Structural aspects of palladium and platinum complexes with chiral diphosphinoferrocenes relevant to the regio- and stereoselective copolymerization of CO with propene

Article abstract of DOI:10.1002/1522-2675(20011017)84:10<3105::AID-HLCA3105>3.0.CO;2-L

A series of chiral diphosphinoferrocene ligands 3a-i, derived from josiphos (=(2R)-1-[(1R)-1-(dicyclohexylphosphino)ethyl]-2-(diphenylphosphino) ferrocene, formerly called {(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}dicycloxexylphosphine) where the electronic properties of the ligand are systematically varied, were prepared. X-Ray studies of five of these new ligands confirmed that these compounds display very similar conformations in the solid state and that no structural criteria could be found indicating the modified electronic properties. These ligands find application in the Pd-catalyzed highly regio- and stereoselective CO/propene copolymerization reaction, where the electronic properties of the ligand show a great impact on the catalyst activity. Coordination-chemical aspects of these diphosphinoferrocenes relevant to the CO/propene copolymerization reaction were addressed by the preparation and characterization of Pd- and Pt-complexes of the general formula [PdCl₂(P-P)] (5), [PdMe₂(P-P)] (6), [PdClMe(P-P)] (7), [PdMe(MeCN)(P-P)]PF₆ (8), and [PtClMe(P-P)] (9) (P-P = chiral diphosphinoferrocene ligand (3a-h), four of which were characterized by X-ray crystallography.

Full text of DOI:10.1002/1522-2675(20011017)84:10<3105::AID-HLCA3105>3.0.CO;2-L

Helvetica Chimica Acta ± Vol. 84 (2001)
3105
Structural Aspects of Palladium and Platinum Complexes With Chiral
Diphosphinoferrocenes Relevant to the Regio- and Stereoselective
Copolymerization of CO with Propene
by C e line Gambs, Giambattista Consiglio, and Antonio Togni*
Department of Chemistry, Swiss Federal Institute of Technology, Hönggerberg, CH-8093 Zürich
(
Tel.: 016322236; e-mail: togni@inorg.chem.ethz.ch)
Dedicated to the memory of Luigi M. Venanzi, mentor, colleague, and friend
A
series of chiral diphosphinoferrocene ligands 3a ± i, derived from josiphos (ˆ(2R)-1-[(1R)-1-
(
dicyclohexylphosphino)ethyl]-2-(diphenylphosphino)ferrocene, formerly called {(R)-1-[(S)-2-(diphenylphos-
phino)ferrocenyl]ethyl}dicycloxexylphosphine) where the electronic properties of the ligand are systematically
varied, were prepared. X-Ray studies of five of these new ligands confirmed that these compounds display very
similar conformations in the solid state and that no structural criteria could be found indicating the modified
electronic properties. These ligands find application in the Pd-catalyzed highly regio- and stereoselective CO/
propene copolymerization reaction, where the electronic properties of the ligand show a great impact on the
catalyst activity. Coordination-chemical aspects of these diphosphinoferrocenes relevant to the CO/propene
copolymerization reaction were addressed by the preparation and characterization of Pd- and Pt-complexes of
the general formula [PdCl
8), and [PtClMe(P� P)] (9) (P� P ˆ chiral diphosphinoferrocene ligand (3a ± h), four of which were
characterized by X-ray crystallography.
2
(P� P)] (5), [PdMe
2
(P� P)] (6), [PdClMe(P� P)] (7), [PdMe(MeCN)(P� P)]PF
6
(
1. Introduction. ± Among the different classes of chiral phosphine ligands available
for asymmetric catalysis, planar chiral phosphinoferrocenes (ˆ ferrocenylphosphines)
belong to the most important ones. They have been successfully used in a variety of
transition metal catalyzed reactions [1 ± 5]. In particular, ligands of the josiphos type [6]
(
josiphos ˆ (2R)-1-[(1R)-1-(dicyclohexylphosphino)ethyl]-2-(diphenylphosphino)fer-
1
rocene ); 3a), i.e., chelating diphosphines comprising two different phosphino groups,
have reached the stage of large-scale industrial applications [7 ± 9].
Very recently, Blaser et al. reported a study of the tuning of ligands of the josiphos
family for the Ir-catalyzed hydrogenation of imines [10]. We had previously
demonstrated that the introduction of peripheral substituents into such ligands may
drastically influence the stereoselectivity of various reactions [11 ± 13]. The diphenyl-
phosphino group is easily amenable to directed modifications of the donor properties of
the P-atom via introduction of electron-donating or -withdrawing groups at the Ph
rings, therefore increasing or diminishing the ꢀelectronic asymmetryꢁ [11] of the ligand.
For small substituents, typically placed in para position, one can assume a negligible
effect on the overall steric features of the ligand, and one is thus in the situation of
investigating, from a purely empirical point of view, ligand electronic effects in
1)
josiphos was formerly called {(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}dicyclohexylphosphine
6].
[

3106
Helvetica Chimica Acta ± Vol. 84 (2001)
asymmetric catalysis. As we recently reported, the electronic nature of such modified
josiphos ligands in the stereoselective Pd-catalyzed CO/propene copolymerization
[14][15] is of great importance in determining the relative activity of the corresponding
catalyst. This means that ligand modifications in electronic terms may seriously alter
the kinetics of the catalytic process. However, to pinpoint the nature of such an
electronic effect, one would need a very detailed knowledge of the reaction mechanism,
unfortunately often not available. Nevertheless, discernable structural ± ground state,
thermodynamic ± effects concerning the involved species may be expected [12]. In this
context, we report the preparation and structural characterization of a series of
II
II
modified josiphos ligands, as well as of their Pd and Pt complexes which are model
compounds relevant to the Pd-catalyzed CO/propene copolymerization.
2
. Results and Discussion. ± 2.1. Synthesis and Characterization of Ligands. The
planar-chiral diphosphinoferrocene ligands 3a ± h (Scheme 1) were prepared by a two-
step procedure [6] starting from the commercially available, enantiomerically pure
(aminoethyl)ferrocene 1. ortho-Lithiation of 1 occurred diastereoselectively [16], and
subsequent treatment with a diaryl(chloro)phosphine generated in moderate to fair
yield (33 ± 64%) the expected derivatives 2a ± h that were isolated each as single
stereoisomer after chromatography and/or recrystallization [17] (Scheme 1). We
limited our attention to Me, CF , and MeO substituents at the aryl moieties because
3
of their relatively small size, relative inertness, and availability of the required
precursors. However, the nature of the substituents may significantly influence the
yield of the functionalization step of (aminoethyl)ferrocene 1, with the more basic
diaryl(chloro)phosphines giving poorer yields. This can be partially explained by the
increased sensitivity to oxidation and, therefore, loss of product during workup, as no
Scheme 1

Helvetica Chimica Acta ± Vol. 84 (2001)
3107
specific precaution was adopted. On the other hand, the presence of electron-donating
groups renders the diaryl(chloro)phosphine less electrophilic and thus less prone to
react with the ferrocene nucleophile. Upon reaction of the racemic chlorophosphane
ClPPh[3,5-(CF ) C H ] with the lithiated form of 1, the corresponding diastereoiso-
3
2
6
3
meric products 2i and 2i , containing a stereogenic P-atom, were formed in equal
a
b
amounts; they could easily be separated by column chromatography.
The introduction of the second phosphino fragment was achieved by nucleophilic
substitution at the ethyl group of 2, which is known to proceed with retention of
configuration at the stereogenic C-center [18]. Derivatives 2a ± h were treated in
AcOH at 1008 with the secondary phosphine HPCy (Cy ˆ cyclohexyl) giving the
2
corresponding diphosphino ligands 3a ± h in good to high yields (up to 93%). The
diphosphinoferrocenes 3a ± h are air-stable and can be stored for a long time without
noticeable oxidation or decomposition.
When the diastereoisomerically pure 2i was reacted at 1008 with HPCy in AcOH,
b
2
it did not retain completely its stereochemical integrity, as partial epimerization at the
P-atom occurred, due to the high temperature required for the reaction. The 31P{ H}-
NMR spectrum of the resulting diastereoisomer mixture 3i /3i revealed a degree of
1
a
b
epimerization of ca. 20%. Attempts to separate the pairs of diastereoisomeric
diphosphinoferrocenes by column chromatography failed. After conversion to the
bis(borane) adduct, a stereochemically pure derivative 4 (ˆ [3i ´ 2 BH ] could be
b
3
obtained as the major product after chromatography, which was structurally
characterized (vide infra, Fig. 3). However, attempts at deprotecting this compound
with morpholine under mild conditions, in order to avoid epimerization, failed, as the
PCy2 group always retained the borane. Due to these synthetic difficulties, the
chemistry with this new P-stereogenic phosphine was not pursued.
Table 1 collects a selection of characteristic spectroscopic features of the modified
31
josiphos ligands, as compared to the parent compound 3a [6]. In their P-NMR spectra,
Table 1. Selected Spectroscopic Properties of the Diphosphino Derivatives 3a ± i (all of absolute configuration
(
R,R)). d in ppm, J in Hz.
3
1
1
a
1H-NMR
d(C
20 c
D
Ligand
P{ H}-NMR )
[a]
)
d(P)
PCy
5
H
5
)
d(MeCHP)b)
PAr
2
4J(P,P)
2
d
3
3
3
3
3
3
3
3
3
3
a (josiphos) )
15.6
15.8
16.7
16.2
15.6
15.6
15.6
15.6
14.3
15.9
� 25.1
� 34.8
� 24.2
� 24.9
� 25.1
� 25.1
� 25.1
� 25.1
� 25.9
� 24.1
36.9
58.7
47.3
46.0
52.0
37.5
32.0
37.9
42.9
47.9
3.93
3.91
3.82
3.83
3.75
3.97
4.01
4.05
3.83
3.86
3.68
3.59
3.54
3.56
3.42
3.72
3.69
3.71
3.57
3.35
� 352
� 360
� 267
� 349
� 288
� 305
� 338
� 281
e
b (o-CF
c (m-CF
3
) )
e
3
) )
e
d (p-CF
3
) )
e
e ((m-CF
3
)
2
) )
e
f ((m-Me)
2
) )
e
g (p-MeO) )
e
2
h ((m-MeO) ) )
(Ph/(m-CF
(Ph/(m-CF
e
f
i
i
a
3
)
2
) )
n.d. )
e
f
b
3
)
2
) )
n.d. )
a
Each P-signal appears as a d (except, for 3b). b) MeCHP appear as dq. c) c ˆ 0.46 ± 0.62 g/cm in CHCl
3
)
3
.
d) Data from [19]. ) The peripheral substituents at the aryl moieties are indicated in parentheses. ) Not
e
f
determined.

3108
Helvetica Chimica Acta ± Vol. 84 (2001)
3
a ± i display an AX spin system, with a relatively large four-bond coupling constant
4
J(P,P), ranging from 32.0 Hz for the p-MeO derivative 3g to 58.7 Hz for the o-CF3
derivative 3b. This latter compound also shows an anomalous high-field shift of ca.
1
0 ppm of the P(Aryl) P-atom with respect to the corresponding signal of all other
2
derivatives, as well as coupling of this P-atom to the F-atoms of the CF groups.
3
2
.2. Solid-State Structure of the Diphosphino Derivatives 3b, 3d, 3e, 3g, 3h, and 4. To
define possible structural consequences of the introduction of peripheral substituents at
the diphosphinoferrocenes of type 3, X-ray crystallographic studies were carried out.
Suitable single crystals could be obtained for the ligands 3b, 3d, 3e, 3h, and 4 by
t
recrystallization from EtOH and for 3g from a BuOMe/EtOH solution layered with
hexane. Due to the structural similarities between these derivatives, only two
representative ORTEP views of the diphosphinoferrocenes 3b and 3h are presented
in Figs. 1 and 2, respectively. The bonding parameters fall in the expected ranges and
are well comparable to those of the parent compound josiphos [19]. From a
conformational point of view, the five diphosphinoferrocenes 3 analyzed are very
similar as far as the conformation of the substituted common backbone is concerned. In
fact, in all compounds, the two aryl groups, here defined as ꢀendoꢁ (pointing toward the
ferrocene moiety) and ꢀexoꢁ (away from the ferrocene) can be viewed as assuming a
pseudoequatorial and pseudoaxial orientation, respectively, as is the case of josiphos.
The position of the PCy group can also be viewed as being pseudoaxial and pointing
2
away from the ferrocene. Furthermore, in all ligands, the Me group at the stereogenic
center is positioned below the plane of the substituted Cp ring (i.e., ꢀendoꢁ). This
conformational preference is well illustrated by the torsion angles given in Table 2.
Significant differences are, however, observed when focusing on the Cy and, to a lesser
extent, on the aryl groups, as visualized by the two structures of Figs. 1 and 2. This
means that there appear to be essentially no restrictions to rotations around the P� Cy
bonds, and that, therefore, this peripheral part of the molecule is conformationally very
flexible. Furthermore, one observes slight displacements of the stereogenic C-atom
(
0.013 ± 0.038 Š) and of the PAr P-atom (0.02 ± 0.1 Š) from the plane of the Cp ring
2
away from the Fe-atom. The small dislocation of the P-atom indirectly implies that the
2
Table 2. Relevant Torsions Angles [8] and Sum of Bond Angles for the PAr Group in Compounds 3a, 3b, 3d, 3e,
3
g, and 3h
a
3
a )
3b
3d
3e
3g
3h
�
24
� 29
� 34
� 15
� 14
� 17
�
70
� 76
� 80
� 59
� 62
� 64
Sum of C� P� C angles for Cp� P(Aryl)
2
group
302.5
302.2
303.4
304.5
302.1
302.2
a) Data for comparison from [19].

Helvetica Chimica Acta ± Vol. 84 (2001)
3109
Fig. 1. ORTEP Drawing (30% probability ellipsoids) and atom-numbering scheme of ligand 3b
Fig. 2. ORTEP Drawing (30% probability ellipsoids) and atom-numbering scheme of ligand 3h
repulsion between the ꢀendoꢁ aryl group and the ferrocene fragment is negligible, as it
does not lead to a significant distorsion.
The introduction of substituents altering the electronic properties of the PAr group
2
could, in principle, change the degree of pyramidalization of the P-atom, as expressed
by the sum of the corresponding three C� P� C angles (Table 2). A larger sum of the
C� P� C angles, i.e., a less pyramidalized P-atom, should correlate with a decreasing s-
character of the P lone-pair, and this should be expected in the case of electron-

3110
Helvetica Chimica Acta ± Vol. 84 (2001)
withdrawing substituents. The experimental data in Table 2, however, show that the
ligands examined cover a very narrow range of C� P� C angles, between 302.1 and
304.48. Although the least degree of pyramidalization is shown, as expected from the
simple considerations made above, by derivative 3e bearing four CF3 groups, the
observed differences are too small and cannot be used as a reliable structural criterion
for judging the electronic effect of the substituents.
The crystal structure of 4 (Fig. 3) allows the assignment of the absolute
configuration (R) of its stereogenic P-atom (therefore, (R ,R ,R )-4). In this
P
C
Cp
compound, the ꢀexoꢁ-axial and ꢀendoꢁ-equatorial orientation of the two aryl groups is
more pronounced than for the other derivatives, probably due to the presence of BH3
attached to the corresponding P-atom. The relative position of the second BH is
3
indicative of the high conformational flexibility of the PCy group. In fact, as shown by
2
the relatively small torsion angle C(7)� C(6)� P(2)� B(2) of 38.48, the B-atom and the
Me group (C(7)) are syn-clinal, whereas a metal center coordinated to both P-atoms
assumes an almost anti-periplanar position with respect to C(7).
Fig. 3. ORTEP Drawing (30% probability ellipsoids) and atom-numbering scheme of compound 4 (ˆ [3i
BH ])
b
´
2
3
2
.3. Synthesis and Characterization of Pd and Pt Complexes. 2.3.1. Syntheses. The
rate of reaction in the CO/propene copolymerization reaction is drastically influenced
by the electronic characteristics of the P-aryl substituents of the ligand [15]. Typically,
II
the highest productivity was obtained with the Pd system modified with ligand
3e, bearing the electron-withdrawing CF3 substituents. Thus, a series of Pd- and
Pt-complexes of general formula [PdCl (P� P)] (5), [PdMe (P� P)] (6),
2
2
[
PdClMe(P� P)] (7), [PdMe(MeCN)(P� P)]PF6 (8), and [PtClMe(P� P)] (9) ±
where P� P is one of the chiral diphosphinoferrocene ligands 3a ± h ± were prepared by
conventional ligand substitution reactions (see Scheme 2 and Table 3). In the case of 5,
7
[21][22], and 9 [23], the corresponding cod (cod ˆ cycloocta-1,5-diene) derivatives

Helvetica Chimica Acta ± Vol. 84 (2001)
3111
Scheme 2
Table 3. Numbering Scheme for All Prepared and Characterized Pd- and Pt-Complexes Containing Ligands 3a ± ha)
Ligand
[PdCl
2
(P� P)] [PdMe
6aa)
2
(P� P)] [PdClMe(P� P)] [PdMe(MeCN)(P� P)]PF
6
[PtClMe(P� P)]
a
b
a
3
3
3
3
3
3
3
3
a (josiphos)
b (o-CF
c (m-CF
d (p-CF
e ((m-CF
f ((m-Me)
g (p-MeO) )
h ((m-MeO)
5a ) )
7a )
8a
9a
9b
9c
9d
9e
9f
c
3
) )
c
3
) )
c
3
) )
7d
7e
7f
8d
8e
) ) 5ea)
c
6e
3
)
2
c
2
) )
c
a
7g )
8g
c
2
) )
9h
a) An X-ray crystal structural study was carried out for 5a, 5e, 6a, 7a, and 7g. b) See [20]. c) The peripheral
substituents at the aryl moieties are indicated in parentheses.
were used as starting materials, whereas [PdMe (tmeda)] (tmeda ˆ N,N,N',N'-tetra-
2
1
methylethane-1,2-diamine) [24] served as precursor of 6. The H-NMR spectra for the
dimethylpalladium complexes 6a and 6e show the two Me ligands as a dd due to the
13
coupling with the two nonequivalent P-atoms. Their C-NMR spectra exhibit

3112
Helvetica Chimica Acta ± Vol. 84 (2001)
2
nonequivalent Me signals with J(P,C) coupling constants of ca. 10 and ca. 100 Hz for
cis and trans relationships of the P and Me ligands, respectively. The cationic complexes
8
were obtained in high yields as a mixture of stereoisomers I and II by ligand-
abstraction reaction with TlPF from 7 in CH Cl in the presence of a small amount of
6
2
2
MeCN.
The complexes 5 ± 9, generally isolated as air-stable solid materials in good to high
yields, are either possible catalyst precursors or constitute models of intermediates in
the CO/propene copolymerization reaction. A comparative characterization of these
compounds, both in solution and in the solid state, is therefore desirable. The Pd
complexes 8 are particularly interesting because of the possible influence of the ligands
onto the ratio of the two different diastereoisomers I and II existing for these
derivatives. These species have been shown to be directly involved as catalysts in the
copolymerization reaction [25][26]. Before reporting on these aspects, we describe the
solid-state structure of four different complexes illustrating the general behavior of
modified josiphos ligands from a conformational point of view.
2
.3.2. Solid-State Structure of Neutral Dichloro-, Dimethyl-, and Chloro(methyl)-
palladium Complexes. For the four new complexes [PdCl (3e)] (5e), [PdMe (3a)]
2
2
(6a), [PdClMe(3a)] (7a), and [PdClMe(3g)] (7g), suitable single crystals could be
obtained and routine X-ray crystallographic studies were carried out. Table 4 provides a
selection of bonding parameters defining the geometry around the Pd centers, and in
Table 5 important torsion angles are presented. These latter assist in quantifying the
conformational features of the chelate ring. Due to the structural similarities between
these complexes, only the representative ORTEP view of the dimethyl complex 6a is
shown in Fig. 4, whereas Fig. 5 displays a schematic superposition of 5a, 5e, 6a, 7a, and
7g.
For all complexes examined, the geometry around the Pd-atom is slightly distorted
square planar. The coordination distances to the Pd-atom fall within the expected
ranges [27]. In the two dichloro complexes 5a and 5e, the Pd� Cl distances are very
Table 4. Selected Bond Lengths [Š] and Bond Angles [8] for the Complexes 5a, 5e, 6a, 7a, and 7g
a
7ab)
[PdClMe(3a)] )
7gb)
[PdClMe(3g)] )
5
[
a )
5e
[PdCl
6a
[PdMe
b
b
PdCl
2
(3a)]
2
(3e)]
2
(3a)]
Pd� PAr
2
2.253(4)
2.281(4)
2.358(4)
2.332(4)
94.46(13)
172.59
83.73(13)
176.94
2.275(3)
2.237(3)
2.359(3)
2.338(2)
96.01(8)
172.65(9)
84.65(10)
174.21(11)
87.98(10)
92.00(10)
2.298(3)
2.327(3)
2.102(8)
2.080(8)
93.26(9)
171.6(3)
95.1(3)
174.6(3)
87.4(3)
84.3(4)
2.198(9)
2.343(3)
2.097(7)
2.346(8)
97.24(12)
171.4(2)
92.27(15)
162.5(1)
86.9(2)
2.2369(13)
2.3639(16)
2.138(6)
2.3802(17)
97.08(5)
176.7(2)
91.25(6)
169.66(7)
85.79(19)
86.08(19)
Pd� PCy
Pd� X1
Pd� X2
2
Cy
Cy
Cy
Ar
Ar
2
2
2
2
2
P� Pd� PAr
P� Pd� X1
P� Pd� X2
P� Pd� X1
P� Pd� X2
2
92.95(14)
88.26(14)
X1� Pd� X2
85.7(2)
a) Data for comparison from [20]. b) For complexes 7a and 7g X1ˆMe and X2ˆCl.

Helvetica Chimica Acta ± Vol. 84 (2001)
3113
Table 5. Relevant Torsions Angles [8] for the Complexes 5a, 5e, 6a, 7a, and 7g
a
5
a )
5e
6a
7a
7g
[
PdCl
2
(3a)]
[PdCl
2
(3e)]
[PdMe
2
(3a)] [PdClMe(3a)] [PdClMe(3g)]
�
65
�
�
68
13
� 61
� 14
� 64
� 21
� 98
� 61
� 14
(
� 70 in 3a)
�
10
(
� 24 in 3a)
�
103
� 96
� 103
�
110
(
� 145 in 3a) (� 150 in 3e)
(� 158 in 3g)
a) Data for comparison from [20].
Fig. 4. ORTEP Drawing (30% probability ellipsoids) and atom-numbering scheme of complex 6a
ˆ [PdMe (3a)]
(
2
similar to those in related derivatives, such as [PdCl (dppe)] (dppe ˆ 1,2-(diphenyl-
2
phosphino)ethane ˆ (ethane-1,2-diyl)bis[phosphine]) [28] and [PdCl (dppb)] (dppbˆ
2
1,4-(diphenylphosphino)butane ˆ (butane-1,4-diyl)bis[phosphine]) [29], with the differ-

3114
Helvetica Chimica Acta ± Vol. 84 (2001)
Fig. 5. Schematic superposition of the structures of complexes 5a, 5e, 6a, 7a, and 7g
ence that the Cl ligand in trans position to the PCy group displays a significantly larger
2
distance from Pd, as one would expect from trans-influence considerations [30]. The
same applies to the Pd� C separations in dimethyl complex 6a, although the difference
between the two Pd� C distances fall within the experimentally observed standard
deviations. The bite angle (P� Pd� P) of the coordinated diphosphino moieties varies
between 93 and 978 and is thus significantly larger than for other typical chelating
phosphines. The combination of large P� Pd� P angles with conformational flexibility
of the ligand backbone has been considered to be an important factor in increasing the
rate of the CO/propene copolymerization process [31]. However, the large differences
in catalytic activity observed with our system [15], for which the bite angle [32] is
essentially constant, clearly show that other factors also play a very important role.
The two torsion angles defining the relative position of the Me group at the
stereogenic center and of the PCy fragment given in Table 5 are very similar in all five
2
complexes examined, and are also comparable within less than Æ108 to those of the free
ligands (Table 2). On the other hand, the orientations of the two aryl groups in the
complexes are clearly different from those observed in the free ligands, as shown by the
torsion angle involving the ꢀendoꢁ-aryl group. The values of this angle given in Table 5
deviate by ca. 508 with respect to those of the free ligands. The two aryl groups, in the
free ligands described as ꢀendoꢁ-equatorial and ꢀexoꢁ-axial, are now better referred to as
ꢀ
endoꢁ-axial and ꢀexoꢁ-equatorial, respectively, this coinciding with the only prominent
conformational change occurring upon coordination. The resulting repulsion between
the ferrocene and the ꢀendoꢁ-axial aryl manifests itself in a distorsion involving a
displacement of the corresponding P-atom out of the plane of the ꢀupperꢁ Cp ring. This
ꢀliftingꢁ of the P-atom ranges from a minimum of 0.3 Š in dichloro complex 5a to a
maximum of 0.37 Š for compounds 5e and 7a. The schematic superposition of the five
complexes of Fig. 5 shows that the structural fitting between the different complexes
extends from the ferrocene unit over the chelate ring to the aryl groups. The flexible

Helvetica Chimica Acta ± Vol. 84 (2001)
3115
parts of the molecules are restricted to the Cy groups that can be viewed as forming a
bulky, however adaptable aliphatic region. Overall, it can be said that the conforma-
tional features of the coordinated ligands do not depend upon the electronic nature of
the peripheral substituents at the aryl groups.
Finally, it is interesting to note that the configuration observed in the solid state for
the chloro(methyl) complexes 7a and 7g is such that the Me ligand is in both cases trans
to the PCy fragment. As these two ligands (an alkyl and a trialkylphosphine) possess
2
the highest trans-influence [30], one would not have expected them in mutual trans-
position.
2
.3.3. Chloro(methyl)palladium, Chloro(methyl)platinum, and Cationic Methylpal-
ladium Complexes in Solution. The neutral chloro(methyl)palladium complexes 7, their
corresponding cationic derivatives 8, as well as the analogous chloro(methyl)platinum
compounds 9 containing the ligands 3a ± h were prepared (see Table 3), with the aim of
ascertaining the influence of the different diphosphinoferrocenes on the distribution of
the two possible isomers I and II (see Scheme 2). In isomer I the Me ligand is located
trans to the trialkylphosphino ligand, and in isomer II, it is trans to the PAr fragment.
2
Isomer identification was straightforward for all three complex types, based on the
NMR parameters of the Pd(Me)(P� P) and Pt(Me)(P� P) units, respectively.
Relevant NMR-spectroscopic data are collected in Table 6 (complexes 7 and 8), and
Table 7 (complexes 9) and were obtained with the help of 2D NMR experiments (P,H
and C,H correlations). For compounds 7a, 7f, and 7g, only isomer I, corresponding to
the structure observed in the solid state (vide supra), was detected by NMR (Table 6).
For the two complexes displaying CF substituents at the PAr moiety, both isomers
3
2
could be identified. Whereas in the case of 7d, isomer I was still predominant with a
ratio I/II of 2.2 :1, the proportion was reversed for 7e. An entirely different situation
was encountered for the analogous Pt complexes 9 (Table 7). Here isomer II, with the
Me ligand trans to the PAr group, was the prevailing species in all seven cases
2
Table 6. Selected NMR-Spectroscopic Data for Complexes
7
([PdClMe(P� P)]) and
8
([PdMe-
(
MeCN)(P� P)]PF
6
). d in ppm, J in Hz.
1H-NMR
31
P{ H}-NMR
1
Ratio I/II
d(Pd� Me)
3J(P,H)
d(P)
2J(P,P)
7
7
aI
dI
0.44
0.42
0.85
0.46
0.92
0.42
0.42
0.30
0.58
0.32
0.66
0.31
0.74
0.34
0.57
7.2, 3.7
7.0, 3.9
7.9, 1.9
7.2, 4.2
7.9, 2.2
7.3, 3.7
7.3, 3.6
6.4, 2.2
7.5, 1.5
6.7, 2.8
7.2, 1.4
6.7, 3.0
7.4, 1.6
6.8, 2.6
7.2, 1.5
40.9, 28.9
40.9, 29.9
60.6, 4.9
42.3, 32.2
60.5, 6.9
41.7, 28.9
41.7, 26.7
44.5, 29.8
67.9, 8.3
43.7, 30.4
66.8, 8.5
44.6, 33.8
66.9, 11.3
44.0, 27.3
68.9, 5.8
39.8
40.5
36.0
41.2
36.0
39.1
39.7
40.7
34.3
41.6
35.3
42.0
35.9
40.1
34.2
> 100: 1
2.2 : 1
II
eI
II
7
1 : 2
7fI
7gI
8aI
> 100 : 1
> 100: 1
2 : 1
II
dI
II
eI
II
gI
II
8
8
8
1.3 : 1
1 : 1.8
1.6 : 1

3116
Helvetica Chimica Acta ± Vol. 84 (2001)
Table 7. Selected NMR-Spectroscopic Data for Complexes 9 ([PtClMe(P� P)]). d in ppm, J in Hz.
1H-NMR
31
P{ H}-NMR
1
Ratio I/II
d (Pt� Me)
3J(P,H)
d(P)
1J(Pt,P)
2J(P,P)
9
aI
II
0.24
0.78
0.90
0.22
0.82
0.23
0.83
0.22
0.86
0.23
0.75
0.32
0.77
6.8, 2.0
7.5, 2.0
9.2, <2
7.5, 2.5
6.8, 2.5
6.8, 2.5
7.5, 2.4
6.9, 4.3
7.3, 2.4
6.9, 4.3
7.3, 2.4
6.9, 4.2
7.4, 2.5
44.0, 8.1
39.2, 11.2
46.7, 36.2
44.1, 9.7
39.0, 12.7
43.5, 9.3
39.1, 12.1
44.9, 7.8
39.1, 10.5
44.9, 7.8
39.1, 10.5
44.4, 11.9
39.1, 14.5
1841, 4315
1680, 4186
1694, 4278
1825, 4322
1664, 4134
1822, 4308
1641, 4137
1852, 4328
1688, 4206
1852, 4328
1688, 4206
1834, 4372
1699, 4176
17.6
17.0
15.0
17.8
16.7
17.9
16.7
17.5
16.7
17.5
16.7
17.9
17.0
1 : 4
9
9
bII
cI
II
1 : > 100
1 : 7
9
9
9
9
dI
II
eI
II
1 : 13
1 : 17
1 : 2.5
1 : 4.5
fI
II
hI
II
examined. The ratios I/II varied between 1:2.5 for 9f and 1:17 for 9e. Interestingly, for
derivative 9b containing o-CF groups, only isomer II could be detected. Although
3
ligands containing electron-withdrawing groups seem to favor the formation of isomer
II, no clear trend can be recognized.
The main species of the cationic Pd-complexes 8 was isomer I in the case of 8a, 8d,
and 8g, and of isomer II in the case of 8e. However, in all cases, the observed mixtures
displayed similar fractions of the two isomers, indicating only very small differences in
stability. Despite the absence of any simple trend with respect to the isomer distribution
in complexes 8, it has nevertheless to be noted that the complex containing ligand 3e is
the one most strongly favoring the isomeric form II, with a trans relationship between
the Me ligand and the PAr moiety. Ligand 3e is the one with the (supposedly) most p-
2
acidic PAr group, by virtue of the four CF substituents, and therefore the highest
2
3
ꢀelectronic asymmetryꢁ.
2
.4. CO/Propene Copolymerization with Isolated Pd Complexes as Catalyst
Precursors. The dimethylpalladium complexes 6a and 6e reacted with HBF ´ OEt to
4
2
afford highly efficient catalyst precursors for the CO/propene copolymerization
reaction (Table 8). The CO/propene copolymers formed were obtained with almost
perfect head-to-tail regioselectivity (> 99% of head-to-tail enchainments) and with
high stereoselectivity, in both cases more than 98% of isotactic diads. Among these two
catalyst systems, the most efficient one contained the ligand 3e. This catalyst showed a
very high productivity reaching up to 956 gCop/g ´ h. In these systems, the steric
Pd
demand and the electronic properties of the ligand are essential to produce highly
regio- and stereoregular materials. Moreover, large electronic differentiation of the two
phosphino moieties is very important to enhance the rate of the reaction, as previously
II
shown [15]. The Pd complex containing 3e was about four times more active than the
one with 3a. NMR Studies indicated that when an excess of acid (HBF ´ OEt ) was
4
2
added to a solution containing a dimethylpalladium complex 6, a dicationic species of
2‡
type [Pd(P� P)(S) ] (S ˆ solvent molecule) was formed by protonolytic cleavage of
2
the Pd� Me bonds. However, it must be noted that the productivity of the catalyst thus

Helvetica Chimica Acta ± Vol. 84 (2001)
3117
Table 8. CO/Propene Copolymerization in the Presence of Isolated Complexes as Catalyst Precursors
Catalyst system Productivity Regioregularity
[% H� T enchainments] [% l-diads]
Stereoregularity [a] a
D
)
De (CD)b)
M
n
c)
[gcop/gPd ´ h]
6
6
8
8
a/HBF
e/HBF
a
a ‡ MeOH
4
4
´ OEt
´ OEt
2
2
224
956
4.3
> 99
> 99
> 99
> 99
98.3
98.8
97.5
97.6
� 32.0 1.37
10970
13680
25300
9600
� 33.0 1.55
� 21.7 0.86
� 26.0 1.01
74.5
a) Measured in 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP). ) Measured in HFIP; 1 ± 2 mg/ml concentration
b
c
1
range. ) Determined by integration of end-group signals in the H-NMR spectrum.
generated from the isolated complexes 6a and 6e was only about half with respect to the
corresponding in situ systems.
The monocationic complex [PdMe(MeCN)(3a)]PF6 (8a) was used as well as
catalyst precursor in the copolymerization process (see Table 8). In the absence of
MeOH, the system showed a very poor activity. In contrast, when a small amount of
MeOH was added, an increase in activity was obtained, though the productivity level of
the in situ generated catalyst could not be reached. It is interesting to note that when
complex 8a was used in the absence of MeOH as the activator, the small amount of
copolymer formed was isolated in the solid state in the form of a 1,4-polyketone,
exclusively. These experiments clearly show that the performance of a catalyst
generated in situ from [Pd(OAc) ], the corresponding ligand, and BF ´ OEt cannot be
2
3
2
matched by the use of isolated complexes.
3
. Conclusion. ± A series of new chiral diphosphinoferrocenes of the josiphos type
and their Pd- and Pt-complexes were prepared and characterized. The degree of
pyramidalization at the PAr P-atom and the overall conformational features of the free
2
ligands are essentially insensitive to the presence of electron-withdrawing or donating
substituents at the aryl groups. The structural analyses reported for Pd and Pt
complexes reveal that the steric environment of the metal center imposed by the ligand
is not influenced by the electronic nature of the peripheral substituents at the aryl
groups to any significant extent. In other words, there are no clearly recognizable
structural criteria that would allow one to pinpoint the reactivity differences observed
when modifying the ligand properties by virtue of such substituents. Also, the factors
determining the isomeric composition displayed by complexes of type 7 ± 9 are not
apparent based solely on simple trans-influence considerations. Therefore, an
interpretation and understanding of the observed effects on the catalyst activity [15]
can only be achieved with a detailed knowledge of the entire reaction mechanism, as
well as of the electronic structure of the intermediate complexes involved, implying the
necessity of computational studies, so far not yet available for our system.
We thank Volker Gramlich, Michael Wörle, and Diego Broggini, ETH-Zürich, for the X-ray-crystallo-
graphic studies and ETH-Zürich for financial support. We are grateful to Solvias AG, Basel, for a generous
donation of compound (R)-1.

3118
Helvetica Chimica Acta ± Vol. 84 (2001)
Experimental Part
General. Diaryl(chloro)phosphines [33][34] were prepared by the reaction of Et
2
NPCl with 2 equiv. of the
2
NPAr with a soln. of HCl
2
corresponding arylmagnesium bromide followed by treatment of the intermediate Et
2
in THF. Dicyclohexylphosphane was obtained from Strem. Monophosphanyl intermediates 2 [17][35], as well as
josiphos derivatives 3 [6][19] were prepared according to reported general procedures; therefore, only yield and
characterization data will be provided here. [PdCl
2
(cod)] [21], [PdClMe(cod)] [22], [PdMe
2
(tmeda)] [24], and
[
2
PtCl
2
(cod)] [23] were prepared as described. CC ˆ Column chromatography. NMR Spectra: Bruker Avance-
1
13
4
50 and -300 spectrometers; chemical shifts d in ppm rel. to internal SiMe ( H and C) or to external 85%
3
1
H
3
PO
Crystallographic data (excluding structure factors) for the routine structures reported in this paper have
been deposited with the Cambridge Crystallographic Data Centre as supplementary publications no. CCDC
63613 (3b), CCDC 163610 (3d), CCDC 163608 (3e), CCDC 163612 (3g), CCDC 163609 (3h), CCDC 163607
4), CCDC 163787 (5e), CCDC 163786 (6a), CCDC 163785 (7a), and CCDC 165115 (7g). Copies of the data
can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (‡44)
223336-033; e-mail: deposit@ccdc.cam.ac.uk).
4
( P), coupling constants J in Hz. MS: in m/z (rel. %).
1
(
1
(
1R)-1-{Bis[2-(trifluoromethyl)phenyl]phosphino}-2-[(1R)-1-(dimethylamino)ethyl]ferrocene (2b). CC
0.29): 2.81 g (35%) of 2b. Orange solid. [a]2
0
ˆ � 360 (c ˆ
(
0
4
(
(
3
silica gel, hexane/AcOEt 1:1 ‡ 0.5% Et
3
N; R
f
D
1
.46, CHCl
3
). H-NMR (CDCl
3
): 7.84± 7.79 (m, 1 arom. H); 7.75 ± 7.21 (m, 6 arom. H); 7.13± 7.10 (m, 1 arom. H);
.44 (m, 1 H, Cp); 4.36 (m, 1 H, Cp); 4.09 (dq, J ˆ 6.75, 2.99, MeCHN); 3.97 (s, C
5
H
5
); 3.94 (m, 1 H, Cp); 1.63
1
3
s, Me
2
N); 1.21 (d, J ˆ 6.75, MeCHN). C-NMR (CDCl
3
): 140.7 ± 122.4 (arom. C); 97.2 (d, J ˆ 24, Cp); 77.1 (Cp
under solvent signal)); 70.9 (d, J ˆ 4, Cp); 69.9 (d, J ˆ 4, Cp); 69.5 (s, Ph); 68.2 (s, Cp); 56.6 (d, J ˆ 8, MeCH);
3
1
1
‡
8.7 (s, Me
2
N); 8.5 (s, MeCHN). P{ H}-NMR (CDCl
3
): � 35.6 (m). FAB-MS: 577 (88, M ), 562 (30, [M �
‡
‡
Me] ), 532 (100, [M � Me
2
NH] ), 432 (23), 389 (7), 255 (13), 212 (35). Anal. calc. for C28
H
26
F
6
FeNP (577.33):
C 58.25, H 4.54, N 2.43; found: C 57.91, H 4.66, N 2.66.
(
1R)-1-{Bis[3-(trifluoromethyl)phenyl]phosphino}-2-[(1R)-1-(dimethylamino)ethyl]ferrocene (2c). CC
0.58): 6.27 g (54%) of 2c. Thick orange oil. [a]2
0
ˆ � 267 (c ˆ 0.5, CHCl
(
silica gel, hexane/AcOEt 2 :1; R
H-NMR (CDCl
f
D
3
).
1
3
): 7.99 (d, J ˆ 7.76, 1 arom. H); 7.65 ± 7.30 (m, 7 arom. H); 4.42 (m, 1 H, Cp); 4.28 (m, 1 H, Cp);
4
.14 (dq, J ˆ 6.73, 2.38, MeCHN); 3.98 (s, C
5
H
5
); 3.72 (m, 1 H, Cp); 1.71 (s, Me
2
N); 1.21 (d, J ˆ 6.73, MeCHN).
13
C-NMR (CDCl
s, C
3
): 142.5 ± 118.9 (arom. C); 97.1 (d, J ˆ 23, Cp); 75.2 (d, J ˆ 9, Cp); 70.8 (d, J ˆ 5, Cp); 69.4
1
(
5
H
5
); 69.3 (d, J ˆ 4, Cp); 68.5 (s, Cp); 56.9 (d, J ˆ 7, MeCHN); 38.0 (s, Me
2
N); 6.9 (s, MeCHN). 31P{ H}-
‡
‡
NMR (CDCl
3
): � 20.7 (s). FAB-MS: 577 (100, M ), 532 (78, [M � Me
2
NH] ), 389 (5), 212 (24). Anal. calc. for
28 26 6
C H F FeNP (577.33): C 58.25, H 4.54, N 2.43; found: C 58.13, H 4.70, N 2.64.
(
1R)-1-{(Bis[4-(trifluoromethyl)phenyl]phosphino}-2-[(1R)-1-(dimethylamino)ethyl]ferrocene (2d). CC
0.49): 4.594 g (50%) of 2d. Orange solid. [a]2
0
ˆ � 272 (c ˆ 0.51,
(
silica gel, hexane/AcOEt 2 :1 ! 1:1; R
f
D
1
CHCl
3
). H-NMR (CDCl
3
): 7.70 ± 7.62 (m, 4 arom. H); 7.47 ± 7.45 (m, 2 arom. H); 7.30 ± 7.25 (m, 2 arom. H);
4
.43 (m, 1 H, Cp); 4.29 (m, 1 H, Cp); 4.16 (dq, J ˆ 6.75, 2.30, MeCHN); 3.99 (s, C
5
H
5
); 3.77 (m, 1 H, Cp); 1.59
): 145.1 ± 122.1 (arom. C); 97.1 (d, J ˆ 23, Cp); 74.6
); 8.3 (s, Cp); 56.9 (d, J ˆ 6, MeCHN); 38.3 (s, Me N); 7.6
N] ), 212 (18).
1
3
(
(
(
s, Me
2
N); 1.23 (d, J ˆ 6.75, MeCHN). C-NMR (CDCl
3
d, J ˆ 8, Cp); 71.1 (d, J ˆ 6, Cp); 69.4 (s, C
5
H
5
2
3
1
1
‡
‡
s, MeCHN). P{ H}-NMR (CDCl
FeNP (577.33): C 58.25, H 4.54, N 2.43; found: C 58.59, H 4.92, N 2.37.
1R)-1-{Bis[3,5-bis(trifluoromethyl)phenyl]phosphino}-2-[(1R)-1-(dimethylamino)ethyl]ferrocene (2e).
FC (silica gel, hexane/AcOEt 10 :1; R 0.32): 9.84 g (64%) of 2e. Orange oil that solidified upon standing.
). H-NMR (CDCl
): 8.12 (d, J ˆ 6.8, 2 arom. H); 7.88 (d, J ˆ 6.3, 2 arom. H); 7.80
s, 1 arom. H); 7.74 (s, 1 arom. H); 4.14 (m, 1 H, Cp); 4.08 (dq, J ˆ 6.8, 2.4, MeCHN); 3.99 (m, 1 H, Cp); 3.83
3
): � 21.0 (s). FAB-MAS: 577 (84, M ); 534 (100, [M � Me
2
Anal. calc. for C28
26 6
H F
(
f
2
0
1
[
a]
D
ˆ � 194 (c ˆ 0.53, CHCl
3
3
(
(
(
(
13
s, C
5
H
5
); 3.54 (m, 1 H, Cp); 1.73 (s, Me
2
N); 1.00 (d, J ˆ 6.8, MeCHN). C-NMR (CDCl
3
): 143.4 ± 116.7
); 68.2
arom. C); 97.6 (d, J ˆ 24, Cp); 73.3 (d, J ˆ 6, Cp); 70.3 (d, J ˆ 6, Cp); 70.2 (d, J ˆ 4, Cp); 69.7 (s, C
5 5
H
N); 7.3 (s, MeCHN). 31P{ H}-NMR (CDCl
1
): � 20.2 (s). MALDI-
s, Cp); 57.3 (d, J ˆ 7, MeCH); 11.2 (s, Me
2
3
‡
TOF-MS: 713 (M ). Anal. calc. for C30
H
24
F
12FeNP (713.33): C 50.51, H 3.39, N 1.96; found: C 50.29, H 3.49,
N 1.84.
(
1R)-1-[Bis(3,5-dimethylphenyl)phosphino]-2-[(1R)-1-(dimethylamino)ethyl]ferrocene (2f). CC (silica
20
gel, hexane/AcOEt 2 :1 ! 1:1): 1.224 g (33%) of 2f. Orange oil that solidified upon standing. [a]
D
ˆ � 277
1
(
(
2
c ˆ 0.475, CHCl
3
). H-NMR (CDCl
3
): 7.29 (s, 1 arom. H); 7.02 (s, 1 arom. H); 6.84 ± 6.81 (m, 4 arom. H); 4.39
m, 1 H, Cp); 4.26 (m, 1 H, Cp); 4.12 (dq, J ˆ 6.81, 2.74, MeCHN); 3.96 (s, C
5
H
5
); 3.92 (m, 1 H, Cp); 2.35 (s,
): 141.4 ± 127.2
); 68.8 (d, J ˆ 4, Cp); 67.9
13
MeC
6
H
3
); 2.22 (s, 2 MeC
6
H
3
); 1.85 (s, Me
2
N); 1.32 (d, J ˆ 6.75, MeCHN). C-NMR (CDCl
3
(
arom. C); 97.1 (d, J ˆ 23, Cp); 77.7 (d, J ˆ 12, Cp); 71.8 (d, J ˆ 6, Cp); 69.5 (s, C
5 5
H

Helvetica Chimica Acta ± Vol. 84 (2001)
3119
); 8.2 (s, MeCHN). 31P{ H}-
1
(
s, Cp); 57.3 (d, J ˆ 7, MeCHN); 38.7 (s, Me
2
N); 20.9 (s, MeC
): � 22.68 (s). FAB-MS (pos.): 497 (73, M ), 453 (100, [M � Me
6
H
3
); 20.8 (s, MeC
6
H
3
‡
‡
NMR (CDCl
3
2
N] ), 212 (24). Anal. calc. for
30
C H36FeNP (497.44): C 72.44, H 7.29, N 2.82; found: C 72.41, H 7.29, N 2.66.
(
1R)-1-[Bis(4-methoxyphenyl)phosphino]-2-[(1R)-1-(dimethylamino)ethyl]ferrocene (2g). CC (silica gel,
1
hexane/AcOEt 2 :1 ! 1:1): 2.755 g (36%) of 2g. Orange solid. H-NMR (CDCl
3
): 7.82 ± 7.76 (m, 2 arom. H);
7
.48 ± 7.42 (m, 2 arom. H); 6.88 ± 6.82 (m, 4 arom. H); 4.44 (br. m, MeCHN); 4.31 (m, 1 H, Cp); 4.20 (m, 1 H,
Cp); 4.09 (m, 1 H, Cp); 4.04 (s, C ); 3.38 (s, 1 MeO); 3.35 (s, 1 MeO); 2.03 (s, Me
N); 1.26 (d, J ˆ 6.7,
): � 26.0 (s).
1R)-1-[Bis(3,5-dimethoxyphenyl)phosphino]-2-[(1R)-1-(dimethylamino)ethyl]ferrocene (2h). CC (silica
5
H
5
2
3
1
1
MeCHN). P{ H}-NMR (CDCl
3
(
2
0
1
gel, hexane/AcOEt 2 :1 ! 1 :1): 1.70 g (39%) of 2h. Orange solid. [a]
D
ˆ � 240 (c ˆ 0.44, CHCl
3
). H-NMR
(
6 6
C D ): 7.33±7.32 (m, 1 arom. H); 7.32±7.29 (m, 1 arom. H); 6.91±6.90 (m, 1 arom. H); 6.89±6.86 (m, 1 arom. H);
6
.69 ± 6.68 (m, 1 arom. H); 6.58 ± 6.56 (m, 1 arom. H); 4.43 (qd, J ˆ 6.8, 2.6, MeCHN); 4.29 (m, 1 H, Cp); 4.28
); 3.42 (s, 2 MeO); 3.35 (s, 2 MeO); 2.06 (s, Me
N); 1.23 (d, J ˆ 6.8,
): 160.9 ± 100.2 (arom. C); 97.3 (d, J ˆ 23.4, Cp); 77.2 (d, J ˆ 9.7, Cp); 72.0 (d, J ˆ 5.7,
(
m, 1 H, Cp); 4.17 (m, 1 H, Cp); 4.04 (s, C
5
H
5
2
1
3
MeCHN). C-NMR (C
Cp); 69.9 (s, C
6 6
D
5
H
5
); 69.2 (d, J ˆ 4, Cp); 68.3 (s, Cp); 57.2 (d, J ˆ 4, MeCHN); 54.6 (s, 2 MeO); 54.5 (s, 2 MeO);
3
1
1
‡
38.9 (s, Me
2
N); 8.1 (br. s, MeCHN). P{ H}-NMR (C
6
D
6
): � 17.7 (s). FAB-MS: 561 (100, M ), 517 (83, [M �
‡
Me
2
N] ). Anal. calc. for C30
H
36FeNO
4
P (561.44): C 64.18, H 6.46, N 2.49; found: C 64.07, H 6.28, N 2.46.
(
1R)-1-{Bis[3,5-bis(trifluoromethyl)phenyl]phenylphosphino]-2-[(1R)-1-(dimethylamino)ethyl]ferrocene
(
(
2i). CC (silica gel, hexane/AcOEt 4 :1 ! 3 :1) allowed the separation of the two isomers (total yield, 3.54 g
a b
44%): 1.87 g of 2i and 1.66 g of 2i .
2
0
1
Isomer 2i
a
: Orange oil. [a]
D
ˆ � 251 (c ˆ 0.465, CHCl
3
). H-NMR (CDCl
3
): 7.65 ± 7.40 (m, 8 arom. H); 4.42
); 3.84 (m, 1 H, Cp); 1.78
): 146.0 ± 120.5 (arom. C); 97.6 (d, J ˆ 24, Cp); 74.5
(
(
(
(
m, 1 H, Cp); 4.29 (m, 1 H, Cp); 4.14 (dq, J ˆ 6.8, 2.8, MeCHN); 3.95 (s, C
5 5
H
1
3
s, Me
2
N); 1.23 (d, J ˆ 6.8, MeCHN). C-NMR (CDCl
3
d, J ˆ 7, Cp); 71.3 (d, J ˆ 6, Cp); 69.7 (s, C
5
H
5
); 68.9 (s, Cp); 68.3 (s, Cp); 57.0 (d, J ˆ 8, MeCHN); 38.6
3
1
1
s, Me
2
N); 7.58 (s, MeCHN). P{ H}-NMR (CDCl
3
): � 19.54 (s).
2
0
1
Isomer 2i
b
: Orange solid. [a]
D
ˆ � 264 (c ˆ 0.575, CHCl
3
). H-NMR (CDCl
3
): 7.98 (d, J ˆ 5.5, 2 arom. H);
7
.81 (s, 1 arom. H); 7.27 ± 7.19 (m, 5 arom. H); 4.42 (m, 1 H, Cp); 4.28 (m, 1 H, Cp); 4.17 (dq, J ˆ 6.7, 2.0,
1
3
MeCHN); 4.03 (s, C
5
H
5
); 3.64 (m, 1 H, Cp); 1.66 (s, Me
2
N); 1.20 (d, J ˆ 6.7, MeCHN). C-NMR (CDCl
); 69.6 (C of Cp,
3
):
1
44.2 ± 121.2 (arom. C); 97.0 (d, J ˆ 22, Cp); 75.8 (d, J ˆ 8, Cp); 71.2 (d, J ˆ 6, Cp); 69.6 (s, C
partially under the C N); 7.9 (s, MeCHN). P{ H}-
FeNP (577.33): C 58.25, H 4.54, N 2.4; found: C 58.14, H 4.75,
5 5
H
31
1
5
H
5
signal); 68.3 (s, Cp); 57.4 (d, J ˆ 5, MeCHN); 38.3 (s, Me
2
NMR (CDCl
N 2.37.
3
): � 20.7 (s). Anal. calc. for C28
26 6
H F
(
1R)-1-{Bis[2-(trifluoromethyl)phenyl]phosphino}-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferrocene
0.28): 723 mg (48%) of 3b. Orange solid. [a]2
0
ˆ � 360 (c ˆ 0.46,
(
3b). CC (silica gel, hexane/AcOEt 20 :1; R
CHCl
solvent. H-NMR (C
5 5
.91 (m, 3 arom. H); 4.33 (m, 1 H, Cp); 4.31 (m, 1 H, Cp); 4.21 (m, 1 H, Cp); 3.91 (s, C H
f
D
3
). Single crystals suitable for X-ray-analysis were grown from an EtOH soln., by slow evaporation of the
1
6
D
6
): 7.71 ± 7.62 (m, 2 arom. H); 7.47 ± 7.43 (m, 2 arom. H); 7.20 ± 7.15 (m, 1 arom. H); 7.01 ±
); 3.59 (dq, J ˆ 7.3, 3.3,
): 140.2 ± 118.2 (arom. C); 102.8 (dd, J ˆ 30, 20,
); 69.3 (dd, J ˆ 5, 2, Cp); 68.9 (s, Cp); 33.2 ± 26.5 (Cy,
): 15.8 (d, J ˆ 58.9, PCy ); � 34.8 (ds, PAr ). FAB-MS: 731
] ), 373 (6), 212 (5). Anal. calc. for
6
13
MeCHP); 1.96 ± 1.21 (m, 25 H, Cy, MeCHP). C-NMR (C
6 6
D
Cp); 74.2 (d, J ˆ 17, Cp); 70.2 (d, J ˆ 5, Cp); 69.5 (s, C
5
H
5
3
1
1
MeCHP); 15.9 (br. s, MeCHP). P{ H}-NMR (C
6
‡
D
6
2
‡
2
‡
‡
(
C
29, M ), 647 (54, [M � Cy] ), 585 (76, [M � Ar] ), 533 (100, [M � HPCy
FeP (730.53): C 62.48, H 5.79; found: C 62.48, H 5.80.
1R)-1-{Bis[3-(trifluoromethyl)phenyl]phosphino}-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferrocene
3c). CC (silica gel, hexane/AcOEt 10 :1). Due to phosphine oxide traces, a second CC was necessary (Alox,
2
38
H
42
F
6
2
(
(
2
0
1
short column, hexane/AcOEt 20 :1): 5.89 g (81%) of 3c. Orange oil. [a]
D
ˆ � 267 (c ˆ 0.5, CHCl
3
). H-NMR
(
(
2
2
(
(
C
6
D
6
): 8.37 (d, J ˆ 8.84, 1 arom. H); 7.91 (d, J ˆ 5.61, 1 arom. H); 7.56 ± 7.26 (m, 4 arom. H); 6.96 ± 6.91
m, 2 arom. H); 4.25 (m, 1 H, Cp); 4.17 (m, 1 H, Cp); 3.96 (m, 1 H, Cp); 3.82 (s, C
.26, MeCHP); 1.99 ± 1.02 (m, 25 H, Cy, MeCHP). 13C{ H}-NMR (C
5
H
5
); 3.54 (dq, J ˆ 7.17,
1
6
D
6
): 138.5 ± 122.6 (arom. C); 101.7 (dd, J ˆ
8, 20, Cp); 72.4 (dd, J ˆ 10, 4, Cp); 70.7 (d, J ˆ 5, Cp); 69.4 (s, C
5
H
5
); 69.3 (s, Cp); 69.0 (dd, J ˆ 5, 2, Cp); 69.3
31
1
s, Cp); 33.1 ± 26.5 (Cy, MeCHP); 15.0 (br. s, MeCHP). P{ H}-NMR (C
6
D
6
): 16.7 (d, J ˆ 47.3, PCy
2
); � 24.2
‡
‡
‡
d, J ˆ 47.3, PAr
2
). FAB-MS: 731 (14, M ), 647 (100, [M � Cy] ), 533 (56, [M � HPCy
2
] ), 388 (5), 212 (42).
Anal. calc. for C38
1R)-1-{Bis[4-(trifluoromethyl)phenyl]phosphino}-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferrocene
3d). CC (silica gel, hexane/AcOEt 20 :1). Due to phosphine oxide traces, a second CC was necessary (Alox,
short column, hexane/AcOEt 20 :1): 1.61 g (63%) of 3d. Orange solid. Single crystals suitable for X-ray-analysis
42 6 2
H F FeP (730.53): C 62.48, H 5.79; found: C 62.50, H 5.80.
(
(
were grown from EtOH by slow evaporation of the solvent. [a]2
0
ˆ � 349 (c ˆ 0.47, CHCl
1
D
3 6 6
). H-NMR (C D ):

3120
Helvetica Chimica Acta ± Vol. 84 (2001)
7
3
.60 ± 7.55 (m, 2 arom. H); 7.42 ± 7.34 (m, 6 arom. H); 4.27 (m, 1 H, Cp); 4.21 (m, 1 H, Cp); 3.93 (m, 1 H, Cp);
13
.82 (s, C
5
H
5
); 3.54 (dq, J ˆ 7.5, 2.9, MeCHP); 1.95 ± 1.18 (m, 25 H, Cy, MeCHP). C-NMR (C
6 6
D ): 146.6 ± 122.6
); 69.3 (s, Cp); 69.0
(
(
arom. C); 101.7 (dd, J ˆ 28, 20, Cp); 72.4 (dd, J ˆ 10, 4, Cp); 70.7 (d, J ˆ 5, Cp); 69.4 (s, C
5
H
5
3
1
1
dd, J ˆ 5, 2, Cp); 33.0 ± 26.5 (Cy, MeCHP); 15.3 (d, J ˆ 1, MeCHP). P{ H}-NMR (C
6
D
6
): 16.3 (d, J ˆ 46.0,
‡
‡
‡
PCy
2
); � 24.8 (d, J ˆ 46.0, PAr
FeP
1R)-1-{Bis[3,5-bis(trifluoromethyl)phenyl]phosphino}-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferro-
cene (3e). CC (silica gel, hexane/AcOEt 10 :1). Due to phosphine oxide traces, a second CC was necessary
2
). FAB-MS: 731 (14, M ), 647 (100, [M � Cy] ), 533 (56, [M � HPCy
2
] ), 388,
2
12. Anal. calc. for C38
H
42
F
6
2
(730.53): C 62.48, H 5.79: found: C 62.40, H 5.78.
(
(
Alox, short column, hexane/AcOEt 20 :1): 2.225 g (91.5%) of 3e. Orange solid. Single crystals suitable for X-
20
ray analysis were grown from EtOH by slow evaporation of the solvent. [a]
D
ˆ � 288 (c ˆ 0.49, CHCl
3
).
1
H-NMR (C
6
D
6
): 8.20 (d, J ˆ 6.6, 2 arom. H); 7.99 (d, J ˆ 5.7, 2 arom. H); 7.79 (s, 1 arom. H); 7.75 (s, 1 arom. H);
); 3.42 (dq, J ˆ 7.25, 2.15, MeCHP); 1.98 ±
): 145.0 ± 120.4 (arom. C); 101.9 (dd, J ˆ
); 33.2 ± 26.4 (Cy, MeCHP); 14.6
4
1
2
(
.18 (m, 1 H, Cp); 4.08 (m, 1 H, Cp); 3.81 (m, 1 H, Cp); 3.75 (s, C H
5 5
13
.25 (m, 22 H, Cy); 1.50 (dd, J ˆ 7.12, 3.55, MeCHP). C-NMR (C
6 6
D
8, 20, Cp); 70.9 (dd, J ˆ 9, 4, Cp); 70.1 (d, J ˆ 5, Cp); 70.0 (s, Cp); 69.6 (s, C
5 5
H
3
1
1
d, J ˆ 2, MeCHP); 1 C of Cp missing. P{ H}-NMR (C
6
D
6
): 17.8 (d, J ˆ 52.0, PCy
2
); � 22.6 (d, J ˆ 52.0, PAr
2
).
‡
‡
‡
FAB-MS: 867 (34, M ), 783 (100, M � HCy] ), 700.9 (6), 669 (85, [M � HPCy
2
] ), 456 (3), 212 (40). Anal. calc.
for C40
H
40
F
12FeP
2
(866.53): C 55.44, H 4.65; found: C 55.41, H 4.82.
(
1R)-1-[Bis(3,5-dimethylphenyl)phosphino]-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferrocene (3f). CC
20
(
0
6
(
(
(
(
Alox, hexane/AcOEt 7:1): 1.168 g (89%) of 3f. Orange oil that solidified upon standing. [a]
.505, CHCl
D
ˆ � 305 (c ˆ
1
3
). H-NMR (C
6
D
6
): 7.69 (d, J ˆ 8.35, 2 arom. H); 7.31 (d, J ˆ 7.44, 2 arom. H); 6.87 (s, 1 arom. H);
.78 (s, 1 arom. H); 4.44 (m, 1 H, Cp); 4.37 (m, 1 H, Cp); 4.29 (m, 1 H, Cp); 3.97 (s, C
); 2.18 (s, 2 MeC
); 1.97 ± 1.21 (m, 25 H, Cy, MeCHP). 1 C-NMR
5 5
H
); 3.72
3
br. dq, MeCHP); 2.19 (s, 2 MeC
6
H
3
6 3
H
C
s, C
6
D
6
): 137.2 ± 127.4 (arom. C); 101.1 (dd, J ˆ 28, 9, Cp); 75.3 (dd, J ˆ 13, 3, Cp); 71.7 (d, J ˆ 5, Cp); 69.6
5
H
5
); 68.8 ± 68.6 (m, 2 C, Cp); 33.1 ± 26.6 (Cy, MeCHP); 21.2 (s, MeC
6
H
3
); 21.0 (s, MeC
6
H
3
); 16.5
3
1
1
‡
s, MeCHP). P{ H}-NMR (C
6
D
6
): 14.8 (d, J ˆ 37.4, PCy
2
); � 25.9 (d, J ˆ 37.5, PAr
2
). FAB-MS: 651 (13, M ),
‡
‡
5
67 (100, [M � HCy] ), 453 (50, [M � HPCy
2
] ), 387 (5), 212 (32). Anal. calc. for C40
H
52FeP
2
(650.65): C 73.84,
H 8.06; found: C 73.98, H 7.94.
1R)-1-[Bis(4-methoxyphenyl)phosphino]-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferrocene (3g). CC
(
(
Alox, hexane/AcOEt 6 :1; R
f
0.46): 1.8474 g (72%) of 3g. Orange solid. Single crystals suitable for X-ray
t
20
analysis were grown from BuOMe/EtOH/hexane by slow evaporation of the solvent mixture. [a]
0
4
D
ˆ � 338 (c ˆ
1
.49, CHCl
3
). H-NMR (C
6
D
6
): 7.80 (dd, J ˆ 7.6, 2, 2 arom. H); 7.52 (dd, J ˆ 6.7, 1.9, 2 arom. H); 6.85 (d, J ˆ 8.1,
); 3.69 (dq, J ˆ 7.3, 3.2, MeCHP); 3.37 (s, 1 MeO); 3.32
5 5
arom. H); 4.36, 4.28, 4.26 (3m, 3 H, Cp); 4.01 (s, C H
s, 1 MeO); 1.93 ± 1.18 (m, 25 H, Cy, MeCHP). 13C-NMR (C
(
6
D
6
): 160.5 ± 113.2 (arom. C); 101.3 (dd, J ˆ 27, 20,
5
H ); 68.7 ± 68.6 (m, 2 C, Cp); 54.4 (s, MeO); 54.2
Cp); 76.1 (dd, J ˆ 12, 3, Cp); 71.2 (d, J ˆ 6, Cp); 69.45 (s, C
5
1
31
(
(
2
s, MeO); 33.3 ± 26.5 (Cy, MeCHP); 16.6 (s, MeCHP). P{ H}-NMR (C
6
D
6
): 15.3 (d, J ˆ 32.0, PCy
2
); � 28.6
‡
‡
‡
d, J ˆ 32.0, PAr
45 (33), 212 (33). Anal. calc. for C38
1R)-1-[Bis(3,5-dimethoxyphenyl)phosphino]-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferrocene (3h).
CC (Alox, hexane/AcOEt 6 :1): 349 mg (86%) of 3h. Orange solid. Single crystals suitable for X-ray analysis
2
). FAB-MS: 654 (11, M ), 571 (100, [M � HCy] ), 457 (56, [M � HPCy
2
] ), 391 (6), 350 (6),
2 2
H48FeO P (654.59): C 69.73, H 7.39; found: C 69.29, H 7.07.
(
were grown from EtOH by slow evaporation of the solvent. [a]2
0
ˆ � 281 (c ˆ 0.49, CHCl
1
D
3 6 6
). H-NMR (C D ):
7.36 (d, J ˆ 2.2, 1 arom. H); 7.33 (d, J ˆ 2.2, 1 arom. H); 6.99 (d, J ˆ 2.1, 1 arom. H); 6.96 (d, J ˆ 2.2, 1 arom. H);
6
4
.68 ± 6.67 (d, 1 arom. H); 6.55 ± 6.54 (m, 1 arom. H); 4.45 (m, 1 H, Cp); 4.35 (m, 1 H, Cp); 4.25 (m, 1 H, Cp);
.05 (s, C
5
H
5
); 3.71 (dq, J ˆ 7.6, 3.2, MeCHP); 3.40 (s, 2 MeO); 3.38 (s, 2 MeO); 2.00 ± 1.21 (m, 25 H, Cy,
31 1
‡
MeCHP). P{ H}-NMR (C
(
6
D
6
): 15.6 (d, J ˆ 38.0, PCy
2
); � 20.7 (d, J ˆ 37.8, PAr
2
). FAB-MS: 716 (8, M ), 632
(714.64): C 67.23, H 7.33;
‡
‡
100, [M � HCy] ), 517 (34, [M � HPCy
2
] ), 212 (5). Anal. calc. for C40
H
52FeO
4
P
2
found: C 67.17, H 7.41.
1R)-1-{Bis[3,5-bis(trifluoromethyl)phenyl]phenylphosphino}-2-[(1R)-1-(dicyclohexylphosphino)ethyl]ferro-
cene (3i). From enantiomerically pure 2i ((R,R); 0.91 g, 1.58 mmol, 1 equiv.) and 350 ml of dicyclohexylphos-
phine (1.73 mmol, 1.1 equiv.) according to the general method. The residue was purified by CC (silica gel,
(
b
hexane/AcOEt 30 :1): 902 mg (78%) of the diastereoisomers 3i
a
/3i
b
which could not be separated by CC. Orange
‡
‡
‡
solid. FAB-MS: 731 (12, M ), 647 (100, [M � HCy] ), 533 (49, [M � HPCy
2
] ), 212 (21). Anal. calc. for
C
38
H
42
F
6
FeP
2
(730.53): C 62.48, H 5.79; found: C 62.24, H 5.97.
1
Isomer 3i
a
:
H-NMR (C
6
D
6
): 8.04 (d, J ˆ 5.2, 2 arom. H); 7.74 (s, 1 arom. H); 7.68 ± 7.62 (m, 2 arom. H);
); 3.57 (dq, J ˆ 7.2, 2.5, MeCHP); 1.99 ±
): 15.9 (d, J ˆ 42.9, PCy ); � 24.1 (d, J ˆ 42.9, PAr ).
5 5
7.14 ± 7.12 (m, 3 arom. H); 4.25, 4.19, 4.06 (3m, 3 H, Cp); 3.83 (s, C H
3
1
1
1.21 (m, 25 H, Cy, MeCHP). P{ H}-NMR (C
6
D
6
2
2

Helvetica Chimica Acta ± Vol. 84 (2001)
3121
Isomer 3i
b
: 1H-NMR (C
6
D
6
): 8.31 (d, J ˆ 8.2, 2 arom. H); 7.83 (s, 1 arom. H); 7.47 ± 7.42 (m, 2 arom. H);
); 3.37 ± 3.34 (br. dq, MeCHP); 1.99 ± 1.21
); � 25.9 (d, J ˆ 48.1, PAr ).
SP-4-3)-{(1R)-1-{Bis[3,5-bis(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexylphosphino-
kP)ethyl]ferrocene}dichloropalladium ([PdCl (3e)]; 5e). CH Cl (10 ml) was added to a Schlenk flask
7
.14 ± 7.12 (m, 3 arom. H); 4.36, 4.12, 3.92 (3m, 3 H, Cp); 3.86 (s, C H
5 5
3
1
1
(
m, 25 H, Cy, MeCHP). P{ H}-NMR (C
6
D
6
): 14.3 (d, J ˆ 47.7, PCy
2
3
(
2
2
2
containing [PdCl
2
(cod)] (50 mg, 0.175 mmol) and a slight excess of 3e (159.35 mg, 0.2 mmol). The mixture was
0
stirred at r.t. for 3 h. After filtration through Celite to remove traces of Pd , the soln. was concentrated in vacuo.
Cold pentane was added to precipitate the complex, which was filtered off, washed with additional pentane
(
10 ml), and dried overnight in vacuo: 167.1 mg (91%) of 5e. Orange powder. Single crystals suitable for X-ray
analysis were grown from a CH Cl
soln. layered with pentane at 48. 1H-NMR (CDCl
): 8.59 (d, J ˆ 12.23,
arom. H); 8.17 (s, 1 arom. H); 7.95 ± 7.90 (m, 3 arom. H); 4.82 (m, 1 H, Cp); 4.58 (m, 1 H, Cp); 4.23 (m, 1 H,
Cp); 3.68 (s, 1 H, C
); 3.54 ± 3.41 (m, 1 H, Cy); 3.22 (m, MeCHP); 2.49 ± 1.12 (m, 24 H, Cy, MeCHP). 13C-
NMR (CDCl signal);
): 136.92 ± 116.08 (arom. C); 94.17 (dd, J ˆ 20.41, 3.35, Cp); 77.2 (C(q) of Cp under CDCl
4.49 (d, J ˆ 3.65, Cp); 70.69 (C of Cp partially under C signal); 70.38 (d, J ˆ 7.61, Cp); 37.63 (d, J ˆ 22.84,
Cy(CH)); 35.21 (d, J ˆ 18.88, Cy(CH)); 30.94 ± 25.39 (Cy, MeCHP); 16.42 (d, J ˆ 6.70, MeCHP). P{ H}-NMR
2
2
3
2
5
H
5
3
3
7
5 5
H
31
1
‡
‡
(
6
CDCl
69 (8), 349 (4). Anal. calc. for C40
Dimethylpalladium Complexes: General Procedure 1 (G.P. 1). [PdMe
3
): 80.47 (br. s, PCy
2
), 22.67 (br. s, PAr
2
). FAB-MS: 2051 (100, [2M � Cl] ), 1550 (5), 1009 ([M � Cl] ),
Pd (1043.86): C 46.03, H 3.86; found: C 46.16, H 4.11.
(tmeda)] (1 equiv.) and the
2 2
H40Cl F12FeP
2
diphosphine ligand (1 ± 1.1 equiv.) were dissolved in benzene. The orange soln. was stirred for 3 h at r.t. After
0
filtration through Celite to remove traces of Pd , the soln. was concentrated in vacuo. A mixture of cold Et
2
O/
pentane was added to precipitate the complex, which was filtered off, washed with additional pentane (10 ml),
and then dried overnight in vacuo: orange solid.
(
SP-4-3)-{(2R)-1-[(1R)-1-(Dicyclohexylphosphino-kP)ethyl]-2-(diphenylphosphino-kP)ferrocene}di-
methylpalladium ([PdMe (3a)]; 6a). According to the G.P. 1 from [PdMe (tmeda)] (60 mg, 0.237 mmol,
equiv.) and 3a (144 mg, 0.242 mmol, 1.02 equiv.): 154.2 mg (89%) of 6a. Orange solid. Single crystals suitable
for X-ray analysis were obtained from a warm soln. of benzene and Et ): 8.27 ± 8.22
O. 1H-NMR (C
m, 2 arom. H); 7.63 ± 7.58 (m, 2 arom. H); 7.32 ± 7.12 (m, 6 arom. H); 4.25 (m, 1 H, Cp); 4.14 (m, 1 H, Cp); 4.05
m, 1 H, Cp); 3.62 (s, C
); 3.28 (dq, J ˆ 7.28, 4.15, MeCHP); 2.68 ± 2.64 (br. m, 1 H, Cy); 2.47 ± 2.41 (br. m,
2
2
1
2
6 6
D
(
(
1
1
6
1
5
H
5
1
3
H, Cy); 2.23 ± 1.00 (m, 27 H, Cy, MeCHP, 1 MePd); 0.83 (dd, J ˆ 8.73, 6.42, 1 MePd). C-NMR (C
6 6
D ): 137.2 ±
26.5 (arom. C); 95.0 (dd, J ˆ 23, 6, Cp); 77.2 (dd, J ˆ 24, 8, Cp); 75.0 (s, Cp); 70.0 (s, C ); 68.7 (d, J ˆ 8, Cp);
5
H
5
7.7 (d, J ˆ 5, Cp); 34.0 ± 26.1 (Cy, MeCHP); 16.2 (d, J ˆ 6, MeCHP); 8.4 (dd, J ˆ 102, 10, 1 MePd); 3.65 (dd, J ˆ
3
1
1
07, 10, 1 MePd). P{ H}-NMR (C
6
D
6
): 40.8 (d, J ˆ 28.0, PCy
2
); 13.2 (d, J ˆ 28.0, PPh
2
). FAB-MS (pos.): 699
Pd (731.03): C 62.44, H 6.89; found: C62.24, H 7.02.
‡
(
83, [M � 2 Me] ), 637 (100). Anal. calc. for C38
H50FeP
2
(
SP-4-3)-{(1R)-1-{Bis[3,5-bis(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexylphosphino-
kP)ethyl]ferrocene}dimethylpalladium ([PdMe (3e); 6e). According to the G.P. 1 from [PdMe (tmeda)]
40 mg, 0.158 mmol, 1 equiv.) and 3e (138.5 mg, 0.159 mmol, 1.01 equiv.). The filtrate was evaporated to give 6e
2
2
(
1
quantitatively. H-NMR (C
6
D
6
): 8.67 (d, J ˆ 9.43, 2 arom. H); 7.97 (d, J ˆ 8.40, 1 arom. H); 7.82 (s, 1 arom. H);
.75 (s, 1 arom. H); 4.20 (m, 1 H, Cp); 3.94 (m, 1 H, Cp); 3.56 (m, 1 H, Cp); 3.45 (s, C
); 3.13 (dq, J ˆ 6.82,
.13, MeCHP); 2.65 ± 2.55 (br. m, 1 H, Cy); 2.35 ± 1.04 (m, 27 H, Cy, MeCHP, 1 MePd); 0.64 (dd, J ˆ 7.03, 1.25,
7
2
1
7
1
5 5
H
1
3
MePd). C-NMR (C
0.0 (Cp, C
6
D
6
): 140.1 ± 121.4 (arom. C); 95.8 (dd, J ˆ 25, 6, Cp); 74.1 (s, Cp); 73.0 (dd, Cp); 70.2 ±
5
H
5
); 69.0 (d, J ˆ 5, Cp); 33.7 ± 26.0 (Cy, MeCHP); 15.9 (d, J ˆ 6, MeCHP); 7.7 (dd, J ˆ 100, 10,
31 1
MePd); 5.6 (dd, J ˆ 107, 10, 1 MePd). P{ H}-NMR (C
6
D
6
): 41.6 (d, J ˆ 26.8, PCy
2
); 16.9 (d, J ˆ 26.8, PAr
2
).
‡
FAB-MS (pos.): 973 (23, [M � 2Me] ), 773 (65), 212 (100). Anal. calc. for C42
H46Cl F12FeP Pd (1003.02):
2 2
C 50.29, H 4.62; found: C 50.24, H 4.66.
Chloromethylpalladium Complexes: General Procedure 2 (G.P. 2). To a soln. of [PdClMe(cod)] (1 equiv.)
in CH Cl , the diphosphino ligand (1 ± 1.1 equiv.), was added and the mixture was stirred at r.t. After 3 h, the
soln. was filtered through a Celite filter aid. The filtrate was evaporated until 0.5 ml of CH Cl was left, and the
O, washed with hexane or pentane, and
2
2
2
2
2 2
product was precipitated by addition of hexane/Et O or pentane/Et
dried in vacuo: orange solid.
(
SP-4-2)-{(2R)-1-[(1R)-1-(dicyclohexylphosphino-kP)ethyl]-2-(diphenylphosphino-kP)ferrocene}chloro-
methyl)palladium ([PdClMe(3a)]; 7a). According to the G.P. 2, from [PdClMe(cod)] (200 mg, 0.754 mmol,
equiv.) and 3a (493 mg, 0.82 mmol, 1.1 equiv.): 527 mg (93%) of 7a. Red-orange crystals. Single crystals
(
1
suitable for X-ray analysis were grown from a CH
2
Cl
2
soln. layered with Et
2
O and pentane. Crystallization
1
afforded a single stereoisomer. H-NMR (CDCl
3
): 8.15 ± 8.08 (m, 2 arom. H); 7.57 ± 7.54 (m, 3 arom. H); 7.37 ±
); 3.12 (dq, J ˆ 7.0, 4.6,
MeCHP); 3.00 ± 2.84 (br. m, 1 H, Cy); 2.35 ± 2.22 (br. m, 1 H, Cy); 1.97 ± 1.10 (m, 23 H, Cy, MeCHP); 0.44
5 5
7.26 (m, 5 arom. H); 4.52 (m, 1 H, Cp); 4.26 (m, 1 H, Cp); 4.11 (m, 1 H, Cp); 3.64 (s, C H

3122
Helvetica Chimica Acta ± Vol. 84 (2001)
(
dd, J ˆ 7.28, 3.73, MePd). 13C-NMR (CDCl
): 136.0 ± 127.4 (arom. C); 94.6 (dd, J ˆ 18, 6, Cp); 75.3 (d, J ˆ 4,
3
Cp); 70.3 (s, C
1
(
(
5
H
5
); 70.1 (s, Cp); 69.1 (dd, J ˆ 8, 1, Cp); 68.0 (d, J ˆ 7, Cp); 33.6 ± 25.8 (Cy, MeCHP); 16.5 (d, J ˆ
31 1
03, MePd); 15.9 (s, MeCHP). P{ H}-NMR (CDCl
pos.): 1467 (64.5, [2M � Cl] ), 737 (100, [M � Me] ), 700 (23, [M � MeCl] ). Anal. calc. for C37
3
‡
): 40.9 (d, J ˆ 39.9, PCy
2
); 29.0 (d, J ˆ 39.8, PPh
2
). FAB-MS
47ClFeP Pd
‡
‡
H
2
751.45): C 59.14, H 6.30; found: C 58.52, H 6.45.
(
SP-4)-{(1R)-1-{Bis[4-(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexylphosphino-kP)ethyl]-
ferrocene}chloro(methyl)palladium ([PdClMe(3d)]; 7d). According to the G.P. 2, from [PdClMe(cod)]
(
100 mg, 0.377 mmol, 1 equiv.) and 3d (281 mg, 0.385 mmol, 1.02 equiv.): 291 mg (87%) of 7d as isomer
‡
‡
mixture I/II 1: 0.45. Small orange crystals. FAB-MS (pos.): 1742 (50, [2M � Me
2
] ), 871 (33, [M � Me] ), 837
‡
(22, [M � ClMe] ). Anal. calc. for C39
H
45ClF
6
FeP
2
Pd (887.44): C 52.78, H 5.11; found: C 52.72, H 5.30.
1
Isomer I (Me trans to PCy
2
; (SP-4-2)): H-NMR (CDCl
3
): 8.23 ± 8.17 (m, 2 arom. H); 7.86 (d, J ˆ 7.67,
);
.09 (dq, J ˆ 7.02, 5.26, MeCHP); 3.02 ± 2.86 (m, 1 H, Cy(CH)); 2.25 ± 1.05 (m, 24 H, Cy, MeCHP); 0.42 (dd, J ˆ
2
3
5 5
arom. H); 7.57 ± 7.37 (m, 4 arom. H); 4.61 (m, 1 H, Cp); 4.34 (m, 1 H, Cp); 4.05 (m, 1 H, Cp); 3.64 (s, C H
3
1
1
7
.02, 3.95, MePd). P{ H}-NMR (CDCl
Isomer II (Me trans to PAr ; (SP-4-3)): (CDCl
.57 ± 7.37 (m, 4 arom. H); 4.59 (m, 1 H, Cp); 4.42 (m, 1 H, Cp); 4.28 (m, 1 H, Cp); 3.61 (s, C
br. dq, J ˆ 7.45, MeCHP); 2.48 ± 2.41 (m, 1 H, Cy); 2.25 ± 1.04 (m, 24 H, Cy, MeCHP); 0.85 (dd, J ˆ 7.89, 1.97,
3
): 40.9 (d, J ˆ 40.5, PCy
): 8.23 ± 8.17 (m, 2 arom. H); 7.77 (d, J ˆ 7.67, 2 arom. H);
); 3.23
2
); 29.9 (d, J ˆ 40.5, PAr
2
).
2
3
7
(
5 5
H
3
1
1
MePd). P{ H}-NMR (CDCl
SP-4)-{(1R)-1-{Bis[3,5-bis(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexylphosphino-
kP)ethyl]ferrocene}chloro(methyl)palladium ([PdClMe(3e)]; 7e). According to the G.P. 2, from [PdClMe-
cod)] (61.2 mg, 0.23 mmol, 1 equiv.) and 3e (200 mg, 0.23 mmol, 1 equiv.). The filtrate was evaporated to give
e quantitatively as isomer mixture I/II 1:2. Due to the high solubility of 7e even in pentane, purification
3
): 60.6 (d, J ˆ 36.0, PCy
2
); 4.9 (d, J ˆ 36.0, PAr
2
).
(
(
7
‡
‡
attempts by precipitation were unsuccessful. FAB-MS (pos.): 2009 (100, [M � Cl] ), 971 (8, [M � MeCl] ), 773
(
21), 669 (7), 471 (8), 351 (5), 212 (8). Anal. calc. for C41 Pd ´ 25C 12 (1022.07): C 49.11, H 4.41;
H
43ClF12FeP
2
8
H
found: C 49.23, H 4.91.
1
2 3
Isomer II (Me trans to PAr ; (SP-4-3)): H-NMR (CDCl ): 8.48 (s, 1 arom. H); 8.45 (s, 1 arom. H); 8.09
(
(
s, 1 arom. H); 7.85 (s, 1 arom. H); 7.80 (d, J ˆ 8.99, 2 arom. H); 4.68 (m, 1 H, Cp); 4.53 (m, 1 H, Cp); 4.30
m, 1 H, Cp); 3.61 (s, C ); 3.31 ± 3.21 (m, 1 H, Cy(CH)); 3.16 ± 3.01 (br. m, MeCHP); 2.58 ± 1.03 (m, 24 H, Cy,
5
H
5
3
1
1
MeCHP); 0.92 (dd, J ˆ 7.89, 2.19, MePd). P{ H}-NMR (CDCl
Isomer I (Me trans to PCy
; (SP-4-2): 1H-NMR (CDCl
s, 1 arom. H); 7.92 (s, 1 arom. H); 7.68 (d, J ˆ 8.99, 2 arom. H); 4.72 (m, 1 H, Cp); 4.46 (m, 1 H, Cp); 4.05
m, 1 H, Cp); 3.66 (s, C ); 3.31 ± 3.21 (m, 1 H, Cy); 3.16 ± 3.01 (br. m, MeCHP); 2.58 ± 1.03 (m, 24 H, Cy,
3
): 60.5 (d, J ˆ 36.0, PCy
2
); 6.9 (d, J ˆ 36.0, PAr
2
).
2
3
): 8.45 (s, 1 arom. H); 8.41 (s, 1 arom. H); 8.16
(
(
5
H
5
31
1
MeCHP); 0.46 (dd, J ˆ 7.23, 4.17, MePd). P{ H}-NMR (CDCl
PAr ).
SP-4-2)-{(1R)-1-[Bis(3,5-dimethylphenyl)phosphino-kP]-2-[(1R)-1-(dicyclohexylphosphino-kP)ethyl]-
ferrocene}chloro(methyl)palladium ([PdClMe(3f)]; 7f). According to the G.P. 2, from [PdClMe(cod)]
3
): 42.3 (d, J ˆ 41.2, PCy
2
); 32.2 (d, J ˆ 41.2,
2
(
(
100 mg, 0.378 mmol, 1 equiv.) and 3f (250.2 mg, 0.385 mmol, 1.02 equiv.): 247.8 mg (81.4%) of 7f. Light
1
orange solid as a single isomer I (Me trans to PCy
2
; (SP-4-2). H-NMR (CDCl
3
): 7.74 (d, J ˆ 12.79, 2 arom. H);
7
(
.17 (s, 1 arom. H); 6.96 ± 6.92 (m, 3 arom. H); 4.49 (m, 1 H, Cp); 4.25 (m, 1 H, Cp); 4.14 (m, 1 H, Cp); 3.67
s, C ); 2.24 (s, 6 H,
); 3.07 (dq, J ˆ 6.92, 4.16, MeCHP); 2.87 ± 2.83 (br. m, 1 H, Cy); 2.44 (s, 6 H, MeC
MeC ): 137.7 ± 130.4
signal); 75.5 (d, J ˆ 5, Cp); 70.2 (s, C ), 68.9
dd, J ˆ 8, 1, Cp); 67.8 (d, J ˆ 7, Cp); 33.7 (d, J ˆ 12, Cy(CH)); 32.9 (d, J ˆ 9, Cy(CH)); 31.6 ± 26.0 (Cy, MeCHP);
5
H
5
6 3
H
13
6
H
3
); 1.92 ± 0.85 (m, 24 H, Cy, MeCHP); 0.42 (dd, J ˆ 7.29, 3.70, MePd). C-NMR (CDCl
3
(
(
2
arom. C); 94.5 (dd, J ˆ 18, 6, Cp); 77.20 (C of Cp under CDCl
3
5 5
H
31
1
1.6 (s, MeC
6
H
3
); 21.5 (s, MeC
6
H
3
); 16.8 (d, J ˆ 6, MeCHP); 9.3 (MePd); 7.7 (MePd). P{ H}-NMR (CDCl
3
):
). FAB-MS (pos.): 1580 (37, [2M � Cl] ),793 (55, [M � Me] ), 757
55ClFeP Pd (807.55): C 60.98, H 6.86; found: C 61.16, H 6.78.
‡
‡
4
(
1.7 (d, J ˆ 39.1, PCy
2
); 28.9 (d, J ˆ 39.1, PAr
2
‡
17, [M � MeCl] ), 665 (100). Anal. calc. for C41
H
2
(
SP-4-2)-{(1R)-1-[Bis(4-methoxyphenyl)phosphino-kP]-2-[(1R)-1-(dicyclohexylphosphino-kP)ethyl]fer-
rocene}chloro(methyl)palladium ([PdClMe(3g)]; 7g). According to the G.P. 2, from [PdClMe(cod)] (50 mg,
0
.188 mmol, 1 equiv.) and 3g (130 mg, 0.198 mmol, 1.05 equiv.): 126.9 mg (83%) of 7g. Orange solid. Single
t
crystals suitable for an X-ray study were grown from a CH
Crystallization afforded a single isomer I (Me trans to PCy
8
1
2
Cl
2
soln. layered with hexane and BuOMe.
1
2
; (SP-4-2)). H-NMR (CDCl
3
): 8.06 (dd, J ˆ 11.51,
.74, 1 arom. H); 7.26 (dd, J ˆ 10.66, 8.95, 1 arom. H); 7.07 (dd, J ˆ 8.74, 1.49, 1 arom. H); 6.83 (dd, J ˆ 8.95, 1.92,
arom. H); 4.50 (m, 1 H, Cp); 4.25 (m, 1 H, Cp); 4.08 (m, 1 H, Cp); 3.89 (s, 1 MeO); 3.81 (s, 1 MeO); 3.73
); 3.07 (dq, J ˆ 7.03, 4.26, MeCHP); 2.96 ± 2.83 (br. m, 1 H, Cy); 2.29 ± 1.11 (m, 24 H, Cy, MeCHP); 0.42
(
(
6
s, C
dd, J ˆ 7.25, 3.62, MePd). C{ H}-NMR (CDCl
8.9 (dd, J ˆ 9, 2, Cp); 67.5 (d, J ˆ 7, Cp); 55.2 (s, MeO); 55.0 (s, MeO); 33.4 (d, J ˆ 12, Cy(CH)); 32.5 (d, J ˆ 9,
5 5
H
1
3
1
3
): 161.5 ± 113.0 (arom. C); 74.9 (d, J ˆ 5, Cp); 70.0 (s, C
5 5
H ),

Helvetica Chimica Acta ± Vol. 84 (2001)
3123
):
31
1
Cy(CH)); 30.5 ± 25.7 (Cy, MeCHP); 16.5 (d, J ˆ 89, MePd); 15.8 (d, J ˆ 2, MeCHP). P{ H}-NMR (CDCl
1.7 (d, J ˆ 39.7, PCy ); 26.7 (d, J ˆ 39.7, PAr ). Anal. calc. for C39 51ClFeO Pd (811.50): C 57.72, H 6.33;
found: C 57.83, H 6.52.
Cationic Pd Complexes [PdMe(P� P)(MeCN)]PF
3
4
2
2
H
2 2
P
6
: General Procedure 3 (G.P. 3). To a soln. of the
Cl /MeCN 9.5 : 0.5 (v/v), TlPF (1.1 equiv.)
was added. After stirring overnight, the soln. was filtered over Celite to remove TlCl. The filtrate was first
concentrated in vacuo to ca. 0.5 ± 1.0 ml, then cooled pentane (30 ml) was added with rapid stirring, to allow
precipitation of the product. The material was filtered off, washed with additional pentane (10 ml), and dried in
chloromethylpalladium complex [PdClMe(P� P)] (1 equiv.) in CH
2
2
6
vacuo to afford product [PdMe(P� P)(MeCN)]PF
SP-4)-(Acetonitrile){(2R)-1-[(1R)-1-(dicyclohexylphosphino-kP)ethyl]-2-(diphenylphosphino-kP)ferro-
; 8a). According to the G.P. 3, from
6
as a mixture of the two isomers.
cene}methylpalladium(‡) Hexafluorophosphate ([PdMe(3a)(MeCN)]PF
6
[
PdClMe(3a)] (89.4 mg, 0.119 mmol, 1 equiv.) and 41.6 mg of TlPF
6
(41.6 mg, 0.130 mmol, 1.1 equiv.): 97.6 mg
‡
(
90%) of 8a as isomer mixture I/II 1.95 :1. Dark orange powder. FAB-MS (pos.): 699 (72, [Pd(5a)] ), 637 (87),
2
05 (100). Anal. calc. for C39
H
60
F
6
FeNP
3
Pd (912.09): C 51.36, H 6.63, N 1.54; found: C 51.34, H 6.52, N 1.28.
1
Isomer I (Me trans to PCy
2
; (SP-4-2)): H-NMR (CD
3
CN): 8.13 ± 7.30 (m, 10 arom. H); 4.73 (m, 1 H, Cp);
4
(
.42 (m, 1 H, Cp); 4.16 (m, 1 H, Cp); 3.74 (s, C
m, 27 H, Cy, MeCHP, MeCNPd); 0.30 (dd, J ˆ 6.36, 2.19, MePd). P{ H}-NMR (CD
PCy ).
); 29.8 (d, J ˆ 40.7, PPh
Isomer II (Me trans to PPh
.51 (m, 1 H, Cp); 4.46 (m, 1 H, Cp); 3.77 (s, C
m, 27 H, Cy, MeCHP, MeCNPd); 0.58 (dd, J ˆ 7.45,1.53, MePd). P{ H}-NMR (CD
PCy ).
); 8.3 (d, J ˆ 34.3, PPh
SP-4)-(Acetonitrile){(1R)-1-{bis[4-(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexylphos-
phino-kP)ferrocene}methylpalladium(‡) Hexafluorophosphate ([PdMe(3d)(MeCN)]PF ; 8d). According to
the G.P. 3, from [PdClMe(3d)] (150 mg, 0.169 mmol, 1 equiv.) and TlPF (64.95 mg, 0.186 mmol, 1.1 equiv.):
63 mg (93%) of 8d as isomer mixture I/II 1.3 :1. Dark red powder. FAB-MS (pos.): 1750 (100), 834 (82), 704
87), 212 (31). Anal. calc. for C41 12FeNP Pd (1038.01): C 47.44, H 4.66, N 1.35; found: C 47.62, H 4.76,
5 5
H ); 3.36 ± 3.26 (m, 1 H); 2.47 ± 2.36 (m, 1 H, Cy); 2.16 ± 0.88
31
1
3
CN): 44.5 (d, J ˆ 40.7,
2
2
1
2
; (SP-4-3)): H-NMR (CD
3
CN): 8.13 ± 7.30 (m, 10 arom. H); 4.77 (m, 1 H, Cp);
4
(
5 5
H
); 3.22 ± 3.13 (m, 1 H); 2.63 ± 2.51 (m, 1 H, Cy); 2.16 ± 0.88
31
1
3
CN): 67.9 (d, J ˆ 34,3,
2
2
(
6
6
1
(
H
48
F
3
N 1.18.
Isomer I (Me trans to PCy
m, 2 arom. H); 7.76 ± 7.73 (m, 2 arom. H); 7.54 ± 7.39 (m, 2 arom. H); 4.80 (m, 1 H, Cp); 4.50 (m, 1 H, Cp); 4.18
m, 1 H, Cp); 3.75 (s, C
); 3.31 (dq, J ˆ 7.23, 4.82, MeCHP); 2.62 ± 2.50 (m, 1 H, Cy); 2.14 ± 1.12 (m, 27 H, Cy,
; (SP-4-2)): 1H-NMR (CD
CN): 8.27 ± 8.18 (m, 2 arom. H); 8.03 ± 8.00
2 3
(
(
5
H
5
31
1
MeCHP, MeCNPd); 0.32 (dd, J ˆ 6.72, 2.83, MePd). P{ H}-NMR (CD
3
CN): 43.7 (d, J ˆ 41.6, PCy
; (SP-4-3)): 1H-NMR (CD
CN): 8.27 ± 8.18 (m, 2 arom. H); 8.03 ± 8.00
3
2
); 30.4
(
d, J ˆ 41.6, PAr
2
).
Isomer II (Me trans to PAr
2
(
(
m, 2 arom. H); 7.76 ± 7.73 (m, 2 arom. H); 7.54 ± 7.39 (m, 2 arom. H); 4.83 (m, 1 H, Cp); 4.58 (m, 1 H, Cp); 4.50
m, 1 H, Cp); 3.77 (s, C ); 3.18 (br. dq, MeCHP); 2.44 ± 2.34 (m, 1 H, Cy); 2.14 ± 1.12 (m, 27 H, Cy, MeCHP,
5
H
5
31
1
MeCNPd); 0.66 (dd, J ˆ 7.24, 1.38, MePd). P{ H}-NMR (CD
PAr ).
SP-4)-(Acetonitrile){(1R)-1-{bis[3,5-bis(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexyl-
phosphino-kP)ethyl]ferrocene}palladium(‡) Hexafluorophosphate ([PdMe(3e)(MeCN)]PF ; 8e). According
to the G.P. 3, from [PdClMe(3e)] (178 mg, 0.174 mmol, 1 equiv.) and TlPF (63.8 mg, 0.183 mmol, 1.05 equiv.):
3
CN): 66.8 (d, J ˆ 35.3, PCy
2
); 8.5 (d, J ˆ 35.3,
2
(
6
6
8
e as isomer mixture I/II 1:1.8 in quant. yield. Dark red powder.
1
Isomer I (Me trans to PCy
2
; (SP-4-2)): H-NMR (CD
3
CN): 8.55 ± 8.51 (m, 2 arom. H); 8.38 (s, 1 arom. H);
8
.17 (s, 1 arom. H); 7.77 (d, J ˆ 11.08, 2 arom. H); 4.89 (m, 1 H, Cp); 4.58 (m, 1 H, Cp); 4.44 (m, 1 H, Cp); 3.74
(
(
s, C
5
H
5
); 3.35 ± 3.21 (m, MeCHP); 2.61 ± 2.45 (m, 1 H, Cy); 2.16 ± 1.11 (m, 27 H, Cy, MeCHP, MeCNPd); 0.31
3
1
1
dd, J ˆ 6.67, 3.04, MePd). P{ H}-NMR (CD
3
CN): 44.6 (d, J ˆ 42.0, PCy
2
); 33.8 (d, J ˆ 42.0, PAr
2
).
1
Isomer II (Me trans to PAr
2
; (SP-4-2)): H-NMR (CD
3
CN): 8.55 ± 8.51 (m, 2 arom. H); 8.41 (s, 1 arom. H);
8
.14 (s, 1 arom. H); 7.71 (d, J ˆ 9.62, 2 arom. H); 4.89 (m, 1 H, Cp); 4.67 (m, 1 H, Cp); 4.65 (m, 1 H, Cp); 3.75
(
(
s, C
dd, J ˆ 7.36, 1.61, MePd). P{ H}-NMR (CD
SP-4)-(Acetonitrile){(1R)-1-[bis(4-methoxyphenyl)phosphino-kP]-2-[(1R)-1-(dicyclohexylphosphino-
; 8g). According to the
(65.5 mg, 0.187 mmol, 1.05 equiv.): 8g
5 5
H
); 3.35 ± 3.21 (m, MeCHP); 2.61 ± 2.45 (m, 1 H, Cy); 2.16 ± 1.11 (m, 27 H, Cy, MeCHP, MeCNPd); 0.74
3
1
1
3
CN): 66.9 (d, J ˆ 36.0, PCy
2
); 11.3 (d, J ˆ 36.0, PAr
2
).
(
kP)ethyl]ferrocene}palladium(‡) Hexafluorophosphate ([PdMe(3g)(MeCN)]PF
6
G.P. 3, from [PdClMe(3g)] (145 mg, 0.179 mmol, 1 equiv.) and TlPF
6
as isomer mixture I/II 1.6 :1 in quant. yield. Dark red powder.
1
Isomer I (Me trans to PCy
2
; (SP-4-2)): H-NMR (CD
3
CN): 8.00 ± 7.93 (m, 2 arom. H); 7.29 ± 7.14
(
m, 4 arom. H); 6.99 ± 6.92 (m, 2 arom. H); 4.61 (m, 1 H, Cp); 4.40 (m, 1 H, Cp); 4.15 (m, 1 H, Cp); 3.93

3124
Helvetica Chimica Acta ± Vol. 84 (2001)
(
s, 1 MeO); 3.86 (s, C
5
H
5
); 3.80 (s, 1 MeO); 3.22 ± 3.14 (m, 1 H); 2.52 ± 1.05 (m, 28 H, Cy, MeCHP, MeCNPd);
3
1
1
0
.34 (dd, J ˆ 6.80, 2.63, MePd). P{ H}-NMR (CD
3
1
CN): 44.0 (d, J ˆ 40.1, PCy
2
); 28.3 (d, J ˆ 40.1, PAr
CN): 8.00 ± 7.93 (m, 2 arom. H); 7.29 ± 7.14
m, 4 arom. H); 6.99 ± 6.92 (m, 2 arom. H); 4.64 (m, 1 H, Cp); 4.47 (m, 1 H, Cp); 4.40 (m, 1 H, Cp); 3.94
s, 1 MeO); 3.84 (s, C ); 3.80 (s, 1 MeO); 3.02 ± 2.94 (m, 1 H); 2.52 ± 1.05 (m, 28 H, Cy, MeCHP, MeCNPd);
.57 (dd, J ˆ 7.23, 1.53, MePd). P{ H}-NMR (CD
Chloromethylplatinum Complexes [PtClMe(P� P)]: General Procedure 4 (G.P. 4). A mixture of
PtClMe(cod)] (1 equiv.) and the corresponding diphosphine ligand (P� P) (1 ± 1.1 equiv.) was stirred in
CH Cl at r.t. for 3 ± 5 h. The resulting clear orange soln. was filtered through Celite. The filtrate was
concentrated to ca. 0.5 ± 1.0 ml, and cold Et O or pentane was added to precipitate the complex. The complex
was filtered off, washed with additional Et O or pentane (10 ml), and dried in vacuo.
SP-4)-{(2R)-1-[(1R)-1-(Dicyclohexylphosphino-kP)ethyl]-2-(diphenylphosphino-kP)ferrocene}chloro-
methyl)platinum ([PtClMe(3a)]; 9a). According to the G.P. 4, from [PtClMe(cod)] (100 mg, 0.28 mmol,
equiv.) and 3a (166 mg, 0.28 mmol, 1 equiv.): 225 mg (96%) of 9a as isomer mixture I/II 1:4. Orange solid.
2
).
2 3
Isomer II (Me trans to PAr ; (SP-4-3)): H-NMR (CD
(
(
0
5
H
5
3
1
1
3
CN): 68.89 (d, J ˆ 34.2, PCy
2
); 5.80 (d, J ˆ 34.2, PAr
2
).
[
2
2
2
2
(
(
1
‡
‡
‡
FAB-MS (pos.): 1665 (100, [2M � Me] ), 824 (70, [M � Me] ), 788 (76, [M � MeCl] ). Anal. calc. for
C
37
H
47ClFeP
2
Pt (840.11): C 52.90, H 5.64; found: C 52.95, H 5.89.
1
Isomer I (Me trans to PCy
2
; (SP-4-2): H-NMR (CDCl
3
): 8.21 ± 8.14 (m, 2 arom. H); 7.56 ± 7.27
); 3.52 ± 3.28
m, MeCHP); 2.71 ± 2.61 (br. m, 1 H, Cy); 2.37 ± 2.29 (br. m, 1 H, Cy); 2.09 ± 1.10 (m, 23 H, Cy, MeCHP);
(
(
5 5
m, 8 arom. H); 4.53 (m, 1 H, Cp); 4.35 (m, 1 H, Cp); 4.12 (m, 1 H, Cp); 3.63 (s, C H
3
3
31
1
1
2
0
PCy
.24 (dd, J(P,H) ˆ 6.8, J(P,H) ˆ 2.0, MePt). P{ H}-NMR (CDCl
3
): 44.0 (d, J(Pt,P) ˆ 1841, J(P,P) ˆ 17.6,
1
2
2
); 8.1 (d, J(Pt,P) ˆ 4315, J(P,P) ˆ 17.6, PPh
2
).
Isomer II (Me trans to PPh
2
; (SP-4-3)): 1H-NMR (CDCl
3
): 8.21 ± 8.14 (m, 2 arom. H); 7.56 ± 7.27
(
m, 8 arom. H); 4.50 (m, 1 H, Cp); 4.31 (m, 1 H, Cp); 4.30 (m, 1 H, Cp); 3.60 (s, C
5 5
H ); 3.52 ± 3.28 (br. m,
MeCHP); 2.71 ± 2.61 (br., 1 H, Cy); 2.37 ± 2.29 (br., 1 H, Cy); 2.09 ± 1.10 (m, 23 H, Cy, MeCHP); 0.78
3
3
31
1
1
2
(
1
dd, J(P,H) ˆ 7.5, J(P,H) ˆ 2.0, MePt). P{ H}-NMR (CDCl
3
): 39.2 (d, J(Pt,P) ˆ 4186, J(P,P) ˆ 17.0, PCy
2
);
1
2
1.2 (d, J(Pt,P) ˆ 1680, J(P,P) ˆ 17.0, PPh
2
).
(
SP-4-2)-{(1R)-1-{Bis[2-(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexylphosphino-
kP)ethyl]ferrocene}chloro(methyl)platinum ([PtClMe(3b)]; 9b). According to the G.P. 4, from [PtClMe-
(
cod)] (100 mg, 0.28 mmol, 1 equiv.) and 3b (204 mg, 0.28 mmol, 1 equiv.): 246 mg (90%) of 9b as a single
1
isomer I (Me trans to P(Cy)
2
; (SP-4-2)). Orange solid. H-NMR (CDCl
3
): 9.37 (dd, J ˆ 18.4, 6.6, 1 arom. H);
7.90 ± 7.32 ( m, 7 arom. H); 4.53 (m, 1 H, Cp); 4.49 (m, 1 H, Cp); 4.37 (m, 1 H, Cp); 3.68 (s, C
5
H
5
); 3.27 ± 3.21
3
(
m, MeCHP); 2.69 ± 2.61 (br. m, 1 H, Cy); 2.16 ± 1.12 (m, 27 H, Cy, MeCHP); 0.90 (dd, J(P,H) ˆ 9.2,
3
31
1
): 46.7 (br. m, 1J(Pt,P) ˆ 1694, PAr
1
J(P,H) < 2, MePt). P{ H}-NMR (CDCl
J(P,P) ˆ 15.0, PCy
3
2
); 36.2 (d, J(Pt,P) ˆ 4278,
2
‡
‡
‡
2
). FAB-MS (pos.): 1915 (46, [2M � Cl] ), 960 (100, [M � Me] ), 940 (72, [M � Cl] ).
Anal. calc. for C39
H
45ClF
6
FeP
2
Pt ´ 0.125C
8
H
12 (976.10): C 48.57, H 4.69; found: C 48.51, H 4.93.
(
SP-4)-{(1R)-1-{Bis[3-(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexylphosphino-
kP)ethyl]ferrocene}chloro(methyl)platinum ([PtClMe(3c)]; 9c). According to G.P. 4, from [PtClMe(cod)]
100 mg, 0.28 mmol, 1 equiv.) and 3c (204 mg, 0.28 mmol, 1 equiv.): 248 mg (91%) of 9c as isomer mixture I/
(
‡
‡
‡
II 1 :7. Orange solid. FAB-MS (pos.): 1915 (100, [2M � Cl] ), 960 (21, [M � Me] ), 924 (43, [M � MeCl] ).
Anal. calc. for C39 FeP Pt ´ 0.2C 12 (840.11): C 48.87, H 4.79; found: C 48.56, H 5.05.
Isomer I (Me trans to PCy
; (SP-4-2)). 1H-NMR (CDCl
): 8.46 ± 8.39 (m, 1 arom. H); 8.26 (d, J ˆ 11.2,
arom. H); 7.86 ± 7.32 (m, 6 arom. H); 4.62 (m, 1 H, Cp); 4.34 (m, 1 H, Cp); 4.09 (m, 1 H, Cp); 3.62 (s, C );
.39 ± 3.28 (br. dq, MeCHP); 2.76 ± 2.73 (br. m, 1 H, Cy); 2.42 ± 2.35 (br. m, 1 H, Cy); 2.02 ± 0.86 (m, 23 H, Cy,
H
45ClF
6
2
8
H
2
3
1
3
5 5
H
3
1
1
1
2
MeCHP); 0.22 (dd, J ˆ 6.7, 4.5, MePt). P{ H}-NMR (CDCl
3
): 44.0 (d, J(Pt,P) ˆ 1825, J(P,P) ˆ 17.8, PCy
2
); 9.7
1
2
(
d, J(Pt,P) ˆ 4322, J(P,P) ˆ 17.8, PAr
2
).
Isomer II (Me trans to PAr
2
; (SP-4-3)). 1H-NMR (CDCl
arom. H); 7.86 ± 7.32 (m, 6 arom. H); 4.59 (m, 1 H, Cp); 4.39 (m, 1 H, Cp); 4.31 (m, 1 H, Cp); 3.58 (s, C );
.44 (dq, J ˆ 7.3, 3.9, MeCHP); 2.76 ± 2.73 (br. m, 1 H, Cy); 2.42 ± 2.35 (br. m, 1 H, Cy); 2.02 ± 0.86 (m, 23 H, Cy,
3
): 8.59 ± 8.53 (m, 1 arom. H); 8.14 (d, J ˆ 9.5,
1
3
5 5
H
3
1
1
1
2
MeCHP); 0.82 (dd, J ˆ 7.5, 2.5, MePt). P{ H}-NMR (CDCl
3
): 39.0 (d, J(Pt,P) ˆ 4134, J(P,P) ˆ 16.7, PCy
2
);
1
2
1
2.7 (d, J(Pt,P) ˆ 1644, J(P,P) ˆ 16.7, PPh
2
).
(
SP-4)-{(1R)-1-{Bis[4-(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexylphosphino-k;P)-
ethyl]ferrocene}chloro(methyl)platinum ([PtClMe(3d)]; 9d. According to the G.P. 4, from [PtClMe(cod)]
(
1
C
100 mg, 0.28 mmol, 1 equiv.) and 3d (204 mg, 0.28 mmol, 1 equiv.): 258 mg (95%) of 9d as isomer mixture I/II
‡
‡
:13. Orange solid. FAB-MS (pos.): 1915 (100, [2M � Cl] ), 924 (36, [M � MeCl] ). Anal. calc. for
39
H
45ClF
6
FeP Pt (976.10): C 47.99, H 4.65; found: C 48.20, H 4.89.
2

Helvetica Chimica Acta ± Vol. 84 (2001)
; (SP-4-2)): 1H-NMR (CDCl
m, 2 arom. H); 7.59 ± 7.41 (m, 4 arom. H); 4.63 (m, 1 H, Cp); 4.33 (m, 1 H, Cp); 4.07 (m, 1 H, Cp); 3.65
s, C ); 3.37 ± 3.26 (br. dq, MeCHP); 2.79 ± 2.72 (br. m, 1 H, Cy); 2.37 (br. m, 1 H, Cy); 1.98 ± 0.88 (m, 23 H,
3125
Isomer I (Me trans to PCy
2
3
): 8.29 (dd, J ˆ 8.6, 2.0, 2 arom. H); 7.86 ± 7.79
(
(
5
H
5
3
1
1
1
2
Cy, MeCHP); 0.23 (dd, J ˆ 6.5, 4.3, MePt). P{ H}-NMR (CDCl ): 43.5 (d, J(Pt,P) ˆ 1822, J(P,P) ˆ 17.8,
3
1
2
PCy
2
); 9.3 (d, J(Pt,P) ˆ 4308, J(P,P) ˆ 17.9, PAr
2
).
1
Isomer II (Me trans to PAr
2
; (SP-4-3)). H-NMR (CDCl
3
): 8.29 (dd, J ˆ 8.6, 2.0, 2 arom. H); 7.86 ± 7.79
(
(
m, 2 arom. H); 7.59 ± 7.41 (m, 4 arom. H); 4.59 (m, 1 H, Cp); 4.38 (m, 1 H, Cp); 4.28 (m, 1 H, Cp); 3.61
s, C
); 3.41 (dq, J ˆ 7.5, 4.0, MeCHP); 2.79 ± 2.72 (br. m, 1 H, Cy); 2.37 (br. m, 1 H, Cy); 1.98 ± 0.88 (m, 23 H,
5
H
5
3
1
1
1
2
Cy, MeCHP); 0.83 (dd, J ˆ 7.5, 2.4, MePt). P{ H}-NMR (CDCl
3
): 39.1 (d, J(Pt,P) ˆ 4137, J(P,P) ˆ 16.7, PCy
2
);
1
2
1
2.1 (d, J(Pt,P) ˆ 1641, J(P,P) ˆ 16.7, PAr
2
).
(
SP-4)-{(1R)-1-{Bis[3,5-bis(trifluoromethyl)phenyl]phosphino-kP}-2-[(1R)-1-(dicyclohexylphosphino-
kP)ethyl]ferrocene}chloro(methyl)platinum ([PtClMe(3e)]; 9e). According to the G.P. 4, from [PtClMe(cod)]
100 mg, 0.28 mmol, 1 equiv.) and 3e (243 mg, 0.28 mmol, 1 equiv.). The resulting clear orange soln. was
(
evaporated to dryness: 9e as isomer mixture I/II 1:17 quantitatively. Pure orange solid. FAB-MS (pos.): 2189
‡
(
100, [2M � Cl] ). Anal. calc. for C41
H
43ClF12FeP
2
Pt (1112.10): C 44.28, H 3.90; found: C 44.50, H 4.01.
): 8.53 ± 8.50 (d, 2 arom. H, (under arom. H of
1
Isomer I (Me trans to PCy
2
; (SP-4-2)): H-NMR (CDCl
3
isomer II)); 8.14 (s, 1 arom. H); 7.90 (s, 1 arom. H); 7.70 (d, J ˆ 10.0, 2 arom.H); 4.72 (m, 1 H, Cp); 4.43 (m, 1 H,
Cp); 4.06 (m, 1 H, Cp); 3.63 (s, C
5
H
5
); 3.29 ± 3.22 (br. dq, MeCHP); 2.78 ± 2.75 (br. m, 1 H, Cy); 2.39 ± 2.32
31
1
(
(
br. m, 1 H, Cy); 2.03 ± 1.10 (m, 23 H, Cy, MeCHP); 0.22 (dd, J ˆ 6.4, 4.8, MePt). P{ H}-NMR (CDCl
3
): 44.4
1
2
1
2
d, J(Pt,P) ˆ 1810, J(P,P) ˆ 17.7, PCy
Isomer II (Me trans to PAr
; (SP-4-3)): 1H-NMR (CDCl
s, 1 arom. H); 7.84 (s, 1 arom. H); 7.78 (d, J ˆ 9.6, 2 arom. H); 4.68 (m, 1 H, Cp); 4.48 (m, 1 H, Cp); 4.28
2
); 11.7 (d, J(Pt,P) ˆ 4332, J(P,P) ˆ 17.6, PAr
2
).
2
3
): 8.53 ± 8.50 (d, J ˆ 10.4, 2 arom. H); 8.09
(
(
m, 1 H, Cp); 3.57 (s, C
5
H
5
); 3.42 (dq, J ˆ 7.1, 4.1, MeCHP); 2.78 ± 2.75 (br. m, 1 H, Cy); 2.39 ± 2.32 (br. m, 1 H,
31
1
1
Cy); 2.03 ± 1.10 (m, 23 H, Cy, MeCHP); 0.86 (dd, J ˆ 7.2, 1.7, MePt). P{ H}-NMR (CDCl
3
): 39.3 (d, J(Pt,P) ˆ
2
1
2
4
076, J(P,P) ˆ 16.1, PCy
2
); 14.7 (d, J(Pt,P) ˆ 1603, J(P,P) ˆ 16.1, PAr
2
).
(
SP-4)-{(1R)-1-[Bis(3,5-dimethylphenyl)phosphino-kP]-2-[(1R)-(dicyclohexylphosphino-kP)ethyl]ferro-
cene}chloro(methyl)platinum ([PtClMe(3f)]; 9f. According to the G.P. 4, from [PtClMe(COD)] (100 mg,
.28 mmol, 1 equiv.) and 3f (182 mg, 0.28 mmol, 1 equiv.): 9f as isomer mixture I/II 1:2.5 in quant. yield. Orange
solid.
Isomer I (Me trans to PCy
m, 4 arom. H); 4.49 (m, 1 H, Cp); 4.23 (m, 1 H, Cp); 4.14 (m, 1 H, Cp); 3.64 (s, C
0
; (SP-4-2)): 1H-NMR (CDCl
): 7.79 ± 7.74 (m, 2 arom. H); 7.10 ± 6.90
); 3.29 ± 3.24 (br. dq,
); 2.35 ± 2.28 (br. m, 1 H, Cy); 2.42 (s, 2 MeC ); 1.84 ±
2
3
(
5 5
H
MeCHP); 2.70 ± 2.67 (br. m, 1 H, Cy); 2.44 (s, 2 MeC
6
H
3
6 3
H
3
1
1
1
2
0
1
.86 (m, 23 H, Cy, MeCHP); 0.23 (dd, J ˆ 6.9, MePt. P{ H}-NMR (CDCl
3
): 44.9 (d, J(Pt,P) ˆ 1852, J(P,P) ˆ
1
2
7.5, PCy
2
); 7.8 (d, J(Pt,P) ˆ 4328, J(P,P) ˆ 17.5, PAr
2
).
1
Isomer II (Me trans to PAr
2
; (SP-4-3)): H-NMR (CDCl
3
): 7.79 ± 7.74 (m, 2 arom. H); 7.10 ± 6.90
(
m, 4 arom. H); 4.47 (m, 1 H, Cp); 4.32 (m, 1 H, Cp); 4.27 (m, 1 H, Cp); 3.59 (s, C
5
H
5
); 3.41 (dq, J ˆ 7.2, 3.8,
); 2.35 ± 2.28 (br. m, 1 H, Cy); 2.22 (s, 2 MeC ); 1.89 ±
): 39.1 (d, J(Pt,P) ˆ 4206,
MeCHP); 2.70 ± 2.67 (br. m, 1 H, Cy); 2.41 (s, 2 MeC
6
H
3
6 3
H
31
1
1
0
.86 (m, 23 H, Cy, MeCHP); 0.75 (dd, J ˆ 7.3, 2.4, MePt). P{ H}-NMR (CDCl
3
2
1
2
J(P,P) ˆ 16.7, PCy
2
); 10.5 (d, J(Pt,P) ˆ 1688, J(P,P) ˆ 16.7, PAr
2
).
(
SP-4)-{(1R)-1-[Bis(3,5-dimethoxyphenyl)phosphino-kP]-2-[(1R)-1-(dicyclohexylphosphino-kP)ethyl]-
ferrocene}chloro(methyl)platinum ([PtClMe(3h)]; 9h). According to the G.P. 4, from [PtClMe(cod)] (62.6 mg,
.175 mmol, 1 equiv.) and 3h (125 mg, 0.175 mmol, 1 equiv.): 147.3 mg (88%) of 9h as isomer mixture I/II 1 :4.5.
0
‡
‡
Orange solid. FAB-MS (pos.): 945 (100, [M � Me] ), 907 (76, [M � MeCl] ), 825 (5), 741 (7), 467 (5), 307 (19),
2
12 (8), 154 (39). Anal. calc. for C41
H
55ClFeO
4
P
2
Pt (960.21): C 51.29, H 5.77; found: C 51.38, H 6.00.
1
Isomer I (Me trans to PCy
2
; (SP-4-2)): H-NMR (CDCl
3
): 7.37 ± 7.33 (m, 2 arom. H); 6.66 ± 6.55
(
(
(
(
m, 3 arom. H); 6.39 ± 6.38 (m, 1 arom. H); 4.51 (m, 1 H, Cp); 4.23 (m, 1 H, Cp); 4.15 (m, 1 H, Cp); 3.86
s, 2 MeO); 3.73 (s, C ); 3.68 (s, 2 MeO); 3.33 ± 3.23 (br. dq, MeCHP); 2.52 ± 2.46 (br. m, 1 H, Cy); 2.34 ± 2.25
5
H
5
31
1
br. m, 1 H, Cy); 1.98 ± 1.09 (m, 23 H, Cy, MeCHP); 0.32 (dd, J ˆ 6.9, 4.2, MePt). P{ H}-NMR (CDCl
3
): 44.4
1
2
1
2
d, J(Pt,P) ˆ 1834, J(P,P) ˆ 17.9, PCy
2
); 11.9 (d, J(Pt,P) ˆ 4372, J(P,P) ˆ 17.9, PAr
2
).
1
Isomer II (Me trans to PAr
2
; (SP-4-3)): H-NMR (CDCl
3
): 7.37 ± 7.33 (m, 2 arom. H); 6.66 ± 6.55
(
(
2
m, 3 arom. H); 6.39 ± 6.38 (m, 1 arom. H); 4.49 (m, 1 H, Cp); 4.32 (m, 1 H, Cp); 4.29 (m, 1 H, Cp); 3.85
s, 2 MeO); 3.71 (s, C
5
H
5
); 3.68 (s, 2 MeO); 3.39 (dq, J ˆ 14.7, 7.3, MeCHP); 2.71 ± 2.68 (br. m, 1 H, Cy); 2.34 ±
31
1
.25 (br. m, 1 H, Cy); 1.98 ± 1.09 (m, 23 H, Cy, MeCHP); 0.77 (dd, J ˆ 7.4, 2.5, MePt). P{ H}-NMR (CDCl
3
):
1
2
1
2
3
9.1 (d, J(Pt,P) ˆ 4176, J(P,P) ˆ 17.0, PCy
2
); 14.5 (d, J(Pt,P) ˆ 1699, J(P,P) ˆ 17.0, PAr
2
).

3126
Helvetica Chimica Acta ± Vol. 84 (2001)
REFERENCES
[1] A. Togni, N. Bieler, U. Burckhardt, C. Köllner, G. Pioda, R. Schneider, A. Schnyder, Pure Appl. Chem.
1
999, 71, 1531.
[
[
2] R. Dorta, C. Köllner, G. Pioda, A. Togni, Pure Appl. Chem. 1998, 70, 1477.
3] A. Togni, in ꢀMetallocenesꢁ, Eds. A. Togni and R. L. Halterman, Wiley-VCH, Weinheim, 1998, Vol. 2,
p. 685.
[
[
[
[
[
4] T. Hayashi, in ꢀFerrocenesꢁ, Eds. A. Togni and T. Hayashi, VCH, Weinheim, 1995, p. 105.
5] C. J. Richards, A. J. Locke, Tetrahedron: Asymmetry 1998, 9, 2377.
6] A. Togni, C. Breutel, A. Schnyder, F. Spindler, H. Landert, A. Tijani, J. Am. Chem. Soc. 1994, 116, 4062.
7] H.-U. Blaser, F. Spindler, Top. Catal. 1997, 4, 275.
8] H.-U. Blaser, H. P. Buser, K. Coers, R. Hanreich, H. P. Jalett, E. Jelsch, B. Pugin, H. D. Schneider, F.
Spindler, A. Wegmann, Chimia 1999, 53, 275.
[9] H.-U. Blaser, W. Brieden, B. Pugin, F. Spindler, M. Studer, A. Togni, Top. Catal. 2001, in print.
[
[
[
[
[
[
[
[
10] H.-U. Blaser, H.-P. Buser, R. Häusel, H.-P. Jalett, F. Spindler, J. Organomet. Chem. 2001, 621, 34.
11] A. Schnyder, L. Hintermann, A. Togni, Angew. Chem. 1995, 107, 996.
12] A. Schnyder, A. Togni, U. Wiesli, Organometallics 1997, 8, 255.
13] G. Pioda, A. Togni, Tetrahedron: Asymmetry 1998, 9, 3903.
14] S. Bronco, G. Consiglio, S. Di Benedetto, M. Fehr, F. Spindler, A. Togni, Helv. Chim. Acta 1995, 78, 883.
15] C. Gambs, S. Chaloupka, G. Consiglio, A. Togni, Angew. Chem., Int. Ed. 2000, 39, 2486.
16] I. Ugi, D. Marquarding, H. Klusacek, G. Gokel, P. Hoffmann, J. Am. Chem. Soc. 1970, 92, 5389.
17] T. Hayashi, T. Mise, M. Fukushima, M. Kagotani, N. Nagashima. Y. Hamada, A. Matsumoto, S. Kawakami,
M. Konishi, K. Yamamoto, M. Kumada, Bull. Chem. Soc. Jpn. 1980, 53, 1138.
18] D. Marquarding, H. Klusacek, G. Gokel, P. Hoffmann, I. Ugi, J. Am. Chem. Soc. 1970, 92, 5389.
19] A. Togni, C. Breutel, M. C. Soares, N. Zanetti, T. Gerfin, V. Gramlich, F. Spindler, G. Rihs, Inorg. Chim.
Acta 1994, 222, 213.
[
[
[
[
[
20] M. Soares, Thesis No. 12178, ETH-Zürich, 1997.
21] D. Drew, J. R. Doyle, A. G. Shaver, Inorg. Synth. 1988, 346.
22] R. E. Rülke, J. M. Ernsting, A. L. Spek, C. J. Elsevier, P. W. N. M. Van Leeuwen, K. Vrieze, Inorg. Chem.
1
993, 32, 5769.
[
[
[
23] J. Chatt, L. M. Vallarino, L. M. Venanzi, J. Chem. Soc. 1957, 3413.
24] W. de Graaf, J. Boersma, W. J. J. Smeets, A. L. Spek, G. van Koten, Organometallics 1989, 8, 2907.
25] K. Nozaki, N. Sato, Y. Tonomura, M. Yasutomi, H. Takaya, T. Hijama, T. Matsubara, N. Koga, J. Am.
Chem. Soc. 1997, 119, 12779.
[
[
26] C. S. Shultz, J. Ledeford, J. M. DeSimone, M. Brookhart, J. Am. Chem. Soc. 2000, 122, 6351.
27] A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G. Watson, R. Taylor, in ꢀStructure Correlationꢁ,
Eds. H.-B. Bürgi and J. Dunitz, VCH, Weinheim, 1994, Vol. 2, p. 751 (Appendix A).
28] W. L. Steffen, G. J. Palenik, Inorg. Chem. 1976, 15, 2432.
[
[
29] V. D. Makhaev, Z. M. Dzhabieva, S. V. Konovalikhin, O. A. DꢁYachenko, G. P. Belov, Koord. Khim. 1996,
2
2, 598.
[
[
[
[
[
[
30] T. G. Appleton, H. C. Clark, L. E. Manzer, Coord. Chem. Rev. 1973, 10, 335.
31] G. P. C. M. Dekker, C. J. Elsevier, K. Vrieze, P. W. N. M. van Leeuwen, Organometallics 1992, 11, 1598.
32] P. W. N. M. van Leeuwen, P. C. J. Kamer, J. N. H. Reek, P. Dierkes, Chem. Rev. 2000, 100, 2741.
33] J. D. Unruh, J. R. Christenson, J. Mol. Catal. 1982, 14, 1434.
34] A. L. Casalnuovo, T. V. RajanBabu, T. A. Ayers, T. H. Warren, J. Am. Chem. Soc. 1994, 116, 9869.
35] T. Hayashi, A. Yamazaki, J. Organomet. Chem. 1991, 413, 295.
Received June 18, 2001