Allylpalladium(II) complexes with aminophosphane ligands: Solution behaviour and X-ray structure of cis-[Pd(η3-CH 2CHCHPh){Ph2PCH2CHPhNH(2,6-C6H 3iPr2)}][PF6]

Article abstract of DOI:10.1002/ejic.200300627

A new β-aminophosphane L² [Ph₂PCH ₂CH(Ph)NH(2,6-C₆H₃iPr₂)], bearing an asymmetric carbon atom and a vicinal prochiral nitrogen centre and (η³-allyl)palladium complexes of general formula [Pd(η³-C₃H₄R)(η²-Ph ₂PCH₂CH(Ph)NHAr)][PF₆] (1-6) (R = H, Me or Ph and Ar = Ph or 2,6-C₆H₃iPr₂) have been synthesised. NMR spectroscopic studies and a crystal structure analysis of complex 6 (R = Ph, Ar = 2,6-C₆H₃iPr₂) confirmed the highly diastereoselective coordination of the nitrogen atom. Because of the allyl fluxionality and the presence of asymmetric centres, all the complexes exist in solution as mixtures of up to four diastereomers. For the monosubstituted allyl complexes [Pd(η³-C₃H ₄R)(Ph₂PCH₂CH(Ph)NHAr)][PF₆] (3-6, R = Me or Ph) only cis/trans-P and endo/exo isomers with syn-oriented allyl substituents have been observed in solution. The diastereomeric distribution is subject to a steric control since a modification of the steric bulk of the allyl substituents and/or N-aryl groups strongly affect the isomers ratio. An X-ray diffraction study of compound 6 reveals a mixture of endo and exo cis-P syn isomers and corresponds to the first cis-P isomer crystal structure for an N,P-ligand allyl complex. A phase-sensitive 2-D NOESY NMR analysis showed that complex 1 undergoes a selective syn-anti exchange isomerisation, involving exclusively a trans-P opening of the η³-allyl moiety. Therefore, η³-η¹-η³ rearrangements in allylic complexes 1-6 were assumed to occur via the regioselective formation of a σ-allyl intermediate. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300627

FULL PAPER
Allylpalladium(II) Complexes with Aminophosphane Ligands:
Solution Behaviour and X-ray Structure of cis-[Pd(η3-CH2CHCHPh)-
{Ph2PCH2CHPhNH(2,6-C6H3iPr2)}][PF6]
Jean-Michel Camus,[a] Jacques Andrieu,*[a] Philippe Richard,[a] and Rinaldo Poli[a][‡]
Keywords: Allyl ligands / N,P ligands / syn-anti exchange / Palladium
A
new β-aminophosphane L2 [Ph2PCH2CH(Ph)NH(2,6-
eric distribution is subject to a steric control since a modifica-
tion of the steric bulk of the allyl substituents and/or N-aryl
groups strongly affect the isomers ratio. An X-ray diffraction
study of compound 6 reveals a mixture of endo and exo cis-
P syn isomers and corresponds to the first cis-P isomer crystal
structure for an N,P-ligand allyl complex. A phase-sensitive
2-D NOESY NMR analysis showed that complex 1 undergoes
C6H3iPr2)], bearing an asymmetric carbon atom and a vicinal
prochiral nitrogen centre and (η3-allyl)palladium complexes
of
(Ph)NHAr}][PF6] (1−6) (R = H, Me or Ph and Ar = Ph or 2,6-
C6H3iPr2) have been synthesised. NMR spectroscopic studies
and a crystal structure analysis of complex 6 (R = Ph, Ar =
general
formula
[Pd(η3-C3H4R){η2-Ph2PCH2CH-
2,6-C6H3iPr2) confirmed the highly diastereoselective coor- a selective syn-anti exchange isomerisation, involving ex-
dination of the nitrogen atom. Because of the allyl flux-
clusively a trans-P opening of the η3-allyl moiety. Therefore,
ionality and the presence of asymmetric centres, all the com- η3-η1-η3 rearrangements in allylic complexes 1−6 were as-
plexes exist in solution as mixtures of up to four diastereo- sumed to occur via the regioselective formation of a σ-allyl
mers. For the monosubstituted allyl complexes [Pd(η3-
C3H4R){Ph2PCH2CH(Ph)NHAr}][PF6] (3−6, R = Me or Ph)
only cis/trans-P and endo/exo isomers with syn-oriented allyl
intermediate.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
substituents have been observed in solution. The diastereom- Germany, 2004)
enantiocontrol.[17Ϫ19] For complexes containing ditopic
Introduction
N,P-ligands, the nucleophilic attack is assumed to occur at
the carbon atom trans to the phosphorus[17,27,28] and the
selectivities strongly depend on the relative abundance of
diastereomeric allylic complexes. In comparison to extens-
ive investigations of complexes with symmetric allyl ligands,
few studies have been devoted to monosubstituted allyl
complexes.[17,20Ϫ26] In the case of the allylic alkylation of
asymmetric substrates, such as cinnamyl acetate or crotyl
acetate, only the trans-P diastereomers lead to the product
containing the new chiral centre; the cis-P isomers lead to
achiral linear Z or E products (see Figure 1). The enantio-
control is therefore subordinate to the regiocontrol.
In a previous contribution, we have described the syn-
thesis and the coordinative behaviour of a chiral aminopho-
sphane Ph2PCH2CH(Ph)NHPh (L1), in allylpalladium()
complexes.[29] This study highlighted a diastereoselective
N-coordination in the cationic complex [Pd(η3-C3H5)(L1)]ϩ,
and an NϪH···ClϪM intramolecular interaction involving
the dangling NϪH moiety for the neutral complex
[PdCl(η3-C3H5)(κ1:P,L1)]ϩ (see Figure 2) which is a feature
of P-coordinated aminophosphanes with a secondary am-
ine function.[30]
Palladium-catalysed allylic substitution is a powerful
methodology for the formation of new CϪC or CϪN
bonds, with the potential to achieve high levels of enantio-
selectivity in the presence of chiral ligands.[1Ϫ4] In particu-
lar, the use of N,P-ligands provides very high enantioselec-
tivities in the allylic alkylation of 1,3-diphenylpropenyl
substrates.[5Ϫ10] One major advantage of hybrid ligands
over ditopic ligands consists in the electronic differentiation
of the coordinating atoms, inducing a nucleophilicity
discrimation of the terminal allylic carbon atoms. There-
fore, other chiral hybrid ligands such as O,P,[11,12] P,S[13,14]
or N,S[15,16] have been studied in order to benefit from these
electronic effects. Cationic allylic [Pd(η3-allyl)L2]ϩ com-
plexes with bidentate L2 ligands are thought to be the key
intermediate in the catalytic cycle and there is a growing
interest in understanding their dynamic behaviour in solu-
tion and in elucidating mechanistic details related to the
[a]
`
`
Laboratoire de Synthese et dЈElectrosynthese
´
´
Organometalliques, UMR 5188 CNRS, Universite de
´
Bourgogne, Faculte des Sciences ‘‘Gabriel’’,
6 Boulevard Gabriel, 21000 Dijon, France
E-mail: Jacques.Andrieu@u-bourgogne.fr
Current address: Laboratoire de Chimie de Coordination,
UPR CNRS 8241, 205 route de Narbonne,
31077 Toulouse Cedex, France
We report here the extension of our synthetic procedure
to a new β-aminophosphane and to its cationic allylpal-
ladium complexes, including ones with asymmetric mono-
[‡]
Eur. J. Inorg. Chem. 2004, 1081Ϫ1091
DOI: 10.1002/ejic.200300627
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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J.-M. Camus, J. Andrieu, P. Richard, R. Poli
FULL PAPER
Figure 1. Regioselectivity and enantioselectivity in palladium-cata-
lysed allylic alkylation arising from different diastereomeric η3-al-
lyl complexes
Scheme 1
The cationic allyl complexes 1Ϫ6 were synthesised by
treatment of the chloro-bridged allylpalladium dimer with
the appropriate ligand in the presence of an excess of the
halide-scavenger NaPF6 in dichloromethane. They were ob-
tained in high yields as air-stable, white or yellow powders
that are soluble in organic solvents, except alkanes and
Et2O. The 31P NMR chemical shifts for compounds 1Ϫ6
are characteristic of the aminophosphane bidentate coordi-
nation. Since the ligands contain an asymmetric centre, the
complexes may exist as different diastereomers arising from
the different face coordination (endo or exo) of the allyl
moiety with respect to the ligand. The endo isomer is de-
fined as having the CϪH bond of the internal allylic carbon
atom pointing in the same direction as the NϪH bond (see
Scheme 2). For the monosubstituted allyl complexes, the al-
lyl substituents can be in a cis-P or trans-P position and
can be positioned syn or anti with respect to the internal
allyl proton. Furthermore, the nitrogen atom becomes a
new asymmetric centre upon coordination. However, be-
cause of the induction by the vicinal chiral carbon atom, its
coordination is expected to be highly diastereoselective, as
previously reported.[29,33] Therefore, only eight different
diastereomers may arise, in principle, from the possible
orientations of the allyl fragment. The diastereomeric distri-
bution in solution at room temperature was determined in
each case by NMR spectroscopy (except for 1, which has
already been reported[29]) and is presented below.
Figure 2. Coordinative features of aminophosphane L1 in neutral
and cationic allyl palladium complexes
substituted allyl ligands, as well as a detailed 2-D NOESY
NMR investigation of the mechanism of interconversion of
the various diastereomers. The diastereomeric ratio is
strongly dependent on the steric bulk of the allyl N-sub-
stituents. The first X-ray structure of a cis-P allyl complex
is also presented.
Results and Discussion
Synthesis of the Aminophosphane Ligand L2 and Cationic
Allylpalladium Complexes
The new aminophosphane ligand L2 was synthesised by
the same one-step procedure previously described for ligand
L1 (Scheme 1).[29] It consists of the nucleophilic attack of an
imine moiety by the diphenylphosphinomethyl anion. After
hydrolysis and workup, the aminophosphane was isolated
in good yield as a light-yellow, microcrystalline powder and
1
was characterised by H, 13C and 31P NMR spectroscopy
and by elemental analysis (see Exp. Sect.). The 31P NMR
spectroscopic data are in agreement with those of other β-
N,P ligands bearing an sp3 nitrogen centre and an ethylenic
backbone linking the heteroatoms.[29,31,32]
Scheme 2
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Allylpalladium(II) Complexes with Aminophosphane Ligands
FULL PAPER
ity. The difference between the 13C NMR chemical shifts of
the external allyl carbon atoms (∆δ ϭ δC1 Ϫ δC3) is a meas-
ure of the difference between their electronic environ-
ments.[14,23,28,37] For complexes 1 and 2, ∆δ lies between
35.7 and 27.2 ppm depending on the isomer (see Table 1).
Such a high ∆δ is usual for N,P ligands, given the very dif-
ferent trans influence of the phosphorus and nitrogen
atoms,[26] and reveals a higher electrophilicity for the C-1
atom (trans-P) than for the C-3 atom (cis-P; see Scheme 2).
This feature has also been observed in the solid state, since
NMR Spectroscopic Studies on Allylic Compounds 1 and 2
The 31P{1H} NMR spectra of complexes 1 and 2 display
two singlets in a 1:1 and 6.8:3.2 ratio, respectively. Because
of the diastereoselective N-coordination and the allyl sym-
metry, compounds 1 and 2 may only afford two dia-
stereomers (endo and exo, see Scheme 2). The dia-
1
stereomeric ratio was confirmed by integration of the H
NMR spectra. The steric bulk of the N-substituents affects
the isomeric proportion, as observed for other allyl com-
pounds (see below). This seems to be an important key for
the enantiocontrol in allylic substitution of 1,3-propenyl
acetate derivatives.[8,18,19,34] For allylic complexes, the endo/
exo ratio can be tuned by adjusting the steric constraints
either around the donor atoms or on the allyl moi-
ety.[14,19,35] You et al. have observed that, for a complex con-
taining the 2-(phenylthio)-1-(4-tert-butyloxazolinyl)ferro-
cene ligand, an inversion of the configuration of the oxazo-
line ring asymmetric carbon slightly affects the endo/exo ra-
tio (3.1:1 vs. 2.1:1), whereas introducing two benzylic
groups at the 4-position of the oxazoline ring strongly dis-
places the equilibrium in favour of the endo dia-
stereomer.[36]
the PdϪC distances are longer for CtransP than those for
[19,38Ϫ40]
CcisP
.
It should be noted that the orientation of the
allyl fragment induces slight differences in ∆δ (35.7:32.5 for
1 and 29.9:27.2 for 2). This feature probably arises from the
steric hindrance caused by the N-substituents onto the al-
lylic trans-P carbon atom, affecting its electrophilicity. Simi-
lar observations have been made for allylic complexes with
phosphinoxazoline ligands.[41] Therefore, there is a close re-
lation between the bulk of the N-substituents and (i) the
endo/exo ratio, and (ii) the electrophilicity of the external
carbon atoms.
The preferential nucleophilic attack at one specific allyl
carbon atom is another way to achieve high enantioselectiv-
NMR Characterisation of Monosubstituted Allylic
Compounds 3؊6
As detailed above, the introduction of one substituent at
an external allyl carbon atom increases the number of pos-
sible isomers from two to eight. NMR investigations for
complexes 3Ϫ6 revealed that all of them exist as mixtures
Table 1. 13C NMR spectroscopic data for allylic carbon atoms in
complexes 1 and 2
(2JH,P in Hz)
13
δ
13
∆δ
C
C
C-1
C-2
C-3
(δC-1 Ϫ δC-3) of four diastereomers in solution in different equilibrium
transP
cisP
ratios. The coupling constants and chemical shifts for the
3
2
1a
1b
2a
2b
87.1 (27)
84.6 (28)
82.3 (27)
80.6 (29)
120.6
123.0
120.3 (5)
122.2 (5)
51.4
52.1
52.4
53.4
35.7
32.5
29.9
27.2
allyl moieties are reported in Table 2. The JH,P, JC,P and
δ13C values are helpful for the assignment of each isomer as
trans-P or cis-P, since the coupling constants to the phos-
phorus nucleus are greater for the trans than for the cis
1
Table 2. Selected 13C and H NMR spectroscopic data for allylic complexes 3Ϫ6 (n.d. ϭ not determined)
13
δ
1
δ
H
(JP,C in Hz)
(JH,P in Hz)
C
Complexes
C-1
C-2
C-3
CH3
1-Hanti
1-Hsyn
2-H
3-Hsyn
3-Hanti
CH3
3a (53%)
3b (30%)
3c (11%)
3d (6%)
102.9 (26)
101.7 (26)
78.3 (23)
74.2 (25)
116.2 (5)
118.9 (5)
123.5 (6)
n.d.
46.7 (4)
47.5 (3)
72.3 (5)
69.2 (4)
14.1 (4)
14.2 (4)
17.2
4.98 (n.d.)
3.92 (n.d.)
4.17 (n.d.)
n.d.
Ϫ
Ϫ
5.23
5.58
5.73
5.68
3.79
3.54
Ϫ
2.56
2.82
3.85
n.d.
0.66 (9.3)
1.04 (9.1)
1.09 (9.1)
1.46 (9.1)
2.72 (n.d.)
2.81 (n.d.)
18.0
Ϫ
4a (78%)
4b (9%)
4c (9%)
4d (4%)
99.5 (26)
103.3 (27)
76.3 (27)
n.d.
119.3 (5)
119.2 (6)
122.5 (5)
n.d.
49.3 (4)
49.1
72.6 (4)
n.d.
15.7 (4)
16.9 (5)
19.6
4.75 (n.d.)
4.05 (n.d.)
3.84 (9.4)
n.d.
Ϫ
Ϫ
5.34
5.72
5.61
5.83
4.10
3.67
Ϫ
2.83
2.92
4.16
n.d.
0.67 (9.4)
1.26 (9.5)
1.62 (9.0)
n.d.
3.52 (n.d.)
n.d.
19.0
Ϫ
5a (55%)
5b (22%)
5c (12%)
5d (11%)
104.7 (24)
104.6 (24)
80.7 (26)
82.0 (25)
111.3 (5)
115.0 (5)
116.7 (5)
119.6 (5)
48.8
49.8
73.9 (5)
74.6 (5)
Ϫ
Ϫ
Ϫ
Ϫ
5.82 (n.d.)
4.67 (9.9)
4.47 (9.2)
3.08 (9.3)
Ϫ
Ϫ
5.82
6.20
6.19
5.83
3.88
3.62
Ϫ
2.77
3.04
4.81
4.62
Ϫ
Ϫ
Ϫ
Ϫ
4.25 (7.2)
3.85 (n.d.)
Ϫ
6a (9%)
6b (7%)
6c (62%)
6d (22%)
n.d.
n.d.
79.4(25)
76.6 (27)
n.d.
n.d.
116.4(5)
118.8 (6)
n.d.
n.d.
74.6(6)
76.1 (5)
Ϫ
Ϫ
Ϫ
Ϫ
5.95 (9.0)
4.92 (9.9)
4.41(8.8)
2.99 (n.d.)
Ϫ
Ϫ
5.68
6.40
6.20
6.40
3.62
n.d.
Ϫ
2.79
2.84
4.79
4.86
Ϫ
Ϫ
Ϫ
Ϫ
3.83(7.8)
4.23 (7.3)
Ϫ
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J.-M. Camus, J. Andrieu, P. Richard, R. Poli
FULL PAPER
nuclei.[26,42] For the 1-butenyl complexes, the coupling con- the greater steric bulk introduced by the addition of the
stants involving the external methyl moiety, 4JH,P and 3JC,P
,
two isopropyl groups at the ortho positions of the N-phenyl
enable the establishment of the cis-P/trans-P ratio, whereas substituent induces a strong variation of the endo/exo (or
δ1 is not diagnostic of the relative orientation. Indeed, for exo/endo) ratio (from 53:30 for 3 to 78:9 for 4), whereas
H
1-butenyl (R ϭ Me) complexes based on other types of N,P the global cis/trans-P ratio is only slightly affected (around
ligands, van Leeuwen has proposed that the signal for the 85:15). The geometry of the least abundant isomer of 4 (4%
methyl group should be found at δ Ͼ 1.3 ppm when in the relative abundance) could not be unambiguously elucidated
trans-P position and at δ Ͻ 0.6 ppm when in the cis-P posi- because of its very low concentration, coupled with the par-
tion.[43] However, several 1H NMR resonances for the tial overlap of its resonances with those of the other iso-
methyl substituents in complexes 3Ϫ6 and other known al- mers. Therefore, it was assumed to correspond to the se-
lyl complexes transgress this ‘‘rule’’.[19,20,44] For instance, cond cis-P isomer of the c/d couple.
the isomers of complexes 3 show resonances at δ ϭ 0.66,
An influence of the steric bulk on the diastereomeric pro-
1.04, 1.09 and 1.46 ppm (Figure 3). In spite of this diffi- portion is also present for the 1-phenylpropenyl complexes
culty, the cis/trans-P orientation could be established unam- 5 and 6, which were observed as 55:22:12:11 and 62:22:9:7
biguously from other NMR characteristics.
isomeric mixtures in solution, respectively. Contrary to the
observations for compounds 3 and 4, introducing a bulky
N-substituent leads to a strong variation of the cis/trans-P
ratio, whereas the global endo/exo ratio is only slightly af-
fected. Nevertheless, the most remarkable observation is
that the major isomer in solution is a cis-P isomer for com-
plex 6. Indeed, the major isomers for most[47] monosubsti-
tuted allyl complexes reported in the literature present a
Figure 3. High field 1H NMR spectrum (CDCl3, 500 MHz, 283 K)
of the CH3 terminal group of complex 3, showing the presence of
four isomers
The analysis of the 3JH ,H1 coupling constants allowed us
to determine the relative 2positions of each allyl proton, re-
vealing the exclusive presence of the syn isomers, i.e. having
the protons 1-H and 2-H in anti positions. This contrasts
with 1,3-disubstituted allylic complexes, for which minor
amounts of isomers with the allylic substituents in the anti
position are present in solution.[28,45] The syn/anti ratio
could be affected by tuning the steric bulk between the li-
gand substituents and the allyl moiety.[18,19,43] The four iso-
mers and their relative proportions are depicted in Figure 4.
Compounds 3 and 4 have been identified as 53:30:11:6 and
78:9:9:4 mixtures, respectively, with the two major isomers
(a and b) having a syn trans-P orientation. The two minor
isomers were assigned to the syn cis-P diastereomers (c and
d). Concerning the trans-P isomers, it can be observed that
Figure 5. ORTEP views of the exo-6c and endo-6d isomers; only
relevant hydrogen atoms are shown; for clarity, the CH2Cl2 solvent
and the hexafluorophosphate anion are omitted.
Figure 4. Schematic representation and distribution of complexes
3Ϫ6 isomers
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Eur. J. Inorg. Chem. 2004, 1081Ϫ1091

Allylpalladium(II) Complexes with Aminophosphane Ligands
FULL PAPER
trans-P orientation.[17,20,23,43,44,46] To confirm this unexpec- Crystal Structure of [Pd(η3-CH2CHCHPh){Ph2PCH2-
ted observation, suitable crystals were therefore grown and CHPhNH(2,6-C6H3iPr2)}][PF6] (6)
used for an X-ray crystallographic study.
Yellow crystals of compound 6 were grown from di-
The solid-state structure (discussed in more detail later)
chloromethane/pentane. As already mentioned above, the
highlights the cis-P orientation of the phenyl group and
structure is quite interesting because it exhibits a solid mix-
corresponds to a solid solution of both endo and exo iso-
ture of two different cis-P diastereomeric cations within the
mers in a 78:22 ratio (see Figure 5). To the best of our
same unit cell. Indeed, due to disorder around the allyl car-
knowledge, this represents the first solid-state structural de-
bon atoms, accompanied by a slight tilting of the phenyl
termination of an allylic complex with an N,P ligand in a
substituent, both endo and exo cis-P isomers have been
identified in the solid state and their relative occupancies
refined to afford a 78:22 ratio in favour of the endo isomer
(6d, see Figure 5). Such a cocrystallisation phenomenon has
cis-P position. The crystals were redissolved in CDCl3 and
the resulting solution was monitored by 31P NMR spec-
troscopy (see Figure 6). The spectrum displays four singlets
whose relative intensities evolved slowly from a 7:9:55:21
many literature precedents for asymmetric allyl
ratio (5 min) to the equilibrium 7:9:22:62 ratio after 24
complexes[17,41,48Ϫ51] and allowed us to fully determine the
hours. Therefore, the configuration of the two major iso-
major diastereomers not only in the solid state but also in
mers is completely established: the major isomer in the solid
solution, as detailed in the previous section. An ORTEP
state (endo cis-P, 6d) displays the 31P NMR resonance at
view of the endo and exo diastereomers and selected bond
lengths and angles are reported in Figure 5 and Table 3,
δ ϭ 29.68 ppm, whereas the major one in solution (31P res-
onance at δ ϭ 21.85 ppm, 6c) corresponds to the exo cis-
P species.
respectively. Both isomers 6c and 6d exhibit a typical dis-
torted square-planar arrangement of the (η3-allyl)Pd-P,N
moiety.[17Ϫ19,28,41] The PϪPdϪN bite angle of 84.89(6)°
falls in the range observed for other compounds with five-
membered rings containing N,P ligands and the PdϪP
˚
˚
[2.284(1) A] and PdϪN [2.165(2) A] bond lengths are simi-
lar to other reported values.[44,52Ϫ55] As a result of the dif-
ferent trans influence of the N and P atoms, the PdϪC(1)
˚
bond [2.187(4) A] is longer than the PdϪC(3) bond
˚
[2.156(4) A]. The tilt angle α between the C(1)ϪC(2)ϪC(3)
and PϪPdϪN planes is 107.6°, which is in the wide range
(100Ϫ120°) reported for other allylic compounds. The en-
velope conformation of the five-membered chelate ring is
characteristic of this kind of ligand in the solid state.[29,33,56]
Figure 6. Kinetic 31P NMR monitoring of crystals of 6 dissolved
in CDCl3
˚
Table 3. Selected bond lengths (A) and bond angles (°) for 6c and
6d (* denotes exo isomer atoms)
endo
exo
As already shown for complexes 3 and 4, the addition of
iPr groups to the aryl ortho positions induces dramatic
changes in the isomeric ratios on going from 5 to 6, since
it approximately inverts the trans-P/cis-P ratio from 77:23
to 16:84. The free rotation around the CArϪN bond and
PdϪN
2.165(2)
2.2839(7)
PdϪP(1)
PdϪC(1)
PdϪC(2)
PdϪC(3)
2.187(4) PdϪC(1*)
2.153(4) PdϪC(2*)
2.156(4) PdϪC(3*)
1.418(6) C(1*)ϪC(2*)
1.413(6) C(2*)ϪC(3*)
2.223(16)
2.11(2)
2.214(15)
1.461(16)
1.415(15)
the sterically demanding iPr group destabilize the trans-P C(1)ϪC(2)
C(2)ϪC(3)
orientation of the allylic phenyl substituents. A similar be-
haviour was already observed by Helmchen and co-work-
NϪPdϪP(1)
C(1)ϪPdϪC(3)
NϪPdϪC(1)
P(1)ϪPdϪC(3)
C(1)ϪC(2)ϪC(3) 116.5(5)
C(2)ϪC(3)ϪC(4) 123.9(4)
84.89(6)
ers.[17,19,27] Therefore the subtle combination of steric repul-
67.31(16) C(1*)ϪPdϪC(3*)
101.91(13) NϪPdϪC(1*)
105.82(10) P(1)ϪPdϪC(3*)
65.0(5)
101.6(4)
104.5(3)
sions between the allyl substituent and the N group allows
a higher discrimination between the diastereomers. For the
1-butenyl complexes 3 and 4, the N-isopropyl groups favour
the endo isomer over the exo (or vice versa) and destabilize
the cis-P vs. the trans-P isomers. The trend of tuning the
endo/exo ratio has been reported mainly for symmetrically
disubstituted allyl complexes, while very few papers have
mentioned cis/trans control.[17,23,43] All the complexes stud-
ied in this paper provide evidence of the influence of the
steric bulkiness of the nitrogen substituent on the dia-
stereomeric ratio.
C(1*)ϪC(2*)ϪC(3*) 111.9(15)
C(2*)ϪC(3*)ϪC(4*) 129.2(16)
NMR NOESY Studies of the Dynamic Behaviour of
Complex 1
The fluxional behaviour of the isomeric forms of [Pd(η3-
allyl)(L-LЈ)]ϩ complexes in solution has been established as
Eur. J. Inorg. Chem. 2004, 1081Ϫ1091
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J.-M. Camus, J. Andrieu, P. Richard, R. Poli
FULL PAPER
a consequence of different possible allyl isomerisation path-
ways or of the dissociation of the L-LЈ ligand.[4] The exist-
ence of a dynamic equilibrium between the two dia-
stereomers of complex 1 in a 1:1 ratio has already been
reported by us[29] and we then wished to clarify the allyl
isomerisation pathway by recurring to 2-D NMR experi-
ments. Therefore, a phase-sensitive 2-D NOESY experiment
was carried out in CDCl3 solution. Similar experiments
have previously been described for related com-
pounds.[37,41,57] Figure 7 shows the results of this experi-
ment and the most relevant exchange cross-peaks are lab-
elled from a to d. The allyl 1H NMR resonances are labelled
on the 1D spectrum for isomers a (endo) and b (exo) follow-
ing the nomenclature of Scheme 2, the primed labels corre-
sponding to the exo isomer.
Figure 8. Exchange allyl protons between isomers 1a and 1b
phorus donor atom, followed by a CϪC bond rotation and
recoordination of the η1-allyl double bond (see Scheme 3).
This is consistent with the absence of any anti cis-P isomers
for the monosubstituted complexes 3Ϫ6. Other exchange
cross-peaks were not observed. Notably, exchange peaks be-
tween 3-Hs and 3-HЈs and between 3-Ha and 3-HЈa are
clearly absent. Because of the extensive overlap between the
1-Ha and 1-HЈa resonances, the absence of cross peaks be-
tween 1-Ha and 1-HЈs or between 1-Hs and 1-HЈa could not
be unambiguously established, because any peak of this
kind would be masked by the NOE peaks. However, we
trust that we have sufficient evidence to conclude that a site-
selective syn-anti exchange occurs at the C-3 atom.
Figure 7. The 1H-1H phase-sensitive NOESY spectrum (CDCl3,
500 MHz, 293 K) of complex 1, showing the exchange cross-peaks
(labelled a to d) in the isomers 1a and 1b
The spectrum shows exchange cross-peaks for all the ex-
ternal allylic protons belonging to the same C atom, indicat-
ing an η3-η1-η3 isomerisation pathway. No exchange was
observed between the H atoms on C1 (trans to P) in 1a and
those on C3 (trans to N) in 1b, or vice versa, thereby exclud-
ing an apparent allyl rotation. At the C1 position, the H1s
proton in 1a exchanges with the HЈ1s proton in 1b (Fig-
ure 8). Correspondingly, the H1a proton in 1a exchanges
with the HЈ1a proton in 1b. Thus, each terminal allyl proton
trans to P keeps its relative position with respect to the in-
Scheme 3. η3-η1-η3 isomerisation pathways involving a selective
trans-P opening; dotted square: only for substituted allyl
complexes 3Ϫ6
Therefore, we can conclude that a selective opening of
ternal allyl proton during the epimerisation process. At the the η3-allyl trans to the phosphorus atom occurs that leads
C3 position, on the other hand, cross-peaks between the 3- exclusively to a cis-P σ-allyl intermediate during the η3-η1-
Hs (and 3-Ha) proton in 1a and 3-HЈa (and 3-HЈs) proton η3 isomerisation process. Such a selective process has al-
in 1b are observed. Thus, only the two terminal allyl pro- ready been described for chiral allyl complexes with P-based
tons trans to N trade places in the process. These two latter hybrid ligands resulting from the stronger trans influence of
observations are in agreement with a syn-anti exchange, the P donor atom.[8,19,39,44] The only exception to this rule
which implies the formation of an η1-allyl intermediate by seems to involve a cis-P opening for a P,S ligand system.[14]
selective decoordination at the position trans to the phos- For the other complexes reported here (2Ϫ6), we can as-
1086
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 1081Ϫ1091

Allylpalladium(II) Complexes with Aminophosphane Ligands
FULL PAPER
cis to P atom, respectively, and Hs and Ha are in the syn and anti
positions, respectively, relative to the internal proton H2. For com-
plexes 1 and 2, the carbon and proton chemical shifts are noted C,
H and CЈ, HЈ respectively, for the endo and exo diastereomers (see
Scheme 2). The elemental analyses were performed on a Fisons EA
1108 apparatus at the L.S.E.O. in Dijon. The reagents nBuLi (1.6
 in hexane), Ph2PCH3 and NaPF6 are commercial products from
Aldrich, and were used as received. N-benzylidene-2,6-diisopro-
pylaniline[58] and the chloro-bridged allylpalladium dimers[59]
[Pd(η3-C3H5)(µ-Cl)]2, [Pd(η3-MeC3H4)(µ-Cl)]2, [Pd(η3-PhC3H4)(µ-
Cl)]2 were prepared as described previously. Compound 1 and the
ligand L1 have already been described in a previous publication.[29]
sume a similar η3-η1-η3 rearrangement by an exclusive
trans-P opening. For the monosubstituted allyl compounds
3Ϫ6, a second isomerisation pathway is necessary in order
to interconvert the cis-P and trans-P isomers and this could
involve an apparent allyl rotation. It seems likely that this
pathway involves a PdϪC bond rotation after the selective
trans-P opening (see Scheme 3). The same proposal was
made by Krishnamurthy et al. to explain the cis/trans iso-
merisation of the minor isomers in [Pd(η3--1-
PhC3H4){Ph2PN(iPr)PPh(3,5-N2C3HMe2)}] complexes.[20]
Synthesis of Ligand L2: According to Peterson’s method,[60] 5.0 mL
of nBuLi (1.6  in hexane, 8 mmol) was slowly added to 1.2 mL of
TMEDA (8 mmol) and the mixture was stirred at room tempera-
ture for 20 minutes. Methyldiphenylphosphane (1.5 mL, 8 mmol)
was then slowly added. The mixture was stirred further leading
within 30 minutes to a bright yellow precipitate, which was dis-
solved by addition of a few mililiters of THF. The solution was
Conclusion
The β-aminophosphane ligands Ph2PCH2CH(Ph)NHAr
[Ar ϭ Ph L1, (2,6-C6H4iPr2) L2] bearing a prochiral nitro-
gen atom display a bidentate coordination mode in allylpal-
ladium complexes. Because of the presence of an asymmet-
ric centre vicinal to the weakly basic amine function, the further stirred for half an hour and a solution of N-benzylidene-
2,6-diisopropylaniline (1.65 g, 6.2 mmol) in 10 mL of THF was
slowly added. The mixture was then stirred overnight, followed by
hydrolysis with 20 mL of water. The water phase was separated and
extracted three times with 20 mL of Et2O. The combined organic
phases were dried over MgSO4 and the solvents were removed in
vacuo. The product was recrystallised from ethanol and yellowish
needles were isolated by filtration and dried in vacuo. Yield: 1.59 g
(59%). C32H36NP (465.6): calcd. C 82.55, H 7.79, N 3.01; found C
metal coordination is highly diastereoselective. Different
(η3-allyl)palladium complexes of formula [Pd(η3-1-
C3H4R)L][PF6] (R ϭ H, Me, Ph; L ϭ L1, L2) have been
synthesised and characterised in solution and in the solid
state. In solution, they display a dynamic behaviour be-
tween the diastereomers because of a regioselective η3-η1-
η3 isomerisation of the allyl moiety interconverting endo/
exo (for 1Ϫ6) and cis/trans-P (for 3Ϫ6) isomers. Complexes
3Ϫ6 show exclusively the syn orientation of the allylic sub-
1
82.25, H 8.05, N 3.48. H NMR (CDCl3, 300.13 MHz): δ ϭ 0.89
3
3
[d, JH,H ϭ 6.5 Hz, 6 H, CH-(CH3)2], 1.02 [d, JH,H ϭ 6.5 Hz, 6
2
3
2
stituents and therefore give rise to a mixture of four dia- H, CH-(CH3)2], 2.77 (ddd, JH,P ϭ 1.0, JH,H ϭ 8.0, JH,H
ϭ
13.5 Hz, 1 H, PCHa), 2.91 (ddd, 2JH,P ϭ 1.0, 3JH,H ϭ 8.0, 2JH,H
ϭ
stereomers. The isomeric proportion depends on the steric
13.5 Hz, 1 H, PCHb), 3.00 [septet, JH,H ϭ 6.7 Hz, 2 H, CH-
3
bulk of the allylic and/or N-substituents. The dynamic be-
haviour of 1 was studied by 2-D NOESY experiments.
These prove that the syn-anti exchange process occurs via a
regioselective η3-allyl opening trans to the phosphorus posi-
tion. On the basis of these results, the exclusive formation
of cis-P η1-allyl intermediates was assumed to occur by an
apparent allyl rotation which equilibrates the cis and trans-
P isomers for the monosubstituted allyl complexes 3Ϫ6.
(CH3)2], 3.44 (broad s, 1 H, exchange with D2O, NH), 3.93 (dt,
3
3
3JH,H ϭ JH,H ϭ 6.7, JH,P ϭ 8.2 Hz, 1 H, NCH), 7.00 (m, 3 H,
4
3
Hm,p N-Ph), 7.14 (dd, JH,H ϭ 1.4, JH,H ϭ 7.9 Hz, 2 H, Hm C-
4
3
Ph), 7.25Ϫ7.35 (m, 15 H, Harom), 7.40 (dt, JH,H ϭ 1.8, JH,H
ϭ
7.0 Hz, 1 H, Ho P-Ph), 7.45 (dt, JH,H ϭ 1.8, 3JH,H ϭ 7.0 Hz, 1 H,
Ho P-Ph) ppm. 13C{1H} NMR (75.5 MHz, CDCl3): δ ϭ 24.3 [2C,
2 CH(CH3)2], 24.5 [2C, 2 CH(CH3)2], 28.2 [2C, 2 CH(CH3)2], 36.1
4
2
3
(d, JC,P ϭ 14 Hz, PCH2), 62.7 (d, JC,P ϭ 17 Hz, NCH), 123.7
Work aimed at obtaining enantiomerically pure forms of (2C, 2 Cm N-Ph), 124.0 (Cp N-Ph), 127.5 (2C, 2 Cm C-Ph), 127.9
(Cp C-Ph), 128.75 (2C, 2 Co C-Ph), 128.85 (2C, 2 Cm P-Ph), 128.9
these aminophosphane ligands is in progress permitting the
study of palladium-catalysed allylic alkylation of monosub-
stituted 1-propenyl substrates in order to correlate (or not)
the regio-, stereo- and enantioselectivities with the obser-
vations described herein.
(2C, 2 Cm P-Ph), 129.0 (Cp P-Ph), 129.2 (Cp P-Ph), 132.9 (d,
2
2JC,P ϭ 19 Hz, 2 C, 2 Co P-Ph), 133.5 (d, JC,P ϭ 21 Hz, 2 C, 2 Co
2
2
P-Ph), 138.9 (d, JC,P ϭ 12 Hz, 1 C, 2 Ci P-Ph), 139.0 (d, JC,P
ϭ
12 Hz, 1 C, 2 Ci P-Ph), 141.1 (Ci C-Ph), 143.0 (2C, Co N-Ph), 143.1
(Ci N-Ph) ppm. 31P{1H} NMR (121.5 MHz, CDCl3):
Ϫ23.2 ppm.
δ ϭ
[Pd(η3-C3H5){Ph2PCH2CHPhNH(2,6-C6H3iPr2)}][PF6] (2): A di-
chloromethane solution (5 mL) of ligand L2 (0.202 g, 0.53 mmol)
was progressively added to a solution of [Pd(η3-C3H5)Cl]2 (97 mg,
Experimental Section
All reactions were performed in Schlenk-type flasks under an argon
atmosphere and solvents were purified and dried by conventional 0.26 mmol) in 5 mL of dichloromethane. The solution was stirred
1
methods and distilled under argon. The H, 13C{1H} and 31P{1H}
for 30 minutes at room temperature and then added to a suspension
of NaPF6 (0.223 g, 1.3 mmol) in 2 mL of dichloromethane. The
NMR spectra were recorded in CDCl3 on a Bruker 300 Advance
or a Bruker 500 DRX instrument. Complete assignment was mixture was stirred for a further 2 hours and filtered through Ce-
achieved by use of COSY, DEPT and HMQC experiments. All
lite. The resulting yellow filtrate was concentrated in vacuo to ca.
chemical shifts are relative to SiMe4 (1H and 13C NMR) or 85% 1 mL. Addition of 15 mL of pentane caused the precipitation of
H3PO4 (31P NMR) and are given in ppm. Numbering scheme used the product, which was washed with pentane (2 ϫ 20 mL). The
for the L2 ligand: Ha, Hb and Hc are the non-equivalent PCH2 and
the NCH protons, respectively. Numbering scheme used for the al-
white powder was filtered and dried under vacuum. Yield: 0.315 g
(89%). C35H41F6NP2Pd (758.1): calcd. C 55.45, H 5.45, N 1.84;
lyl ligand: C1, C2 and C3 are trans to P atom, central carbon and found C 55.34, H 5.70, N, 2.11. Major isomer (2a, 68%): 1H NMR
Eur. J. Inorg. Chem. 2004, 1081Ϫ1091
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J.-M. Camus, J. Andrieu, P. Richard, R. Poli
FULL PAPER
(CDCl3, 500.13 MHz): δ ϭ 0.34 [d, JH,H ϭ 4.9 Hz, 3 H, CH-
aromatic protons, Harom) ppm. 13C{1H} NMR: δ ϭ 14.2 (d, 3JC,P ϭ
3
2
2
(CH3)2], 0.62 [d, 3JH,H ϭ 4.9 Hz, 3 H, CH-(CH3)2], 0.95 [d, 3JH,H ϭ 4 Hz, C4), 35.5 (d, JC,P ϭ 23 Hz, PCH2), 47.5 (d, JC,P ϭ 3 Hz,
3
3
2
4.9 Hz, 3 H, CH-(CH3)2], 1.15 [d, JH,H ϭ 4.9 Hz, 3 H, CH-
(CH3)2], 2.86 [m, 1 H, CH-(CH3)2], 3.00 (dd, JH,P ϭ 3.7, JH,H
C3), 68.8 (d, JC,P ϭ 10 Hz, NCH), 101.7 (d, JC,P ϭ 26 Hz, C1),
3
3
2
ϭ
118.9 (d, JC,P ϭ 5 Hz, C2), 144.4Ϫ121.5 (m, 24C, Carom) ppm.
13.8 Hz, 1 H, H3a), 3.14 (dt, 3JH,H ϭ 2.9, 2JH,P ϭ 2JH,H ϭ 15.0 Hz, 31P{1H} NMR: δ ϭ 32.05 (s) ppm. Isomer cis-P (3c, 11%). 1H
1 H, PCH), 3.24 [m, 1 H, CH-(CH3)2], 3.66 (dt, JH,H ϭ 3.6, NMR: δ ϭ 1.09 (dd, 3JH,H ϭ 6.3, 4JH,P ϭ 9.1 Hz, 3 H, C4H3), 2.72
3
2JH,P ϭ JH,H ϭ 15.0 Hz, 1 H, PCH), 3.84 (t, JH,P ϭ JH1s,H2
ϭ
(broad d, JH,H ϭ 6.9 Hz, H1s), 4.17 (m,1 H, H1a), 5.73 (m, 1 H,
2
3
3
3
5.9 Hz, 1 H, H1s), 4.03(m, 1 H, NCH), 4.16 (d, JH,H ϭ 6.8 Hz, 1 H2), 6.25 (d, 3JH,H ϭ 11.1 Hz, 1 H, NH) ppm. 13C{1H} NMR: δ ϭ
3
3
3
2
2
H, H3s), 4.21 (dd, JH,P ϭ 8.9, JH,H ϭ 14.1 Hz, 1 H, H1a), 5.51
17.2 (C4), 72.3 (d, JC,P ϭ 5 Hz, C3), 78.3 (d, JC,P ϭ 23 Hz, C1),
3
3
2
(apparent tt, JH2,H1s
ϭ
3JH2,H3s ϭ 6.9, JH2,H1a
ϭ
3JH2,H3a
ϭ
123.5 (d, JC,P ϭ 6 Hz, C2) ppm. 31P{1H} NMR: δ ϭ 32.10 (s)
3
1
3
13.8 Hz, 1 H, H2), 6.68 (d, JH,H ϭ 10.8 Hz, 1 H, NH), 6.91Ϫ7.76 ppm. Isomer cis-P (3d, 6%): H NMR: δ ϭ 1.46 (dd, JH,H ϭ 6.3,
(m, merged with second diastereomer aromatic protons, Harom
)
4JH,P ϭ 9.1 Hz, 3 H, C4H3), 2.81 (m, 1 H, H1s), 5.68 (m, 1 H, H2),
ppm. 13C{1H} NMR (125.7 MHz, CDCl3): δ ϭ 23.9 [CH-(CH3)2], 6.40 (d, 3JH,H ϭ 11.0 Hz, 1 H, NH) ppm. 13C{1H} NMR: δ ϭ 18.0
24.2 [CH-(CH3)2], 24.5 [CH-(CH3)2], 24.8 [CH-(CH3)2], 28.3 [2 (C4), 69.2 (d, JC,P ϭ 4 Hz, C3), 74.2 (d, JC,P ϭ 25 Hz, C1) ppm.
2
2
CH-(CH3)2], 35.7 (d, JC,P ϭ 25 Hz, PCH2), 52.4 (C3), 66.9 (d, 31P{1H} NMR: δ ϭ 28.63 (s) ppm.
2
3JC,P ϭ 7 Hz, NCH), 82.3 (d, 2JC,P ϭ 27 Hz, C1), 120.3 (d, JC,P
ϭ
2
[Pd(η3-CH2CHCHMe){Ph2PCH2CHPhNH(2,6-C6H3iPr2)}][PF6]
(4): Starting materials: [Pd(η3-MeC3H4)Cl]2 (47 mg, 0.12 mmol), L2
(112 mg, 0.24 mmol) and NaPF6 (48 mg, 0.29 mmol). Yield:
0.149 g (81%). C36H43F6NP2Pd (772.1): calcd. C 56.00, H 5.61, N
5 Hz, C2), 124.6Ϫ140.4 (m, 24 C, Carom) ppm. 31P{1H} NMR
(202.5 MHz, CDCl3): δ ϭ 30.71 (s), Ϫ142.75 (sept, 1JF,P ϭ 716 Hz,
PF6Ϫ) ppm. Minor isomer (2b, 32%): 1H NMR: δ ϭ 0.28 [d,
3JH,H ϭ 5.3 Hz, 3 H, CH-(CH3)2], 0.69 [d, JH,H ϭ 5.3 Hz, 3 H,
3
3
1.81; found C 55.81, H 5.77, N 2.14%. Major trans-P isomer (4a,
CH-(CH3)2], 1.09 [d, JH,H ϭ 5.3 Hz, 3 H, CH-(CH3)2], 1.13 [d,
3
78%): 1H NMR (CDCl3, 500.13 MHz): δ ϭ 0.36 [d, JH,H
ϭ
3JH,H ϭ 5.3 Hz, 3 H, CH-(CH3)2], 2.77 [m, 1 H, CH-(CH3)2],
3
4
2.96Ϫ3.00 (m, 2 H, H1s and H3a), 3.10 (dt, JH,H ϭ 3.0, JH,P
ϭ
3
2
6.6 Hz, 3 H, CH-(CH3)2], 0.67 (dd, JH,H ϭ 6.6, JH,P ϭ 9.4 Hz, 3
H, C4H3), 0.69 [d, JH,H ϭ 6.6 Hz, 3 H, CH-(CH3)2], 1.03 [d,
3
2JH,H ϭ 14.8 Hz, 1 H, PCH), 3.46 (dt, 3JH,H ϭ 4.0, 2JH,P ϭ 2JH,H ϭ
3JH,H ϭ 6.6 Hz, 3 H, CH-(CH3)2], 1.17 [d, JH,H ϭ 6.6 Hz, 3 H,
3
3
14.8 Hz, 1 H, PCH), 3.61 [m, 1 H, CH-(CH3)2], 3.90 (d, JH,H
ϭ
CH-(CH3)2], 2.68 [sept, 3JH,H ϭ 6.6 Hz, 1 H, CH-(CH3)2], 2.83 (dd,
5.9 Hz, 1 H, H3s), 4.19 (m, NCH), 4.35 (dt, JH,H ϭ 2.1, JH,P
ϭ
2
3
2JH,H ϭ 1.9, 3JH,H ϭ 12.2 Hz, 1 H, H3a), 3.20 [sept, 3JH,H ϭ 6.4 Hz,
3JH,H ϭ 8.1 Hz, 1 H, H1a), 6.02 (apparent tt, 3JH2,H1s ϭ 3JH2,H3s ϭ
3
2
2
3
3
6.4, JH2,H1a
ϭ ϭ
3JH2,H3a ϭ 12.9 Hz, 1 H, H2), 6.47 (d, JH,H
1 H, CH-(CH3)2], 3.27 (dt, JH,H ϭ 3.0, JH,P ϭ JH,H ϭ 15.0 Hz,
3
2
2
1 H, PCH), 3.55 (dt, JH,H ϭ 3.5, JH,P ϭ JH,H ϭ 14.8 Hz, 1 H,
PCH), 4.10 (dd, 2JH,H ϭ 2.6, 3JH3s,H2 ϭ 7.0 Hz, 1 H, H3s), 4.14 (m,
1 H, NCH), 4.75 (m, 1 H, H1a), 5.34 (dt, 3JH2,H3s ϭ 7.0, 3JH2,H1a ϭ
3JH2,H3a ϭ 12.4 Hz, 1 H, H2), 6.26 (d, 3JH,H ϭ 10.9 Hz, 1 H, NH),
6.94Ϫ7.47 (m, merged with other diastereomers aromatic protons,
Harom) ppm. 13C{1H} NMR (125.7 MHz, CDCl3): δ ϭ 15.7 (d,
3JC,P ϭ 4 Hz, C4), 23.1 [CH-(CH3)2], 24.3 [CH-(CH3)2], 24.9 [CH-
(CH3)2], 25.2 [CH-(CH3)2], 28.2 [CH-(CH3)2], 29.2 [CH-(CH3)2],
9.8 Hz, 1 H, NH), 6.88Ϫ7.76 (m, merged with major diastereomer
aromatic proton, Harom) ppm. 13C{1H} NMR: δ ϭ 23.4 [CH-
(CH3)2], 23.7 [CH-(CH3)2], 24.2 [CH-(CH3)2], 24.4 [CH-(CH3)2],
28.2 [2 CH-(CH3)2], 35.7 (d, JC,P ϭ 25 Hz, PCH2), 53.4 (C3), 66.9
2
3
2
(d, JC,P ϭ 5 Hz, NCH), 80.6 (d, JC,P ϭ 29 Hz, C1), 122.2 (d,
3JC,P ϭ 5 Hz, C2), 124.4Ϫ139.8 (m, 24C, Carom) ppm. 31P{1H}
NMR: δ ϭ 29.61 (s) ppm.
2
2
Complexes 3Ϫ6 were synthesised by following the same procedures
as described above for the preparation of complex 2.
35.4 (d, JC,P ϭ 25 Hz, PCH2), 49.3 (d, JC,P ϭ 4 Hz, C3), 66.6 (d,
2
2
3JC,P ϭ 8 Hz, NCH), 99.5 (d, JC,P ϭ 26 Hz, C1), 119.3 (d, JC,P
ϭ
5 Hz, C2), 124.2Ϫ141.5 (m, 24C, Carom) ppm. 31P{1H} NMR
(202.5 MHz, CDCl3): δ ϭ 30.74 (s), Ϫ142.74 (sept, 1JF,P ϭ 716 Hz,
PF6Ϫ) ppm. Minor trans-P Isomer (4b, 9%): 1H NMR: δ ϭ 1.26
[Pd(η3-CH2CHCHMe)(Ph2PCH2CHPhNHPh)][PF6] (3): Starting
materials: [Pd(η3-MeC3H4)Cl]2 (54 mg, 0.14 mmol), L1 (104 mg,
0.27 mmol) and NaPF6 (95 mg, 0.56 mmol). Yield: 0.164 g (88%).
C30H31F6NP2Pd (687.9): calcd. C 52.37, H 4.54, N 2.04; found C
(dd, JH,H ϭ 6.6, JH,P ϭ 9.5 Hz, 3 H, C4H3), 2.92 (br. d, JH,H
ϭ
3
4
3
10.5 Hz, H3a), 3.67 (dd, JH,H ϭ 2.4, JH3s,H2 ϭ 6.2 Hz, 1 H, H3s),
2
3
1
4.05 (m, 1 H, H1a) 5.72 (dt, JH2,H3s ϭ 6.8, JH2,H1a ϭ JH2,H3a
ϭ
3
3
3
52.23, H 4.89, N 2.34. Major trans-P isomer (3a, 53%): H NMR
3
4
3
12.4 Hz, 1 H, H2), 6.22 (d, JH,H ϭ 10.9 Hz, 1 H, NH) ppm.
(CDCl3, 500.13 MHz): δ ϭ 0.66 (dd, JH,H ϭ 6.3, JH,P ϭ 9.3 Hz,
2
3
3 H, C4H3), 2.56 (dd, JH,H ϭ 2.1, JH,H ϭ 11.8 Hz, 1 H, H3a),
3
2
13C{1H} NMR: δ ϭ 16.9 (d, JC,P ϭ 5 Hz, C4), 30.6 (d, JC,P
ϭ
3
2
2.96 (dt, JH,H ϭ 2.9, JH,P
ϭ
2JH,H ϭ 14.6 Hz, 2 H, PCH and
24 Hz, PCH2), 49.1 (broad, C3), 66.8 (d, 3JC,P ϭ 7 Hz, NCH), 103.3
PCHЈ), 3.32 (dt, 3JH,H ϭ 2.6, 2JH,P ϭ 2JH,H ϭ 14.3 Hz, 1 H, PCH),
(d, JC,P ϭ 27 Hz, C1), 119.2 (d, JC,P ϭ 6 Hz, C2) ppm. 31P{1H}
2
2
2
3
3.79 (dd, JH,H ϭ 2.6, JH,H ϭ 6.8 Hz, 1 H, H3s), 3.94 (m, 1 H,
NMR: δ ϭ 28.90 (s) ppm. cis-P isomer (4c, 9%): 1H NMR: δ ϭ
NCH), 4.98 (m, 1 H, H1a), 5.23 (dt, JH,H ϭ 6.3, JH,H ϭ JH,H
ϭ
3
3
3
1.62 (dd, 3 H, JH,H ϭ 6.6, JH,P ϭ 9.0 Hz, C4H3), 3.52 (masked,
3
4
14.6 Hz, 1 H, H2), 6.21 (d, JH,H ϭ 11.4 Hz, 1 H, NH), 6.87Ϫ7.83
3
3
3
H1s), 3.84 (dd, JH,P ϭ 9.5, JH1a,H2 ϭ 13.5 Hz, 1 H, H1a), 4.16
(masked, H3a), 5.61 (dt, JH2,H3s ϭ 7.7, JH2,H1a
ϭ
3JH2,H3a
ϭ
3
3
(m, merged with others diastereomers aromatic protons, Harom
)
ϭ
ppm. 13C{1H} NMR (125.7 MHz, CDCl3): δ ϭ 14.1 (d, JC,P
3
3
12.2 Hz, 1 H, H2), 6.41 (d, JH,H ϭ 10.9 Hz, 1 H, NH) ppm.
2
2
4 Hz, C4). 35.9 (d, JC,P ϭ 23 Hz, PCH2), 46.7 (d, JC,P ϭ 4 Hz,
13C{1H} NMR: δ ϭ 19.6 (C4), 66.3 (d, JC,P ϭ 7 Hz, NCH), 72.6
3
3
2
C3), 68.4 (d, JC,P ϭ 10 Hz, NCH), 102.9 (d, JC,P ϭ 26 Hz, C1),
(d, 2JC,P ϭ 4 Hz, C3), 76.3 (d, 2JC,P ϭ 27 Hz, C1), 122.5 (d, 2JC,P ϭ
2
116.2 (d, JC,P ϭ 5 Hz, C2), 121.4Ϫ144.1 (m, 24C, Carom) ppm.
5 Hz, C2) ppm. 31P{1H} NMR: δ ϭ 28.35 (s) ppm. cis-P isomer
31P{1H} NMR (202.5 MHz, CDCl3): δ ϭ 32.95 (s), Ϫ142.69 (sept,
1JF,P ϭ 716 Hz, PF6Ϫ) ppm. Minor trans-P isomer (3b, 30%): 1H
NMR: δ ϭ 1.04 (dd, 3JH,H ϭ 6.3, 4JH,P ϭ 9.1 Hz, 3 H, C4H3), 2.82
1
(4d, 4%): H NMR: δ ϭ 2.80 (masked, H), 4.03 (masked, H), 5.78
3
3
3
(dt, JH2,H3s ϭ 7.7, JH2,H1a ϭ JH2,H3a ϭ 12.2 Hz, 1 H, H2), 5.83
(d, JH,H ϭ 10.9 Hz, 1 H, NH) ppm. 31P{1H} NMR: δ ϭ 25.44
3
3
3
2
(d, JH,H ϭ 10.1 Hz, 1 H, H3a), 3.18 (dt, JH,H ϭ 3.2, JH,P
ϭ
(s) ppm.
2JH,H ϭ 14.6 Hz, 1 H, PCH), 3.54 (dd, 2JH,H ϭ 2.2, 3JH,H ϭ 6.8 Hz,
1 H, H3s), 3.92 (m, 1 H, H1a), 4.08 (m, 1 H, NCH), 5.58 (dt,
[Pd(η3-CH2CHCHPh)(Ph2PCH2CHPhNHPh)][PF6] (5): Starting
3JH,H ϭ 6.9, 3JH2,H1a ϭ 3JH,H ϭ 13.8 Hz, 1 H, H2), 5.87 (d, 3JH,H ϭ materials: [Pd(η3-PhC3H4)Cl]2 (54 mg, 0.10 mmol), L1 (80 mg,
11.3 Hz, NH), 6.96Ϫ7.91 (m, merged with others diastereomers
0.21 mmol) and NaPF6 (43 mg, 0.26 mmol). Yield: 0.133 g (85%).
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2004, 1081Ϫ1091

Allylpalladium(II) Complexes with Aminophosphane Ligands
FULL PAPER
4.05 (m, 1 H, NCH), 4.23 (t, JH,P ϭ JH,H ϭ 7.3 Hz, 1 H, H1s),
3
3
C35H33F6NP2Pd (750.0): calcd. C 56.06, H 4.40, N 1.90; found C
1
3
55.92, H 4.79, N 2.41. Major trans-P isomer (5a, 55%): H NMR 4.86 (d, JH,H ϭ 11.8 Hz, 1 H, H3a), 6.40 (m, 1 H, H2), 6.44 (d,
(CDCl3, 500.13 MHz): δ ϭ 2.77 (d, 3JH,H ϭ 8.1 Hz, 1 H, H3a), 2.90
3JH,H ϭ 10.7 Hz, 1 H, NH), 6.85Ϫ7.79 (m, merged with other dia-
stereomers aromatic protons, Harom) ppm. 13C{1H} NMR: δ ϭ 23.3
2
2
2
2
(t, JH,P ϭ JH,H ϭ 14.6 Hz, 1 H, PCH), 3.40 (t, JH,P ϭ JH,H
ϭ
13.9 Hz, 1 H, PCH), 3.88 (m, 2 H, NCH and H3s), 5.82 (m, 2 H, [CH-(CH3)2] 24.6 [CH-(CH3)2], 25.6 [CH-(CH3)2], 25.9 [CH-
H2 and H1a), 5.93 (d, JH,H ϭ 11.1 Hz, 1 H, NH), 6.23Ϫ7.92 (m,
(CH3)2], 28.0 [CH-(CH3)2], 29.4 [CH-(CH3)2], 35.5 (d, JC,P
ϭ
3
2
3
merged with other diastereomers aromatic protons, Harom) ppm.
21 Hz, PCH2), 66.5 (d, JC,P ϭ 8 Hz, NCH), 76.1 (d, 2JC,P ϭ 5 Hz,
2
2
2
13C{1H} NMR (125.7 MHz, CDCl3): δ ϭ 37.1 (d, JC,P ϭ 24 Hz, C3), 76.6 (d, JC,P ϭ 27 Hz, C1), 118.8 (d, JC,P ϭ 6 Hz, C2),
3
2
PCH2), 48.8 (C3), 69.7 (d, JC,P ϭ 10 Hz, NCH), 104.7 (d, JC,P
ϭ
124.8Ϫ141.0 (Carom) ppm. 31P{1H} NMR: δ ϭ 29.68 (s) ppm. Iso-
24 Hz, C1), 111.3 (d, JC,P ϭ 5 Hz, C2), 120.8Ϫ142.9 (m, 30 C, mer trans-P (6a, 9%): H NMR: δ ϭ 2.79 (d, JH,H ϭ 11.9 Hz, 1
2
1
3
Carom) ppm. 31P{1H} NMR (202.5 MHz, CDCl3): δ ϭ 35.50 (s),
H, H3a), 3.62 (d, JH,H ϭ 6.8 Hz, 1 H, H3s), 5.68 (dt, JH,H ϭ 7.0,
3
3
Ϫ142.70 (sept, JF,P ϭ 716 Hz, PF6Ϫ) ppm. Minor trans-P isomer 3JH,H ϭ 11.9 Hz, 1 H, H2), 5.95 (dt, JH,H ϭ 8.9, JH,P ϭ 13.7 Hz,
1
3
3
(5b, 22%): 1H NMR: δ ϭ 3.04 (d, 3JH,H ϭ 10.8 Hz, 1 H, H3a), 3.32 1 H, H1a) ppm. 31P{1H} NMR: δ ϭ 31.60 (s) ppm. Isomer trans-
(m, 2 H, PCH2), 3.62 (d, 3JH,H ϭ 5.9 Hz, 1 H, H3s), 3.99 (m, NCH),
P (6b, 7%): 1H NMR: δ ϭ 2.84 (masked, H3a), 4.92 (dt, JH,H
ϭ
3
4.67 (t, 3JH,P ϭ 3JH,H ϭ 9.9 Hz, 1 H, H1a), 5.38 (d, 3JH,H ϭ 10.9 Hz, 9.9, JH,P ϭ 13.7 Hz, 1 H, H1a), 6.40 (masked, H2) ppm. 31P{1H}
3
1 H, NH), 6.20 (m, H2), 6.19Ϫ7.88 (m, merged with other dia-
stereomers aromatic protons, Harom) ppm. 13C{1H} NMR: δ ϭ 37.8
(d, 2JC,P ϭ 24 Hz, PCH2), 49.8 (C3), 69.7 (d, 3JC,P ϭ 10 Hz, NCH),
NMR: δ ϭ 32.33 (s) ppm.
Crystal Structure Determination for 6: Crystal and refinement data
are reported in Table 4. The data set was collected on an
EnrafϪNonius KappaCCD diffractometer at 110 K using Mo-Kα
radiation. The structure was solved with a Patterson search pro-
gram[61] and refined with full-matrix least-squares methods[62]
based on |F2| with the aid of the WINGX program.[63] The allylic
fragment (CH2···CH···CHPh) was found to be disordered with two
different orientations (endo/exo). The occupation factors refined to
m1 ϭ 0.78 (endo isomer) and m2 ϭ 1 Ϫ m1 ϭ 0.22 (exo isomer).
104.6 (d, JC,P ϭ 24 Hz, C1), 115.0 (d, JC,P ϭ 5 Hz, C2),
121.4Ϫ147.3 (Carom) ppm. 31P{1H} NMR: δ ϭ 33.45 (s) ppm. Iso-
mer cis-P (5c, 12%): 1H NMR: δ ϭ 4.25 (t, 3JH,P ϭ 3JH,H ϭ 7.2 Hz,
2
2
1 H, H1s), 4.47 (dd, JH,H ϭ 9.9, JH,P ϭ 13.6 Hz, 1 H, H1a), 4.81
3
3
(d, JH,H ϭ 11.5 Hz, 1 H, H3a), 6.19 (masked, H2) ppm. 13C{1H}
3
2
3
NMR: δ ϭ 36.3 (d, JC,P ϭ 25 Hz, PCH2), 67.7 (d, JC,P ϭ 10 Hz,
NCH), 73.9 (d, 2JC,P ϭ 5 Hz, C3), 80.7 (d, 2JC,P ϭ 26 Hz, C1), 116.7
(d, JC,P ϭ 5 Hz, C2) ppm. 31P{1H} NMR: δ ϭ 25.86 (s) ppm.
2
Isomer cis-P (5d, 11%): 1H NMR: δ ϭ 3.08 (dd, JH,H ϭ 9.4,
3
3JH,P ϭ 13.7 Hz, 1 H, H1a), 3.85 (masked, H3s), 4.62 (d, JH,H
ϭ
3
Table 4. Crystallographic and refinement data for complexes 6
11.5 Hz, 1 H, H3a), 5.83 (masked, H2) ppm. 13C{1H} NMR: δ ϭ
36.3 (d, 2JC,P ϭ 25 Hz, PCH2), 68.1 (d, 3JC,P ϭ 10 Hz, NCH), 74.6
(d, 2JC,P ϭ 5 Hz, C3), 82.0 (d, 2JC,P ϭ 25 Hz, C1), 119.6 (d, 2JC,P ϭ
5 Hz, C2) ppm. 31P{1H} NMR: δ ϭ 25.61 (s) ppm.
Formula
C41H45NPPd·PF6·0.5(CH2Cl2)
Mol. mass
T (K)
876.58
110(2)
Crystal system
Space group
monoclinic
C2/c
13.8841(2)
17.5047(2)
33.1026(5)
95.590(1)
8006.9(2)
8
[Pd(η3-CH2CHCHPh){Ph2PCH2CHPhNH(2,6-C6H3iPr2)}][PF6]
(6): Starting materials: [Pd(η3-PhC3H4)Cl]2 (64 mg, 0.12 mmol), L2
(115 mg, 0.25 mmol) and NaPF6 (81 mg, 0.48 mmol). Yellow crys-
tals suitable for X-ray diffraction were obtained from dichloro-
methane solution by layering with pentane. Yield: 0.172 g (82%).
C41H46F6NP2Pd (835.2): calcd. C 58.96, H 5.55, N 1.67; found C
˚
a (A)
˚
b (A)
˚
c (A)
β (deg)
3
˚
V (A )
Z
F(000)
1
59.19, H 5.78, N 1.94%. Major cis-P isomer (6c, 63%): H NMR
3592
1.454
3
(CDCl3, 500.13 MHz): δ ϭ 0.32 [d, JH,H ϭ 6.4 Hz, 3 H, CH-
Dcalcd. (g/cm3)
Diffractometer
Scan type
(CH3)2], 0.61 [d, 3JH,H ϭ 6.7 Hz, 3 H, CH-(CH3)2], 1.11 [d, 3JH,H ϭ
EnrafϪNonius KappaCCD
mixture of ϕ rotations and ω scans
0.71073
3
6.7 Hz, 3 H, CH-(CH3)2], 1.17 [d, JH,H ϭ 6.5 Hz, 3 H, CH-
3
˚
(CH3)2], 2.86 [sept, JH,H ϭ 6.7 Hz, 1 H, CH-(CH3)2], 3.02 (dt,
λ (A)
2
2
3JH,H ϭ 2.8, JH,P ϭ JH,H ϭ 14.8 Hz, 1 H, PCH), 3.41 [m, 1 H,
µ (mmϪ1
)
0.669
0.35 ϱ 0.25 ϱ 0.20
0.65
h: Ϫ17; 18
k: Ϫ21; 22
l: Ϫ42; 42
SCALEPACK
16441
9042 [R(int) ϭ 0.032]
6538
CH-(CH3)2], 3.66 (dt, JH,H ϭ 3.4, JH,P ϭ JH,H ϭ 14.8 Hz, 1 H, Crystal size (mm3)
3
2
2
Ϫ1
˚
3
PCH), 3.83 (dd, 3JH,P ϭ 6.1, JH,H ϭ 7.8 Hz, 1 H, H1s), 3.97 (m, 1
sin(θ)/λ max (A
)
3
3
H, NCH), 4.41 (dd, JH,P ϭ 8.8, JH1a,H2 ϭ 13.8 Hz, 1 H, H1a),
Index ranges
4.79 (d, JH,H ϭ 11.8 Hz, 1 H, H3a), 6.20 (ddd, JH2,H1s ϭ 7.9,
3
3
3JH2,H3a ϭ 11.8, JH2,H1a ϭ 13.7 Hz, 1 H, H2), 6.62 (d, JH,H
10.8 Hz, 1 H, NH), 6.79Ϫ7.79 (m, merged with other diastereomers
aromatic protons, Harom
ppm. 13C{1H} NMR (125.7 MHz,
ϭ
3
3
Absorption correction
RC ϭ Refl. Collected
IRC ϭ independent RC
IRCGT ϭ IRC and
[I Ͼ 2σ(I)]
)
CDCl3): δ ϭ 23.0 [CH-(CH3)2], 23.8 [CH-(CH3)2], 25.8 [CH-
(CH3)2], 25.9 [CH-(CH3)2], 27.9 [CH-(CH3)2], 29.5 [CH-(CH3)2],
2
3
35.2 (d, JC,P ϭ 24 Hz, PCH2), 67.0 (d, JC,P ϭ 8 Hz, NCH), 74.6 Refinement method
Full-matrix L.S. on F2
9042/9/506
(d, 2JC,P ϭ 6 Hz, C3), 79.4 (d, 2JC,P ϭ 25 Hz, C1), 116.4 (d, 2JC,P ϭ
5 Hz, C2), 124.7Ϫ140.8 (m, 30 C, Carom) ppm. 31P{1H} NMR
(202.5 MHz, CDCl3): δ ϭ 21.85 (s), Ϫ142.62 (sept, 1JF,P ϭ 716 Hz,
Data/restraints/parameters
R for IRCGT
R1[a] ϭ 0.0419, wR2[b] ϭ 0.0938
R1[a] ϭ 0.0697, wR2[b] ϭ 0.1032
1.067
R for IRC
Goodness-of-fit[c]
Largest diff. peak and hole
1
PF6Ϫ) ppm. Minor cis-P isomer (6d, 22%): H NMR: δ ϭ 0.28 [d,
0.80 and Ϫ1.10
3
3JH,H ϭ 6.4 Hz, 3 H, CH-(CH3)2], 0.70 [d, JH,H ϭ 6.7 Hz, 3 H,
Ϫ3
˚
(e·A
)
3
CH-(CH3)2], 1.20 [d, JH,H ϭ 6.6 Hz, 3 H, CH-(CH3)2], 1.27 [d,
3JH,H ϭ 6.7 Hz, 3 H, CH-(CH3)2], 2.80 [sept, 3JH,H ϭ 6.7 Hz, 1 H,
[a] R1 ϭ Σ(||Fo|Ϫ|Fc||)/Σ|Fo|. [b] wR2 ϭ [Σw(Fo2 ϪFc ) /Σ[w(Fo2) ]
,
2 2
2 2 1/2
3
CH-(CH3)2], 2.99 (m, 2 H, PCH and H3s), 3.52 (dt, JH,H ϭ 3.6,
where w ϭ 1/[σ2(Fo ) ϩ (0.045P)2 ϩ 4.95P] and P ϭ [Max(Fo ,0) ϩ
2
2
2
[c]
2
2 2
2JH,P ϭ JH,H ϭ 14.7 Hz, 1 H, PCH), 3.78 [m, 1 H, CH-(CH3)2],
2*Fc )/3.
Goodness of fit ϭ [Σw(Fo Ϫ Fc ) /(No Ϫ NH2,H3a)]1/2
.
Eur. J. Inorg. Chem. 2004, 1081Ϫ1091
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1089

J.-M. Camus, J. Andrieu, P. Richard, R. Poli
FULL PAPER
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ameters except for the atoms belonging to the minor allylic frag-
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fragment. The positions of the hydrogen atoms were either calcu-
lated or located in final Fourier difference maps and refined, after
idealisation, with a riding model with isotropic temperature factors
fixed to 1.5- or 1.2-times those of the corresponding parent atoms.
CCDC-218899 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
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