 Hz, 2%-H), 7.54–7.09 (m, 19H),
6.55 (d, 1H, 4JP=8.4 Hz, CHꢀCꢁCO), 3.96 (q, 2H,
5a: (83%), yellow prisms, m.p. 262–264°C, Rf=0.40.
IR (Nujol): w=1706, 1615, 1316, 1252, 1161, 1102,
3J=7.2 Hz, CH2), 1.13 (t, 3H, J=7.2 Hz, CH2CH3).
3

A. Arques et al. / Journal of Organometallic Chemistry 598 (2000) 329–338
337
3
1049, 1006, 888, 846, 824, 739, 712, 701 cm−1
.
31P-
(d, P(V)), 0.26 (d, P(III)), JPP=37.0 Hz. MS (FAB);
m/z (%): 839 (23), 838 (54), 837 (41), 836 (97), 835 (58),
834 (100) [M+−Cl], 833 (63), 832 (30), 798 (25) [M+
−2Cl], 678 (86), 502 (69), 425 (86). C41H37NCl2-
O2P2FePd (869.00): Anal. Calc. C, 56.55; H, 4.28;
N, 1.61; found C, 56.40; H, 4.16; N 1.70. *Interchange-
able.
NMR ([D6]DMSO): l=11.6 (d, P(V)), 5.07 (d, P(III)),
3JPP=48.1 Hz. MS (FAB); m/z (%): 745 (23), 744 (58),
743 (39), 742 (99), 741 (56), 740 (100) [M+−Cl], 739
(67), 738 (30), 705 (21) [M+−2Cl], 632 (14), 502 (22),
425 (21). C38H35NCl2O2P2Pd (776.96): Anal. Calc. C,
58.74; H, 4.54; N, 1.80; found C, 58.63; H, 4.40; N,
1.85.
5f: (56%), yellow prisms, m.p. 145–148°C, Rf=0.40.
IR (CH2Cl2): w=1714, 1620, 1590,1440, 1326, 1267,
5b: (97%), yellow prisms, m.p. 251–253°C, Rf=0.70.
IR (Nujol): w=1706, 1602, 1509, 1316, 1305, 1246,
1173, 1155, 1117, 1030, 996, 884, 846, 832, 737, 691
1158, 1108, 1038, 885, 808, 736, 701 cm−1
.
31P-NMR
3
(CD2Cl2): l=12.20 (d, P(V)), 6.27 (d, P(III)), JPP
=
cm−1
.
31P-NMR ([D6]DMSO): l=12.66 (d, P(V)), 6.78
45.6 Hz. MS (FAB); m/z (%): 733 (19), 732 (26), 731
(59), 730 (40), 729 (100), 728 (55), 727 (100) [M+−Cl],
726 (70), 725 (34), 692 (49) [M+−2Cl], 615 (20), 502
(67). C36H32N2Cl2O2P2Pd (763.92): Anal. Calc. C,
56.60; H, 4.22; N, 3.67; found C, 56.73; H, 4.30; N,
3.61.
3
(d, P(III)), JPP=51.7 Hz. MS (FAB); m/z (%): 762
(14), 761 (22), 760 (56), 759 (42), 758 (99), 757 (57), 756
(100) [M+−Cl], 755 (68), 754 (30), 721 (17) [M+−
2Cl], 648 (10), 502 (17), 425 (17). C38H35NCl2O3P2Pd
(792.96): Anal. Calc. C, 57.56; H, 4.45; N, 1.77; found
C, 57.42; H, 4.32; N, 1.70.
5g: (58%), yellow prisms, m.p. 185–189°C, Rf=0.33.
IR (Nujol): w=1715, 1632, 1613, 1319, 1250, 1156,
5c: (80%), yellow prisms, m.p. 249–251°C, Rf=0.60.
IR (Nujol): w=1711, 1614, 1592, 1306, 1268, 1245,
1119, 1029, 999, 843, 735, 692 cm−1
.
1H-NMR
1
3
1121, 1045, 1002, 911, 858, 752, 735, 701 cm−1. H-
(CD2Cl2): l=3.99 (q, 2H, J=7.2 Hz, CH2), 1.05 (t,
NMR ([D6]DMSO): l=3.99 (q, 2H, 3J=6.6 Hz, CH2),
1.09 (t, 3H, 3J=6.6 Hz, CH2CH3). 31P-NMR
([D6]DMSO): l=14.98 (d, P(V)), 5.21 (d, P(III)),
3JPP=41.3 Hz. MS (FAB); m/z (%): 762 (14), 761 (22),
760 (56), 759 (42), 758 (99), 757 (57), 756 (100) [M+−
Cl], 755 (68), 754 (30), 721 (17) [M+−2Cl], 648 (10),
502 (17), 425 (17). C38H35NCl2O3P2Pd (792.96): Anal.
Calc. C, 57.56; H, 4.45; N, 1.77; found C, 57.39; H,
4.38; N, 1.80.
3H, J=7.2 Hz, CH2CH3). 31P-NMR (CD2Cl2): l=
3
18.50 (d, P(V)), 6.71 (d, P(III)), 3JPP=37.7 Hz. MS
(FAB); m/z (%): 733 (18), 732 (26), 731 (61), 730 (42),
729 (100), 728 (57), 727 (99) [M+−Cl], 726 (72), 725
(28), 692 (14) [M+−2Cl], 615 (9), 502 (14).
C36H32N2Cl2O2P2Pd (763.92): Anal. Calc. C, 56.60; H,
4.22; N, 3.67; found C, 56.77; H, 4.15; N, 3.59.
5d: (89%), yellow prisms, m.p. 239–241°C, Rf=0.63.
IR (Nujol): w=1707, 1597, 1308, 1288, 1256, 1183,
1160, 1110, 1033, 1005, 941, 897, 882, 837, 745, 700
6. X-ray crystallographic studies
Crystal data are given in Table 1. A crystal of 5e
suitable for X-ray diffraction was prepared by slow
difussion of methanol–ethanol (1:1) in a dichloro-
methane solution. A crystal of 5e was mounted in inert
oil on a glass fiber and transferred to the diffractometer
(Siemens P4 with LT2 low-temperature attachment).
Measurements were made at 100°C using monochro-
cm−1
.
31P-NMR ([D6]DMSO): l=12.48 (d, P(V)), 6.69
3
(d, P(III)), JPP=51.7 Hz. MS (FAB); m/z (%): 762
(16), 761 (23), 760 (59), 759 (39), 758 (100), 757 (54),
756 (100) [M+−Cl], 755 (64), 754 (29), 721 (16) [M+
−2 Cl], 502 (15). C38H35NCl2O3P2Pd (792.96): Anal.
Calc. C, 57.56; H, 4.45; N, 1.77; found C, 57.66; H,
4.48; N, 1.72.
,
mated Mo–Ka radiation (u=0.71073 A).
5e: (56%), red prisms, m.p. \300°C, Rf=0.53. IR
Unit cell parameters were determined from a least-
squares analysis of ca. 63 accurately centered reflections
(9.4B2qB23.7°). Intensities were measured using ꢀ
scans. Absorption corrections were based on „ scans.
The structures were solved by the heavy-atom method
and refined anisotropically on F2 (program SHELXL-93)
[23]. Hydrogen atoms were included using a riding
model.
1
(Nujol): w=1692, 1613, 1595, 1261, 1149 cm−1. H-
3
3
NMR (CD2Cl2): l=8.43 (dd, 2H, JP=12.7, J=7.1
3
3
Hz, 2%%-H), 7.97 (dd, 2H, JP=11.1, J=7.2 Hz, 2%-H),
7.72–7.44 (m, 6H), 7.39–6.95 (m, 13H), 5.14 (s, 1H,
H2/H5), 4.27 (s, 1H, H3/H4), 4.30 (s, 7H, Cp+2H),
4.00–3.83 (m, 2H, 2JAB=9.8, 3JAX=3JBX=7.0 Hz),
1.16 (t, 3H, 3J=7.0 Hz, CH2CH3). 13C{1H}-NMR
3
(CD2Cl2): l=167.61 (d, J=1.4 Hz, CO), 141.02 (dd,
1JP(V)=104.5, JP(III)=7.2 Hz, ꢀCHꢁP(V)), 135.63 (dm,
2
1JP(III)=34.6 Hz, ꢀCHꢁP(III)), 134.44 (d, J=11.1 Hz,
7. Supplementary material
2
C-2%%), 133.78 (d, 3J=11.8 Hz, C-3%%), 133.76 (d, 2J=9.7
Hz, C-2%), 131.57 (d, 4J=3.0 Hz, C-4%%)*, 130.92 (d,
4J=2.7 Hz, C-4%)*, 128.16 (d, 3J=12.1 Hz, C-3%), 78.29
(C-1), 71.62, 70.52, 70.33, 69.51 (Cp), 69.44, 61.07
(CH2), 13.78 (CH2CH3). 31P-NMR (CD2Cl2): l=15.80
Crystallographic data (excluding structure factors)
for the structures reported in this paper have been
deposited with the Cambridge Crystallographic Data
Centre as supplementary publication no. CCDC-

338
A. Arques et al. / Journal of Organometallic Chemistry 598 (2000) 329–338
Org. Chem. 62 (1997) 1568. (f) J.P. Wolfe, S.L. Buchwald,
Table 1
Crystal data for compound 5e a
Tetrahedron Lett. 38 (1997) 6359. (g) P. Barbaro, A. Togni,
Organometallics 14 (1995) 3570.
Empirical formula
Mr
C41H37Cl2FeNO4P2Pd·EtOH·MeOH
948.92
[3] (a) P. Molina, A. Arques, A. Garc´ıa, M.C. Ram´ırez de Arellano,
Tetrahedron Lett. 38 (1997) 7613. (b) P. Molina, A. Arques, A.
Garc´ıa, M.C. Ram´ırez de Arellano, Eur. J. Inorg. Chem. (1998)
1359.
[4] (a) H. Staudinger, J. Meyer, Helv. Chim. Acta 2 (1919) 635. (b)
Y.G. Gololobov, I.N. Zhmurova, L.F. Kasukhin, Tetrahedron
37 (1981) 437.
[5] (a) P. Molina, A. Pastor, M.J. Vilaplana, M.C. Ram´ırez de
Arellano, Tetrahedron Lett. (1996) 7829. (b) P. Molina, A.
Pastor, M.J. Vilaplana, M.D. Velasco, M.C. Ram´ırez de Arel-
lano, Organometallics 16 (1997) 5836.
[6] R.W. Reed, B. Santarsiero, R.G. Cavell, Inorg. Chem. 35 (1996)
4292.
,
a (A)
11.4729(9)
12.5465(10)
16.2722(12)
83.281(5)
71.648(6)
64.801(5)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
Z
Dcalc. (Mg m−3
Crystal system
Space group
)
1.567
Triclinic
(
P1
Crystal size (mm)
q range (°)
0.60×0.30×0.20
3.16–25.00
8483
[7] P. Molina, A. Ta´rraga, M.J. Lido´n, J. Chem. Soc. Perkin Trans.
1 (1990) 1727.
Reflections measured
Independent reflections
6985
1.065
0.91965/0.83798
485
972
0.745
0.0334
0.0833
[8] P. Molina, A. Lorenzo, E. Aller, Tetrahedron 48 (1992) 4601.
[9] (a) R.B. King, J.C. Cloyd Jr, Inorg. Chem. 14 (1975) 1550. (b) S.
Hietkamp, D.J. Stufkens, K. Urieze, J. Organomet. Chem. 169
(1979) 107. (c) I. McLeod, L. Manojlovic-Muir, D. Millington,
K.W. Muir, D.W.A. Sharp, R. Walker, J. Organomet. Chem. 97
(1975) C7. (d) T.G. Appleton, M.A. Bennett, Inorg. Chem. 17
(1978) 738.
v (mm−1
)
Max./min. transmission
Parameters
F(000)
−3
,
Max. Dz (e A
)
a
R1
b
wR2
[10] H.K. Gupta, S. Brydges, M.J. McGlinchey, Organometallics 18
(1999) 115.
a R1=SꢀꢀFoꢀ−ꢀFcꢀꢀ/SꢀFoꢀ for reflections with I\2|(I).
[11] F.H. Allen, O. Kennard, Chem. Des. Autom. News 8 (1993) 31.
[12] D. Cremer, J.A. Pople, J. Am. Chem. Soc. 97 (1975) 1354.
[13] G. Giacovazzo (Ed.), Fundamentals of Crystallography, Oxford
University Press, Oxford, UK, 1992, Chapter 7, pp. 490–499.
[14] (a) P. Imhoff, C.J. Elsevier, J. Organomet. Chem. 361 (1989)
C61. (b) P. Imhoff, R. van Asselt, C.J. Elsevier, M.C. Zoutberg,
C.H. Stam, Inorg. Chim. Acta 184 (1991) 73. (c) M.W. Avis, K.
Urieze, H. Kooijman, N. Veldman, A.L. Spek, C.J. Elsevier,
Inorg. Chem. 34 (1995) 4092.
[15] (a) K.V. Katti, R.J. Batchelor, F.W.B. Einstein, R.G. Cavell,
Inorg. Chem. 29 (1990) 808. (b) M.W. Avis, M.E. van der Boom,
C.J. Elsevier, W.J.J. Smeets, A.L. Spek, J. Organomet. Chem.
527 (1997) 263.
b wR2=[S[w(Fo2−Fc2)2]/S[w(Fo2)2]]0.5 for all reflections; w−1
=
|2(F2)+(aP)2+bP, where P=(2Fc2+F2o)/3 and a and b are constants
set by the program.
121658. Copies of the data can be obtained free of
.
charge on application to The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (Fax: +44-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk).
[16] W. Oberhauser, C. Bachmann, P. Brueggeller, Inorg. Chem.
Acta 238 (1995) 35.
Acknowledgements
[17] J. Albert, J. Granell, J. Sales, X. Solans, M. Font-Altaba,
Organometallics 5 (1996) 2567.
[18] H. Brunner, A. Winter, J. Breu, J. Organomet. Chem. 553 (1998)
285 and references cited therein.
We gratefully acknowledge the financial support of
the Direccio´n General de Investigacio´n Cient´ıfica y
Te´cnica, project number PB95-1019.
[19] (a) P.D. Harvey, L.L. Gan, Inor. Chem. 31 (1991) 3239. (b) J.C.
Kotz, E.E. Getty, L. Lin, Organometallics 4 (1985) 610. (c) T.
Kawamoto, Y. Kushi, J. Chem. Soc. Dalton Trans. (1992) 3137.
[20] M. Sato, H. Asano, J. Organomet. Chem. 452 (1993) 105.
[21] (a) M. Pomerantz, D.S. Marynick, K. Rajeshwar, W. Chou, L.
Throckmorton, E.W. Tsai, P.C.Y. Chen, T. Cain, J. Org. Chem.
51 (1986) 1223. (b) E.W. Tsai, M.K. Witczack, K. Rajeshwar,
M. Pomerantz, J. Electroanal. Chem. 236 (1987) 219.
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