New chiral ferrocene-bridged phosphole-phosphane ligands

Article abstract of DOI:10.1002/ejic.200600771

A convenient synthesis of new chiral ferrocenene-bridged phosphole-phosphane ligands in an enantiomerically pure form has been developed. These new chiral P,P ligands have been tested in a palladium-catalysed allylic substitution reaction. High activities and moderate enantioselectivities (up to 61 %) were observed. A palladium(II) complex has been isolated and its crystal structure established. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200600771

FULL PAPER
DOI: 10.1002/ejic.200600771
New Chiral Ferrocene-Bridged Phosphole–Phosphane Ligands
Jose Guadalupe Lopez Cortes,[a][‡] Olivier Ramon,[a] Sandrine Vincendeau,[a] Daniel Serra,[a]
Franck Lamy,[a] Jean-Claude Daran,[a] Eric Manoury,*[a] and Maryse Gouygou*[a]
Keywords: Ferrocenes / Phospholes / P,P ligands / Asymmetric catalysis / X-ray diffraction
A convenient synthesis of new chiral ferrocenene-bridged
phosphole–phosphane ligands in an enantiomerically pure
form has been developed. These new chiral P,P ligands have
been tested in a palladium-catalysed allylic substitution reac-
tion. High activities and moderate enantioselectivities (up to
61%) were observed. A palladium(II) complex has been iso-
lated and its crystal structure established.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
Introduction
Considerable efforts have been devoted to the develop-
ment of new chiral ligands owing to the growing impor-
tance of transition-metal-catalysed asymmetric synthesis.[1]
Among these chiral ligands, ferrocene-containing ligands
are among the most interesting because of their stability,
easy introduction of planar chirality and special electronic
and stereoproperties of the ferrocene skeleton.[2] Amongst
the chiral ferrocene-based ligands, enantiopure 1,2-disubsti-
tuted ferrocene derivatives, especially ferrocenediyldiphos-
phane ligands, played a dominant role.[3] Typical examples
are Trap ligands,[4] and diphosphane Josiphos ligands,[5] in
particular the industrially important Xyliphos,[6] Tania-
phos[7] or Walphos-type ligands[8] (Figure 1). Common
characteristics of these ligands include the ferrocenylethyl
backbone and the presence of both planar and central chi-
ralities. Little attention has been paid to ligands based on
a ferrocenylmethyl backbone or more generally to those
having ferrocene possessing planar chirality as their only
element of chirality. Reported examples include Trap (I),[9]
Josiphos[10] analogues (II) or diphosphanes (III)[11] devel-
oped by Kagan et al. (Figure 2).
Figure 1. Well-known ferrocenyldiphosphane ligands combining
both planar and central chiralities.
Recently, we have extended the family of 1,2-disubsti-
tuted planar-chiral ferrocene by introduction of a phos-
phole group leading to planar-chiral ferrocene-bridged
phosphole–amine ligands.[12] Chiral phosphole-based li-
gands[13] have been rather infrequently used for asymmetric
catalysis,[14] despite the fact that phospholes are efficient li-
gands in homogeneous transition-metal catalysis.[15] How-
Figure 2. Ferrocenyldiphosphane ligands possessing planar chiral-
ity as their only element of chirality.
[a] Laboratoire de Chimie de Coordination, UPR-CNRS 8241,
205 Route de Narbonne, 31077 Toulouse Cedex, France
Fax: +33-5-61553131
ever, introduction of a phosphole group, which possesses
different steric and electronic effects with respect to phos-
phanes, may modulate the ligand properties. Other advan-
tages of this type of ligand are related to chiral flexibility
of unsymmetrically substituted phosphole due to the low
inversion barrier of the phosphorus atom in phosphole.[16]
E-mail: manoury@lcc-toulouse.fr
gouygou@lcc-toulouse.fr
[‡] Present address: Instituto de Quimica UNAM, Circuito Ex-
terior, Ciudad Universitaria, Coyoacan, 04510 México, D. F.,
Mexico
5148
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New Chiral Ferrocene-Bridged Phosphole–Phosphane Ligands
FULL PAPER
A chirally flexible phosphole can (i) adjust the configura- cules. This strategy required the introduction of the planar
tion to accommodate the metal centre and (ii) magnify the chirality in the first step by a stereoselective ortho metalla-
chiral part of the catalytic system.[17]
tion step, which required a chiral auxiliary to achieve ste-
As part of our continuing interest in ferrocene chemis- reochemically controlled addition of the phospholyl group
try[18] and in the design and synthesis of new chiral phos- on the ferrocene moiety. The stereoselective ortho metalla-
phole-based ligands,[19] we were interested in ferrocene-de- tions reported to date include cyclopalladation of [(dimeth-
rived phosphole ligands with only planar chirality for asym- ylamino)methyl]ferrocene, ortholithiation of ferrocenyl sulf-
metric catalysis. In this paper, we describe the synthesis of oxides, dioxanes, amines, oxazolines, hydrazones or oxaza-
new 1,2-disubstituted ferrocene-bridged phosphole–phos- phospholidine oxides and so forth.[2c,22,23]
phane ligands involving the introduction of various phos-
To control planar chirality, we chose Kagan’s method[24]
pholyl groups on Kagan’s acetal derivatives. The coordina- starting from a chiral dioxane. So, the synthetic pathway
tion chemistry and the catalytic properties of these new chi- used is based on six stereochemically controlled reactions,
ral ferrocene-bridged phosphole–phosphane ligands are as shown in Scheme 2. In the first step, diastereoselective
also reported.
ortho lithiation of acetal 1 was achieved with tBuLi. The
lithio intermediate reacted cleanly with various 1-cyano-
phospholes (2a,[25] 2b[14k] and 2c) as electrophilic reagents
to afford the corresponding ferrocenylphosphole products.
To facilitate the purification and the characterisation of
these compounds, they were converted in situ into air-stable
sulfur derivatives 3a–c by using an excess of sulfur in
dichloromethane at room temperature. Compounds 3a, 3b
and 3c, isolated after column-chromatographic purification,
were obtained in each case as an enantiomerically pure dia-
stereoisomer as confirmed by 1H, 31P and 13C NMR analy-
sis and X-ray diffraction studies. The (S) configuration for
the planar chirality, which is expected from the literature,[24]
was confirmed by X-ray analysis on monocrystals in the
case of 3b. A molecular view of compounds (S)-3b is shown
in Figure 3 with the atom-labelling scheme. As expected,
the phosphole ring is planar, with the largest deviation
[0.028(2) Å] at C11. The phosphorus atom P1 deviates
slightly by 0.132(5) Å from the plane of the Cp ring to
Results and Discussion
The synthetic approach of 1,2-disubtituted ferrocene-
based phosphane by nucleophilic displacement of a leaving
group (Scheme 1), as described by Hayashi et al.[20] or
Togni et al.,[21] could be used to prepare the target mole-
Scheme 1. Retrosynthetic synthesis of ferrocene-bridged phos-
phole–phosphane ligands.
Scheme 2. Synthesis of 8: (i) tBuLi, –78 °C to room temperature; 1-cyanophosphole 2, –30 °C; S8, CH2Cl2, room temperature; (ii) H+,
H2O/CH2Cl2, reflux; (iii) NaBH4, room temperature; (iv) AcCl/NEt3, 0 °C to room temperature; CH2Cl2; (v) R2PH, toluene, reflux, S8,
CH2Cl2, room temperature; (vi) P(NMe2)3, toluene reflux; (vii) PdCl2(CH3CN)2, CH2Cl2, room temperature.
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which it is attached, whereas the atom S1 is endo with re-
spect to this Cp ring. The phosphole and the Cp rings are
roughly perpendicular, with a dihedral angle of 83.1(1)°.
The dioxane ring is distorted and the puckering param-
eters[26] show that its conformation is close to that of a
chair: the θ and φ angles calculated for the atom sequence
C21–O22–C23–C24–C25–O26 are 177.2(3)° and 147(6)°,
respectively. Owing to steric hindrance, the dioxane ring is
twisted by 53.3(1)° with respect to the Cp ring. The two Cp
rings are nearly eclipsed, with a twisted angle of only 2.9°.
Figure 4. Molecular view of 5b with atom-labelling scheme. Ellip-
soids represent 30% probability. Selected bond lengths [Å] and
bond angles [°]: P(1)–S(1) 1.9677(6), P(1)–C(1) 1.790(2), P(1)–C(11)
1.797(2), P(1)–C(14) 1.799(2), C(2)–C(21) 1.505(3), C(21)–O(21)
1.423(2), Fe(1)–Cg(1) 1.636(8), Fe(1)–Cg(2) 1.646(8), Cg(1)–Fe(1)–
Cg(2) 176.6(3). Cg(1) and Cg(2) are the centroids of the
(C1,C2,C3,C4,C5) Cp ring and the (C6,C7,C8,C9,C10) Cp ring,
respectively.
Alcohols (S)-5a–c were quantitatively transformed into
acetates (S)-6a–c by treatment with acetyl chloride. Subse-
quent nucleophilic substitution reactions with secondary
phosphanes followed by sulfuration reaction led to ferro-
cene-bridged phosphole–phosphanes as disulfide deriva-
tives 7a–c. Compounds (S)-7a, (S)-7b and (S)-7c, obtained
in 57%, 74% and 78% yield, respectively, were fully charac-
Figure 3. Molecular view of 3b with atom-labelling scheme. Ellip-
soids represent 50% probability. Selected bond lengths [Å] and
bond angles [°]: P(1)–S(1) 1.9487(11), P(1)–C(1) 1.790(3), P(1)–
C(11) 1.796(3), P(1)–C(14) 1.809(3), C(2)–C(21) 1.504(4), Fe(1)–
Cg(1) 1.645(9), Fe(1)–Cg(2) 1.660(9); Cg(1)–Fe(1)–Cg(2) 178.2(6).
Cg(1) and Cg(2) are the centroids of the (C1,C2,C3,C4,C5) Cp ring
and the (C6,C7,C8,C9,C10) Cp ring, respectively.
In the next step, the acid hydrolysis of the acetal (S)-3a–c terised.
was performed with p-toluenesulfonic acid to quantitatively
In the last step, deprotection was successfully achieved
yield the corresponding aldehydes (S)-4a–c. Reduction of with tris(dimethylamino)phosphane in refluxing toluene
the crude aldehydes (S)-4a–c of low stabilities was then providing the ferrocene-bridged phosphole–phosphanes
readily achieved by using an excess of sodium tetrahydrobo- (S)-8b and (S)-8c. However, this procedure gave only low
rate. The corresponding alcohols (S)-5a–c were obtained in yields of (S)-8a, which could not be isolated in a pure form
good yields after column-chromatographic purification. and was only identified by mass spectrometry. The structure
The (S) configuration of compound 5b was again confirmed of (S)-8b was determined by X-ray diffraction analysis. A
by X-ray diffraction analysis. A molecular view of alcohol molecular view of complex (S)-8b is shown in Figure 5. As
(S)-5b is shown in Figure 4 with the atom-labelling scheme. already observed in free phosphole ligands,[27] the phospho-
As previously noticed, the phosphole ring is planar, with rus atom is located above the butadiene fragment [0.208
the largest deviation [–0.022(1) Å] at C14 and a dihedral (5) Å]. The atom P1 deviates from the plane of the Cp ring
angle of 89.93(7)° with the Cp ring to which it is attached. by 0.189(5) Å. The atom P2 is oriented exo with respect to
The atom P1 deviates from the plane of the Cp ring by the Cp ring and is located 1.518(6) Å above it. The two Cp
0.223(3) Å, certainly minimising steric hindrance, whereas rings are perfectly eclipsed with a twist angle of only 0.5°.
the atom S1 is slightly endo by 0.341(4) Å with respect to The two phenyl rings are roughly perpendicular with a dihe-
this Cp ring. The two Cp rings are twisted relative to each dral angle of 87.1(1)°. It is interesting to note that the lone
other by 10.7°. An interesting feature is the occurrence of pairs of the two phosphorus atoms are in the correct ar-
an O–H···S intermolecular hydrogen bond [O–H = 0.84 Å, rangement for chelating on a metal precursor.
H···S = 2.53 Å, O···S = 3.2700(15) Å, O–H···S = 147.3°]
linking the molecules to form a chain developing parallel by forming palladium(II) complexes. Ligand 8b reacted
to the a-axis. in dichloromethane at room temperature with
The mode of complexation of new ligands 8 was checked
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New Chiral Ferrocene-Bridged Phosphole–Phosphane Ligands
FULL PAPER
Figure 5. Molecular view of 8b with atom-labelling scheme. Ellipsoids represent 30% probability. Selected bond lengths [Å] and bond
angles [°]: P(1)–C(1) 1.809(3), P(1)–C(11) 1.800(3), P(1)–C(14) 1.807(3), C(2)–C(21) 1.515(5), C(21)–P(2) 1.842(3), P(2)–C(211) 1.835(4),
P(2)–C(221) 1.842(3), Fe(1)–Cg(1) 1.6391(4), Fe(1)–Cg(2) 1.6587(4), Cg(1)–Fe(1)–Cg(2) 176.03(3). Cg(1) and Cg(2) are the centroids of
the (C1,C2,C3,C4,C5) Cp ring and the (C6,C7,C8,C9,C10) Cp ring, respectively.
[PdCl2(CH3CN)2] in 30 min to afford complex (S)-9b (80% diffraction study. There are two molecules in the asymmet-
1
yield) of formula [PdCl2(8b)] as indicated by H, 13C and ric unit with nearly identical geometry. A view of molecule
31P NMR spectroscopy and mass spectrometry. The molec- A is depicted in Figure 6. If the phosphole and the Cp form
ular structure of complex (S)-9b was established by X-ray a dihedral angle of 86.3(4)° [88.5(4) for molecule B], a value
close to that observed in the free ligand, the atom P2 of the
diphenylphosphanyl group is now oriented endo with re-
spect to the Cp ring to accommodate the PdCl2 unit. The
geometry of the chelating group is closely related to the
recently reported structure of {1-(diphenylphosphanyl)-
2,1Ј-[(1-diphenylphosphanyl)butane-1,3-diyl]ferrocene}-
PdCl2.[28] As expected, the PdII atom is square-planar coor-
dinated, with the largest deviation from the least-squares
plane being 0.016(2) Å [0.010(2) Å for molecule B] at the
Pd atom. The chelating six-membered ring Pd1–P1–C1–
C2–C21–P2 is folded around the P1···C21 axis with a dihe-
dral angle of 30.0(4)° [32.8(3)° for molecule B]. The coordi-
nation results in a larger twist angle between the two Cp
rings of 10.8° (12.2° for molecule B).
The chiral ligands (S)-8b and (S)-8c were evaluated in
the palladium-catalysed asymmetric allylic substitution.[29]
The reaction of 1,3-diphenylprop-2-enyl acetate (10) with
the anion of dimethyl malonate (11) was carried out in the
presence of [Pd(C3H5)Cl]2 (1 mol-%) and the chiral ligands
8b,c (1 mol-%) (see Scheme 3). Using the ligand (S)-8b, the
allylic acetate 10 in CH2Cl2 was quantitatively converted
within 1 h at room temperature to the desired product (S)-
Figure 6. Molecular view of 9b with atom labelling. Ellipsoids rep-
12 in 38% ee. Under similar conditions, the ligand (S)-8c
resent 30% probability. Selected bond lengths [Å] and bond angles
[°]: Pd–Cl(1) 2.347(3) [2.348(3)], Pd–Cl(2) 2.360(3) [2.363(3)], Pd–
P(1) 2.237(3) [2.245(3)], Pd–P(2) 2.261(3) [2.262(3)], P(1)–C(1)
1.791(10) [1.788(10)], C(2)–C(21) 1.487(15) [1.510(15)], P(2)–C(21)
1.828(10) [1.823(11)], Fe(1)–Cg(1) 1.656(3) [1.665(3)], Fe(1)–Cg(2)
1.669(3) [1.666(3)]; Cg(1)–Fe(1)–Cg(2) 174.8(4). Cg(1) and Cg(2)
are the centroids of the (C1,C2,C3,C4,C5) Cp ring and the
(C6,C7,C8,C9,C10) Cp ring, respectively. The values in square
brackets refer to molecule B.
Scheme 3. Asymmetric allylic substitution reaction.
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were evaporated in vacuo to yield an orange oil. This oil was dis-
solved in dichloromethane (30 mL). Sulfur (5.7 equiv.) was added
and the mixture was stirred overnight. After concentration, the
mixture was chromatographed on silica gel using a pentane/dichlo-
romethane mixture (3:7, v/v).
led also to the quantitative conversion of 10 within 1 h to
(S)-12, but with a better enantioselectivity (61% ee).
Conclusions
(2S,4S,SFc)-2-[(2,3,4,5-Tetramethyl-1-thioxo-1H-1λ5-phosphol-1-yl)-
ferrocenyl]-4-(methoxymethyl)-1,3-dioxane (3b): Yellow-orange oil
(yield 68%). Crystals suitable for X-ray analysis were obtained by
diffusion of pentane into a dichloromethane solution. 1H NMR
(CDCl3): δ = 1.51 (br. d, J = 13.3 Hz, 1 H, CH2CH2CH), 1.83 (m,
1 H, CH2CH2CH), 1.85 (br. s, 3 H, CH3), 1.94 (br. s, 3 H, CH3),
2.01 (d, JH,P = 13.3 Hz, 3 H, CH3), 2.13 (d, JH,P = 12.8 Hz, 3 H,
CH3), 3.32 (s, 3 H, OCH3), 3.35 (dd, ABX system, J = 10.1 and
5.1 Hz, 1 H, CH2OCH3), 3.44 (dd, ABX system, J = 10.1 and
5.2 Hz, 1 H, CH2OCH3), 3.95–4.10 (m, 2 H, CH, OCH2CH2), 4.02
(m, 1 H, subst. Cp), 4.25–4.30 (m, 1 H, OCH2CH2), 4.27 (m, 1 H,
subst. Cp), 4.39 (s, 5 H, Cp), 4.76 (m, 1 H, subst. Cp), 6.15 (s, 1
H, OCHO) ppm. 13C NMR (CDCl3): δ = 10.5 (d, JC,P = 13.8 Hz,
CH3 α phosphole), 11.3 (d, JC,P = 13.1 Hz, CH3 α phosphole), 14.0
(d, JC,P = 15.3 Hz, CH3 β phosphole), 14.2 (d, JC,P = 15.3 Hz, CH3
β phosphole), 28.5 (CH2CH2CH), 59.6 (OCH3), 67.5 (OCH2CH2),
69.9 (d, JC,P = 10.2 Hz, subst. Cp), 71.2 (d, JC,P = 8.1 Hz, subst.
A new and convenient preparation of ferrocene-bridged
phosphole–phosphane ligands in an enantiomerically pure
form has been achieved. Their coordination chemistry and
their abilities for catalysis in a palladium-catalysed asym-
metric allylic substitution reaction have been checked. Use
of these new unusual chiral P,P ligands in other asymmetric
catalytic reactions as well as optimisation of ligands by
modifying the phosphole ring part or the phosphane part
are currently being developed in our laboratories.
Experimental Section
General: All reactions were carried out under dry argon by using
Schlenk glassware and vacuum-line techniques. Solvents were
freshly distilled from standard drying agents. 1H, 13C{1H, 31P} and
31P{1H} NMR spectra were recorded with a Bruker WMX 400
instrument operating at 400, 162 and 100 MHz respectively. Chemi-
cal shifts are reported in ppm relative to Me4Si (1H and 13C) or
85% H3PO4 (31P). Mass spectra were obtained with a Nermag R10-
10 instrument (DCI, FAB) and with an Applied Biosystem API
365 instrument (APCI). Elemental analysis was performed by the
“Service d’Analyse du Laboratoire de Chimie de Coordination” at
Toulouse. Optical rotations were measured with a Perkin–Elmer
241 polarimeter. Acetal 1,[24b] 1-cyano-2,3,4,5-tetramethyl-
phosphole (2b),[14k] 1-phenyldibenzophosphole[30] and compounds
3a, 4a, 5a and 6a[12] were prepared as described in the literature.
Cp), 71.4 (Cp), 71.5 (d, JC,P = 79.0 Hz, quat. Cp), 71.9 (d, JC,P
10.5 Hz, subst. Cp), 75.7 (CH2OCH3), 76.0 (CH), 89.1 (d, JC,P
=
=
10.5 Hz, quat. Cp), 98.8 (OCHO), 128.4 (d, JC,P = 84.0 Hz, CH3 α
phosphole), 132.3 (d, JC,P = 82.7 Hz, CCH3 α phosphole), 143.2
(d, JC,P = 27.1 Hz, CCH3 β phosphole), 145.8 (d, JC,P = 27.2 Hz,
CCH3 β phosphole) ppm. 31P NMR (CDCl3): δ = 57.0 ppm. [α]D
= 3.4 (c = 0.5, CHCl3). MS (DCI, NH3): m/z (%) = 487 (100) [M
+ 1]. C24H32FeO3PS (487.40): calcd. C 59.14, H 6.62; found 59.27,
H 6.42.
(2S,4S,SFc)-2-[(Dibenzo-1-thioxo-1H-1λ5-phosphol-1-yl)ferro-
cenyl]-4-(methoxymethyl)-1,3-dioxane (3c): Yellow solid (yield
64%). M.p. 78 °C. 1H NMR (CDCl3): δ= 1.48 (d of m, J = 13 Hz,
1 H, CH2CH2CH), 1.81 (br. q of d, J = 13 and 5 Hz, 1 H,
CH2CH2CH), 3.42 (dd, AB system, J = 10.3 and 3.9 Hz, 1 H,
CH2OCH3), 3.43 (s, 3 H, OCH3), 3.56 (dd, AB system, J = 10.3
and 6.3 Hz, 1 H, CH2OCH3), 3.59 (m, 1 H, subst. Cp), 4.00 (td, J
= 11.9 and 2.5 Hz, 1 H, OCH2CH2), 4.15 (m, 1 H, subst. Cp), 4.19
(m, 1 H, CH), 4.3–4.25 (m, 1 H, OCH2CH2), 4.50 (s, 5 H, Cp),
4.80 (m, 1 H, subst. Cp), 6.40 (s, 1 H, OCHO), 7.35 (tdd, J = 7.5
and 1.0 Hz, JH,P = 3.8 Hz, 1 H, Ar), 7.44 (tt, J = 7.5 Hz, J = JH,P
= 1.2 Hz, 1 H, Ar), 7.51 (tdd, J = 7.4 and 1.1 Hz, JH,P = 3.7 Hz, 1
H, Ar), 7.57 (tt, J = 7.5 Hz, J = JH,P = 1.3 Hz, 1 H, Ar), 7.69 (dd,
1-Cyanodibenzophosphole (2c): A solution of 1-phenyldibenzophos-
phole (2 g, 7.7 mmol) in THF (15 mL) was added at room tempera-
ture to a suspension of lithium (0.16 g, 23 mmol) in THF (5 mL).
The reaction mixture was stirred at room temperature for 4 h. The
red suspension was filtered (to remove unreacted lithium) into an-
other Schlenk tube, cooled to –20 °C, and anhydrous AlCl3 (0.35 g,
2.6 mmol) was added. The reaction mixture was warmed to 0 °C,
stirred for 0.5 h and then transferred by cannula to a solution of
BrCN (1.63 g, 15.4 mmol) in THF (5 mL) cooled to –78 °C. The
mixture was stirred at –78 °C for 0.5 h, then warmed to room tem-
perature and stirred overnight. The mixture was concentrated to
dryness and the resulting residue was extracted with small portions
of diethyl ether. The combined diethyl ether extracts were filtered
through Celite and the solvents were evaporated to give crude com-
pound 2c as a white solid (0.93 g, 58%). This was used without
J = 7.6 Hz, JH,P = 3.1 Hz, 1 H, Ar), 7.78 (dd, J = 7.6 Hz, JH,P
=
3.0 Hz, 1 H, Ar), 7.99 (ddd, J = 7.4 and 1 Hz, JH,P = 10.3 Hz, 1
H, Ar), δ = 8.27 (ddd, J = 7.5 and 1 Hz, JH,P = 9.7 Hz, 1 H, Ar)
ppm. 13C NMR (CDCl3): δ= 28.3 (CH2CH2CH), 59.6 (OCH3),
67.4 (OCH2CH2), 69.9 (d, JC,P = 10.9 Hz, subst. Cp), 71.4 (Cp),
71.7 (d, JC,P = 9.0 Hz, subst. Cp), 73.0 (d, JC,P = 14.1 Hz, subst.
Cp), 74.0 (d, JC,P = 90.0 Hz, quat. Cp), 75.8 (CH), 76.0
(CH2OCH3), 89.4 (d, JC,P = 12.1 Hz, quat. Cp), 98.6 (OCHO),
121.3 (d, JC,P = 9.5 Hz, Ar), 121.8 (d, JC,P = 9.5 Hz, Ar), 129.5 (d,
1
purification. H NMR (CDCl3): δ = 7.47 (m, 2 H, Ar), 7.59 (m, 2
H, Ar), 7.90 (m, 4 H, Ar) ppm. 31P NMR (CDCl3): δ = –51.6 ppm.
General Procedure for Synthesis of Dioxanes 3: In a Schlenk tube, a
1.5  solution of tert-butyllithium in pentane (8.1 mL, 12.1 mmol,
1.1 equiv.) was added dropwise, at –78 °C under argon, to a solu-
tion of acetal 1 (3.47 g, 11 mmol) in dry diethyl ether (40 mL). The
solution was stirred at –78 °C for 15 min, then at room temperature
for 2 h. The solution was cooled to –30 °C and a solution of 1-
cyanophosphole 2 (1.2 equiv.) in dry diethyl ether (20 mL) was in-
troduced by cannula. The reaction mixture was stirred at room
temperature overnight. Dry triethylamine (0.5 mL) was introduced
by syringe, followed by water (2 mL). Under argon, the reaction
mixture was extracted with diethyl ether and washed with brine.
The organic fraction was dried with sodium sulfate and the solvents
JC,P = 11.5 Hz, Ar), 130.0 (d, JC,P = 12.1 Hz, Ar), 130.1 (d, JC,P
=
10.4 Hz, Ar), 130.9 (d, JC,P = 11.3 Hz, Ar), 132.5 (d, JC,P = 2.3 Hz,
Ar), 133.1 (d, JC,P = 2.3 Hz, Ar), 135.7 (d, JC,P = 93.3 Hz, quat.
Ar), 138.1 (d, JC,P = 91.6 Hz, quat. Ar), 139.6 (d, JC,P = 19.7 Hz,
quat. Ar), 141.7 (d, JC,P = 19.7 Hz, quat. Ar) ppm. 31P NMR
(CDCl3): δ = 42.9 ppm. [α]D = –24 (c = 0.5, CHCl3). MS (DCI,
NH3): m/z (%) = 531 (100) [M + 1]. C28H28FeO3PS (531.42): calcd.
C 63.41, H 5.13; found C 63.43, H 5.07.
General Procedure for the Synthesis of Ferrocenecarbaldehyde 4:
Acetal 3 (7.3 mmol), dichloromethane (120 mL) and an aqueous
5152
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Eur. J. Inorg. Chem. 2006, 5148–5157

New Chiral Ferrocene-Bridged Phosphole–Phosphane Ligands
FULL PAPER
solution (50 mL) of p-toluenesulfonic acid monohydrate (1.5 equiv.
for 3b or 2 equiv. for 3c) were introduced into a round-bottomed
flask equipped with a condenser and placed under argon. The reac-
tion mixture was stirred at reflux for 26 h (3b) or 54 h (3c). After
cooling to room temperature, the dark red solution was extracted
with dichloromethane, washed with distilled water, dried with so-
dium sulfate and the solvents were evaporated. Compounds 4, ob-
tained quantitatively as red oils, were only characterised by 31P and
1H NMR spectroscopy and used without purification.
(SFc)-2-(2,3,4,5-Tetramethyl-1-thioxo-1H-1λ5-phosphol-1-yl)ferro-
cenecarbaldehyde (4b): 1H NMR (CDCl3): δ = 1.89 (br. s, 3 H,
CH3), 1.95 (br. s, 3 H, CH3), 1.98 (d, JH,P = 13.7 Hz, 3 H, CH3),
2.07 (d, JH,P = 13.7 Hz, 3 H, CH3), 4.52 (s, 5 H, Cp), 4.61 (m, 1
H, subst. Cp), 4.72 (m, 1 H, subst. Cp), 5.16 (m, 1 H, subst. Cp),
10.58 (s, 1 H, CHO) ppm. 31P NMR (CDCl3): δ = 55.8 ppm.
73.3 (d, JC,P = 14.4 Hz, subst. Cp), 74.6 (d, JC,P = 9.8 Hz, subst.
Cp), 75.1 (d, JC,P = 90.4 Hz, quat. Cp), 92.0 (d, JC,P = 13.3 Hz,
quat. Cp), 121.7 (d, JC,P = 9.5 Hz, Ar), 121.9 (d, JC,P = 9.7 Hz,
Ar), 129.7 (d, JC,P = 11.7 Hz, Ar), 129.9 (d, JC,P = 10.7 Hz, Ar),
130.08 (d, JC,P = 11.8 Hz, Ar), 130.12 (d, JC,P = 10.6 Hz, Ar), 133.0
(d, JC,P = 2.3 Hz, Ar), 133.3 (d, JC,P = 2.3 Hz, Ar), 136.1 (d, JC,P
= 93.8 Hz, quat. Ar), 136.8 (d, JC,P = 91.5 Hz, quat. Ar), 140.2 (d,
JC,P = 19.5 Hz, quat. Ar), 141.5 (d, JC,P = 19.5 Hz, quat. Ar) ppm.
31P NMR (CDCl3): δ = 44.6 ppm. [α]D = –104.6 (CHCl3, c = 0.5).
MS (DCI, NH3): m/z (%) = 413 (100) [M – OH]+, 430 (15) [M]+.
C23H19FeOPS (430.29): calcd. C 64.20, H 4.45; found C 64.11, H
4.64.
General Procedure for Synthesis of Acetates 6: Alcohol 5 (0.7 mmol)
was dissolved in dry dichloromethane (7 mL) and anhydrous trieth-
ylamine (0.25 mL) in a Schlenk tube under argon. The solution
was then cooled to 0 °C and acetyl chloride (1.5 equiv.) was added
with a syringe. The solution was stirred at 0 °C for 30 min, then at
room temperature for 1 h. The solution was washed with diluted
hydrochloric acid then water and dried with sodium sulfate. After
evaporation of the solvents, crude compound 6 was quantitatively
obtained as an oil that was used without further purification in the
next step.
(SFc)-2-(Dibenzo-1-thioxo-1H-1λ5-phosphol-1-yl)ferrocenecarb-
aldehyde (4c): 1H NMR (CDCl3): δ = 3.38 (m, 1 H, subst. Cp),
4.25 (m, 1 H, subst. Cp), 4.43 (s, 5 H, Cp), 5.56 (m, 1 H, subst.
Cp), 7.48–7.88 (m, 8 H, Ar), 10.57 (s, 1 H, CHO) ppm. 31P NMR
(CDCl3): δ = 38.6 ppm.
General Procedure for Synthesis of Alcohols 5: Crude compound 4
(7.3 mmol) was dissolved in methanol (200 mL) and an aqueous
solution (140 mL) of sodium borohydride (2.78 g, 18.3 mmol) and
sodium hydroxide (11.2 g, 280 mmol) was added. The solution
turned rapidly from red to orange. After 15 min of stirring at room
temperature, the reaction mixture was extracted with dichlorometh-
ane. The organic phase was washed with diluted hydrochloric acid,
then water, and finally dried with sodium sulfate. After evaporation
of the solvents, the crude material was purified by flash chromatog-
raphy on silica gel using a pentane/diethyl ether mixture (2:8, v/v).
(SFc)-[2-(2,3,4,5-Tetramethyl-1-thioxo-1H-1λ5-phosphol-1-yl)ferro-
cenyl]methanol (5b): Yellow-orange oil (yield 51% from 3b). Crys-
tals suitable for X-ray analysis were obtained by diffusion of pen-
tane into a dichloromethane solution. M.p. 85 °C. 1H NMR
(CDCl3): δ = 1.86 (br. s, 3 H, CH3 β), 1.93 (br. d, JH,P = 12.1 Hz,
3 H, CH3 α), 1.96 (br. s, 3 H, CH3 β), 2.15 (br. d, JH,P = 13.0 Hz,
3 H, CH3 α), 3.39 (dd, J = 7.8 and 5.9 Hz, 1 H, OH), 4.03 (m, 1
H, subst. Cp), 4.24 (m, 1 H, subst. Cp), 4.38 (s, 5 H, Cp), 4.47 (dd,
(SFc)-(Acetoxy)[2-(2,3,4,5-tetramethyl-1-thioxo-1H-1λ5-phosphol-1-
1
yl)ferrocenyl]methane (6b): Yellow-orange. H NMR (CDCl3): δ =
1.89 (d, J = 10 Hz, 6 H, CH3), 1.99 [s, 3 H, C(O)CH3], 2.04 (d, J
= 13 Hz, 6 H, CH3), 4.26 (m, 1 H, subst. Cp), 4.33 (m, 1 H, subst.
Cp), 4.40 (m, 5 H, Cp), 4.53 (m, 1 H, subst. Cp), 5.14 (d, J =
11.9 Hz, 1 H, CH2), 5.33 (d, J = 11.9 Hz, 1 H, CH2) ppm. 31P
NMR (CDCl3): δ = 53.9 ppm.
(SFc)-(Acetoxy)[2-(dibenzo-1-thioxo-1H-1λ5-phosphol-1-yl)ferro-
1
cenyl]methane (6c): Orange-red oil. H NMR (CDCl3): δ = 1.98 [s,
3 H, C(O)CH3], 4.02 (m, 1 H, subst. Cp), 4.26 (m, 1 H, subst. Cp),
4.48 (s, 5 H, Cp), 4.51 (m, 1 H, subst. Cp), 5.11 (d, J = 12.1 Hz, 1
H, CH2), 5.27 (d, J = 12.1 Hz, 1 H, CH2), 7.3–8.1 (m, 8 H, Ar)
ppm. 31P NMR (CDCl3): δ = 39.8 ppm.
General Procedure for Synthesis of Compounds 7: Diphenylphos-
phane (2.5 equiv.) was added at room temperature to a solution of
crude 6 (0.7 mmol) in degassed toluene (10 mL). The reaction mix-
ABX system, J = 12.6 and 5.5 Hz, 1 H, CH2), 4.49 (m, 1 H, subst. ture was stirred under reflux for 24 h (7a, 7b) or 36 h (7c) and then
Cp), 4.59 (dd, ABX system, J = 12.8 and 7.8 Hz, 1 H, CH2) ppm. concentrated in vacuo to yield an orange oil. This oil was dissolved
13C NMR (CDCl3): δ = 10.6 (d, JC,P = 13.6 Hz, CH3 α), 11.3 (d,
in dichloromethane (10 mL). Sulfur (5 equiv.) was added and the
JC,P = 13.3 Hz, CH3 α), 14.0 (d, JC,P = 15.1 Hz, CH3 β), 14.3 (d, mixture was stirred overnight. After concentration, the mixture was
JC,P = 15.3 Hz, CH3 β), 59.4 (s, CH2), 69.3 (d, JC,P = 10.2 Hz,
subst. Cp), 70.7 (s, Cp), 71.8 (d, JC,P = 14.1 Hz, subst. Cp), 72.0
(d, JC,P = 80.2 Hz, quat. Cp), 74.4 (d, JC,P = 9.0 Hz, subst. Cp),
92.5 (d, JCP = 11.5 Hz, quat. Cp), 128.7 (d, JC,P = 84.2 Hz, CCH3
α), 131.5 (d, JC,P = 82.8 Hz, CCH3 α), 143.8 (d, JC,P = 26.9 Hz,
CCH3 β), 146.4 (d, JC,P = 27.1 Hz, CCH3 β) ppm. 31P NMR
(CDCl3): δ = 58.1 ppm. [α]D = –125 (CHCl3, c = 0.5). MS (DCI,
NH3): m/z (%) = 387 (100) [M + 1]. C19H23FeOPS (386.28): calcd.
C 59.07, H 6.00; found C 59.24, H 6.10.
chromatographed on silica gel using a pentane/diethyl ether mix-
ture (80:20).
(SFc)-[2-(3,4-Dimethyl-1-thioxo-1H-1λ5-phosphol-1-yl)ferrocenyl]-
(diphenylthioxophosphanyl)methane (7a): Yellow solid (yield 57%
1
from 5a). H NMR (CDCl3): δ = 1.95 (br. t, J = 3 Hz, 3 H, CH3),
2.09 (br. t, J = 3 Hz, 3 H, CH3), 4.11 (td, JH,H = 2.9 Hz, JH,P1
1.5 Hz, 1 H, subst. Cp), 4.31 (s, 5 H, Cp); 4.12 (t, JH,H = JH,P2
13.1 Hz, 1 H, CH2), 4.32–4.30 (m, 1 H, subst. Cp), 4.39 (t, JH,H
=
=
=
JH,P2 = 13.1 Hz, 1 H, CH2), 4.48 (ddd, J = 4.1 and 2.4 Hz, JH,P1
(SFc)-[(Dibenzo-1-thioxo-1H-1λ5-phosphol-1-yl)ferrocenyl]- = 2.8 Hz, 1 H, subst. Cp), 6.06 (br. d, JH,P = 30.5 Hz, 1 H, CH),
methanol (5c): Yellow solid (yield 56% from 3c). M.p. 200 °C (de-
composition). 1H NMR (CDCl3): δ = 3.58 (br. t, J ≈ 6 Hz, 1 H,
OH), 3.72 (m, 1 H, subst. Cp), 4.18 (m, 1 H, subst. Cp), 4.24 (s, 5
H, Cp), 4.56–4.5 (m, 2 H, subst. Cp, CH2), 5.00 (dd, J = 12.6 and
6.24 (br. d, JH,P = 30.6 Hz, 1 H, CH), 7.55–7.25 (m, 6 H, PPh2),
7.9–7.8 (m, 4 H, PPh2) ppm. 13C NMR (CDCl3): δ = 17.9 (d, JC,P1
= 17.8 Hz, CH3 phosphole), 18.0 (d, JC,P1 = 17.8 Hz, CH3 phos-
phole), 31.5 (d, JC,P2 = 5 Hz, CH2), 69.0 (d, JC,P1 = 87.5 Hz, quat.
5.7 Hz, 1 H, CH2), 7.44 (tdd, J = 7.5 and 0.9 Hz, JH,P = 3.8 Hz, 1 Cp), 70.1 (d, JC,P1 = 11.1 Hz, subst. Cp), 71.2 (Cp), 73.7 (d, JC,P1
H, Ar), 7.62–7.55 (m, 2 H, Ar), 7.66 (m, 1 H, Ar), 7.82 (dd, J =
7.7 Hz, JH,P = 3.1 Hz, 1 H, Ar), 7.88 (dd, J = 7.6 Hz, JH,P = 3.1 Hz,
1 H, Ar), 7.94 (dd, J = 7.4 Hz, JH,P = 10.5 Hz, 1 H, Ar), 8.11 (dd,
= 14.8 Hz, subst. Cp), 74.8 (d, JC,P1 = 8.9 Hz, subst. Cp), 87.2 (dd,
JC,P1 = 11.4 Hz, JC–P2 = 5.8 Hz, quat. Cp), 126.2 (d, JC,P1
71.7 Hz, CH phosphole), 126.6 (d, JC,P1 = 71.7 Hz, CH phosphole),
=
J = 7.3 Hz, JH,P = 10.6 Hz, 1 H, Ar) ppm. 13C NMR (CDCl3): δ 126.8 (d, JC,P2 = 13.4 Hz, PPh2), 129.1 (d, JC,P2 = 13.1 Hz, PPh2),
= 59.9 (s, CH2), 69.5 (d, JC,P = 10.9 Hz, subst. Cp), 70.7 (s, Cp), 131.6 (d, JC,P2 = 11.3 Hz, PPh2), 132.1 (d, JC,P2 = 3.3 Hz, PPh2),
Eur. J. Inorg. Chem. 2006, 5148–5157
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E. Manoury, M. Gouygou et al.
FULL PAPER
132.2 (d, JC,P2 = 11.4 Hz, PPh2), 132.4 (d, JC,P2 = 3.2 Hz, PPh2),
134.0 (d, JC,P2 = 69.3 Hz, quat. PPh2), 134.8 (d, JC,P2 = 71.1 Hz,
quat. PPh2), 152.7 (d, JC,P1 = 18.7 Hz, CCH3 phosphole), 152.9 (d,
JC,P1 = 18.5 Hz, CCH3 phosphole) ppm. 31P NMR (CDCl3): δ =
48.1 (P1, phosphole), 66.7 (P2, PPh2) ppm. MS (DCI, NH3): m/z
(%) = 559 (100) [M + 1].
(SFc)-[2-(3,4-Dimethyl-1H-1λ5-phosphol-1-yl)ferrocenyl](diphenyl-
phosphanyl)methane (8a): MS (DCI, NH3): m/z (%) = 495 (100)
[M + 1].
(SFc)-(Diphenylphosphanyl)[2-(2,3,4,5-tetramethyl-1H-1λ5-phosphol-
1-yl)ferrocenyl]methane (8b): Dark yellow solid (87 %). Crystals
suitable for X-ray analysis were obtained by diffusion of pentane
1
(SFc)-(Diphenylthioxophosphanyl)[2-(2,3,4,5-tetramethyl-1-thioxo-
1H-1λ5-phosphol-1-yl)ferrocenyl]methane (7b): Yellow oil (yield
into a dichloromethane solution. H NMR (CDCl3): δ = 1.89 (br.
s, 3 H, CH3 β phosphole), 1.93 (br. s, 3 H, CH3 β phosphole), 2.11
(br. d, JH,P1 = 10.7 Hz, 3 H, CH3 α phosphole), 2.22 (br. d, JH,P1
74% from 5b). 1H NMR (CDCl3): δ = 1.85 (br. s, 3 H, CH3
β
phosphole), 1.91 (br. s, 3 H, CH3 β phosphole), 1.92 (br. d, 3 H,
JH,P1 = 12.4 Hz, CH3 α phosphole), 2.12 (br. d, 3 H, JH,P1
13.1 Hz, CH3 α phosphole), 3.95 (t, 1 H, JH,H = JH,P2 = 13.3 Hz,
CH2), 4.15 (t, 1 H, JH,H = JH,P2 = 13.3 Hz, CH2), 4.16 (m, 1 H, Cp), 4.12 (t, J = 2.5 Hz, 1 H, subst. Cp), 4.24 (s, 5 H, Cp), 7.4–7.3
subst. Cp), 4.27 (m, 1 H, subst. Cp), 4.34 (s, 5 H, Cp), 4.46 (m, 1
(m, 8 H, PPh2), 7.5–7.4 (m, 2 H, PPh2) ppm. 13C NMR (CDCl3):
H, subst. Cp), 7.55–7.3 (m, 6 H, PPh2), 7.9–7.5 (m, 4 H, PPh2) δ = 14.0 (d, JC,P1 = 21.0 Hz, CH3 α phosphole), 14.3 (d, JC,P1
ppm. 13C NMR (CDCl3): δ = 10.4 (d, JC,P1 = 13.4 Hz, CH3
3.0 Hz, CH3 β phosphole), 14.5 (d, JC,P1 = 3.0 Hz, CH3 β phos-
phosphole), 11.4 (d, JC,P1 = 13.6 Hz, CH3 α phosphole), 14.1 (d, phole), 14.6 (d, JC,P1 = 21.4 Hz, JC,P2 = 3.9 Hz, CH3 α phosphole),
JC,P1 = 15.1 Hz, CH3 β phosphole), 14.5 (d, JC,P1 = 15.2 Hz, CH3 28.6 (dd, JC,P1 = 4.6 Hz, JC,P2 = 15.4 Hz, CH2), 69.0 (d, JC,P1
β phosphole), 31.3 (s, CH2), 70.3 (d, JC,P1 = 10.6 Hz, subst. Cp), 5.3 Hz, subst. Cp), 70.2 (Cp), 71.4 (dd, JC,P1 = 2.0 Hz, JC,P2
71.1 (Cp), 71.5 (d, JC,P1 = 79.0 Hz, quat. Cp), 73.3 (d, JC,P1
13.8 Hz, subst. Cp), 73.9 (d, JC,P1 = 7.9 Hz, subst. Cp), 85.9 (dd,
JC,P1 = 10.6 Hz, JC,P2 = 5.6 Hz, quat. Cp), 128.8 (d, JC,P2
= 10.6 Hz, 3 H, CH3 α phosphole), 3.15 (d, AB system, JH,P2
14.5 Hz, 1 H, CH2), 3.23 (dd, ABX system, JH,H = 1.4 Hz, JH,P2
=
=
=
14.5 Hz, 1 H, CH2), 3.86 (m, 1 H, subst. Cp), 3.97 (m, 1 H, subst.
=
α
=
=
=
7.0 Hz, subst. Cp), 72.0 (d, JC,P1 = 16.2 Hz, subst. Cp), 73.4 (dd,
JC,P = 3.9 Hz, JC,P = 12.8 Hz, CP), 88.7 (dd, JC,P = 9.5 Hz, JC,P
16.8 Hz, CCH2), 128.6 (CHAr), 128.8 (d, JC,P = 5.7 Hz, CHAr),
=
=
13.3 Hz, PPh2), 128.9 (d, JC,P1 = 82.7 Hz, CH3 α phosphole), 129.1
(d, JC,P2 = 13.3 Hz, PPh2), 130.2 (d, JC,P1 = 82.7 Hz, CH3 α phos-
phole), 131.4 (d, JC,P2 = 11.1 Hz, PPh2), 132.2 (d, JC,P2 = 11.2 Hz,
PPh2), 132.3 (d, JC,P2 = 4.7 Hz, PPh2), 132.4 (d, JC,P2 = 3.1 Hz,
128.9 (d, JC,P = 7.0 Hz, CHAr), 129.3 (CHAr), 132.5 (d, JC,P
17.7 Hz, CHAr), 133.9 (d, JC,P = 20.0 Hz, CHAr), 134.6 (d, JC,P
4.7 Hz, CCH3βP), 135.5 (CCH3βP), 139.8 (d, JC,P = 16.4 Hz, CArP),
140.0 (d, JC,P = 16.2 Hz, CArP), 142.3 (d, JC,P = 12.3 Hz, CCH3αP),
142.6 (d, JC,P = 12.5 Hz, CCH3αP) ppm. 31P NMR (CDCl3): δ =
–12.3 (P2, PPh2), 1.7 (P1, phosphole) ppm.
=
=
PPh2), 134.1 (d, JC,P2 = 71.4 Hz, quat. PPh2), 134.8 (d, JC,P2
=
71.1 Hz, quat. PPh2), 134.9 (d, JC,P2 = 73.5 Hz, quat. PPh2), 144.5
(d, JC,P1 = 26.7 Hz, CCH3 β phosphole), 147.1 (d, JC,P1 = 27.1 Hz,
CCH3 β phosphole) ppm. 31P NMR (CDCl3): δ = 56.7 (P1, phos-
phole), 66.7 (P2, PPh2) ppm. MS (APCI): m/z = 587 [M + 1].
(SFc)-(Diphenylphosphanyl)[2-(dibenzo-1H-1λ5-phospholyl)ferro-
cen-1-yl]methane (8c): Yellow solid (94%). Crystals suitable for X-
ray analysis were obtained by diffusion of pentane into a dichloro-
(SFc)-(Diphenylthioxophosphanyl)[2-(dibenzo-1-thioxo-1H-1λ5-
phosphol-1-yl)ferrocenyl]methane (7c): Orange solid (yield 77 %
from 5c). 1H NMR (CDCl3): δ = 3.84 (dd, JH,H = 16.0 Hz and
JH,P2 = 11.8 Hz, 1 H, CH2), 4.06 (br. s, 1 H, subst. Cp), 4.19 (m,
1 H, subst. Cp), 4.27 (s, 5 H, Cp), 4.40 (dd, JH,H = 16.0 Hz and
JH,P2 = 10.8 Hz, 1 H, CH2), 4.81 (br. s, 1 H, subst. Cp), 7.65–7.3
methane solution. 1H NMR (CDCl3): δ = 3.38 (br. d, JH,H
=
14.2 Hz, 1 H, CH2), 3.38 (br. s, 1 H, subst. Cp), 3.58 (br. d, JH,H
= 14.2 Hz, 1 H, CH2), 3.76 (br. s, 1 H, subst. Cp), 3.92 (br. s, 1 H,
subst. Cp), 4.26 (s, 5 H, Cp), 7.3–7. 55 (m, 14 H, Ar), 7.90 (br. d,
JH,H = 7.8 Hz, 1 H, Ar), 7.98 (br. d, JH,H = 7.4 Hz, 1 H, Ar), 8.02
(m, 1 H, Ar), 8.17 (m, 1 H, Ar) ppm. 13C NMR (CDCl3): δ = 29.3
(m, 12 H, Ar), 7.82–7.74 (m, 3 H, Ar), 7.95–7.85 (m, 3 H, Ar) ppm. (dd, JC,P2 = 15.7 Hz, JC,P1 = 8.1 Hz, CH2), 68.7 (d, JC,P1 = 2.0 Hz,
13C NMR (CDCl3): δ = 33.9 (d, JC,P2 = 54.1 Hz, CH2), 71.1 (d, subst. Cp), 69.6 (s, subst. Cp), 69.8 (s, Cp), 71.6 (dd, JC,P2 = 5.2 Hz,
JC,P1 = 11.4 Hz, subst. Cp), 71.7 (Cp), 72.6 (d, JC–P1 = 15.0 Hz,
subst. Cp), 73.7 (d, JC–P1 = 7.8 Hz, JC,P2 = 4.4 Hz, subst. Cp), 74.2
JC,P1 = 3.2 Hz, subst. Cp), 76.8 (quat. Cp), 89.3 (dd, JC,P1 =
23.0 Hz, JC,P2 = 16.2 Hz, quat. Cp), 121.1 (s, benzophosphole),
121.3 (s, benzophosphole), 126.9 (d, JC,P1 = 8.3 Hz, benzophos-
phole), 127.4 (d, JC,P1 = 7.4 Hz, benzophosphole), 128.26 (s, PPh2),
(dd, JC,P1 = 78.9 Hz, JC,P2 = 6.1 Hz, quat. Cp), 82.6 (dd, JC,P1
=
12.1 Hz, JC,P2 = 1.8 Hz, quat. Cp), 121.7 (d, JC,P1 = 9.5 Hz, 2 C,
benzophosphole), 129.1 (d, JC,P1 = 12.1 Hz, 2 C, PPh2), 129.9 (d,
JC,P1 = 12 Hz, benzophosphole), 130.0 (d, JC,P1 = 11 Hz, 2 C,
benzophosphole), 130.3 (d, JC,P1 = 11.0 Hz, benzophosphole),
131.5 (d, JC,P2 = 10.1 Hz, PPh2), 131.8 (d, JC,P2 = 2.8 Hz, PPh2),
132.0 (d, JC,P2 = 10.3 Hz, PPh2), 132.1 (d, JC,P2 = 2.7 Hz, PPh2),
128.30 (s, PPh2), 128.4 (d, JC,P2 = 7.1 Hz, PPh2), 128.5 (d, JC,P2
=
5.7 Hz, PPh2), 128.6 (s, benzophosphole), 129.0 (s, benzophos-
phole), 130.9 (dd, JC,P1 = 21.0 Hz, JC,P2 = 11.8 Hz, benzophos-
phole), 131.1 (d, JC,P1 = 21.0 Hz, benzophosphole), 132.0 (d, JC,P2
= 17.3 Hz, PPh2), 133.9 (d, JC,P2 = 19.8 Hz, PPh2), 138.5 (d, JC,P2
= 15.7 Hz, quat. PPh2), 139.3 (d, JC,P2 = 15.3 Hz, quat. PPh2),
141.8 (s, quat. benzophosphole), 142.6 (d, JC,P1 = 3.7 Hz, quat.
benzophosphole), 144.4 (d, JC,P1 = 3.9 Hz, quat. benzophosphole),
144.8 (d, JC,P1 = 4.0 Hz, quat. benzophosphole) ppm. 31P NMR
133.0 (d, JC,P1 = 2.2 Hz, benzophosphole), 133.1 (d, JC,P2
=
79.5 Hz, quat. PPh2), 133.2 (d, JC,P1 = 2.2 Hz, benzophosphole),
133.5 (d, JC,P2 = 78.0 Hz, quat. PPh2), 136.6 (d, JC,P1 = 92.7 Hz,
quat. benzophosphole), 136.8 (d, JC,P1 = 91.3 Hz, quat. benzophos-
phole), 140.7 (d, JC,P1 = 19.6 Hz, quat. benzophosphole), 141.0 (d,
JC,P1 = 19.4 Hz, quat. benzophosphole) ppm. 31P NMR (CDCl3):
δ = 41.7 (P2, PPh2), 43.4 (P1, phosphole) ppm. MS (DCI, NH3):
m/z (%) = 631 (80) [M + 1].
(CDCl3): δ = –13.5 (d, JP,P = 6.4 Hz, P2, PPh2), –26.5 (d, JP,P
=
6.4 Hz, P1, phosphole) ppm. MS (DCI, NH3): m/z (%) = 567 (100)
[M + 1].
Dichloro{(SFc)-(diphenylphosphanyl)[2-(2,3,4,5-tetramethyl-1H-1λ5-
phospholyl)ferrocen-1-yl]methane}palladium(II) (9b): Diphosphane
7b (0.025 g, 0.048 mmol) was dissolved in dry dichloromethane
(25 mL) in a Schlenk tube under argon and [PdCl2(CH3CN)2]
(0.015 mg, 0.058 mmol) was then added. The yellow solution
turned immediately orange then deep red and finally brown. After
30 min of stirring at room temperature, the solution was partially
General Procedure for Desulfurisation of Compounds 7: Tris(dime-
thylamino)phosphane (0.2 mL, 1.2 mmol, 4 equiv.) was added at
room temperature to a solution of 7 (0.3 mmol) in toluene (10 mL).
The reaction mixture was stirred at reflux for 24 h. After concentra-
tion, the mixture was chromatographed on alumina using pentane
and then a pentane/diethyl ether mixture (90:10).
5154
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Eur. J. Inorg. Chem. 2006, 5148–5157

New Chiral Ferrocene-Bridged Phosphole–Phosphane Ligands
FULL PAPER
concentrated (10 mL) and dry pentane (5 mL) was added dropwise.
A brown precipitate appeared. The red solution was filtered and
concentrated with a high-vacuum pump to yield a red-orange solid
1.8 mmol) and [(Pd(C3H5)Cl)]2 (3.3 mg, 0.009 mmol) in dry dichlo-
romethane (20 mL) was stirred at room temperature for 2 h. Di-
methyl malonate (11) (0.411 mL, 3.6 mmol), potassium acetate and
(28 mg) (yield 80%). Crystals suitable for X-ray analysis were ob- BSA (0.880 mL, 3.6 mmol) were added to the resulting solution.
tained by diffusion of pentane into a chloroform solution. 1H
NMR (CDCl3): δ = 2.00 (br. s, 3 H, CH3 β phosphole), 2.066 (br.
s, 3 H, CH3 β phosphole), 2.07 (br. d, JH,P1 = 13 Hz, 3 H, CH3 α
phosphole), 2.40 (br. d, JH,P1 = 13.8 Hz, 3 H, CH3 α phosphole),
3.40 (dd, JH,P1 = 2.3 Hz, JH,P2 = 10.5 Hz, 2 H, CH2), 3.95 (s, 5 H,
Cp), 4.13 (m, 1 H, subst. Cp), 4.26 (m, 1 H, subst. Cp), 4.34 (br.
s, 1 H, subst. Cp), 7.37 (m, 2 H, PPh2), 7.45 (m, 1 H, PPh2), 7.6–
7.5 (m, 3 H, PPh2), 7.75–7.65 (m, 2 H, PPh2), 8.1–8.0 (m, 2 H,
PPh2) ppm. 13C NMR (CDCl3): δ = 14.0 (d, JC,P1 = 15.3 Hz, CH3
α phosphole), 14.3 (d, JC,P1 = 12 Hz, CH3 β phosphole), 14.5 (d,
JC,P1 = 12 Hz, CH3 β phosphole), 14.7 (d, JC,P1 = 17 Hz, CH3 α
phosphole), 30.6 (dd, JC,P1 = 8.0 Hz, JC,P2 = 28.0 Hz, CH2), 63.2
The reaction was carried out at room temperature and monitored
by TLC for the disappearance of the acetate. After the reaction was
complete, the resulting mixture was diluted with diethyl ether
(5 mL) and quenched with a saturated aqueous solution of ammo-
nium chloride (5 mL). The aqueous phase was extracted with di-
ethyl ether, the combined organic layers were dried with magnesium
sulfate, filtered and the solvents evaporated. The conversion was
calculated from the crude reaction mixture by 1H NMR spec-
troscopy. Subsequent purification by chromatography on silica
eluting with ethyl acetate/pentane (15:85) afforded the product as
a white solid. The enantiomeric excess was determined by 1H NMR
using the chiral shift reagent Eu(hfc)3.
(dd, JC,P1 = 63.1 Hz, JC,P2 = 13.4 Hz, quat. Cp), 69.1 (d, JC,P1
=
X-ray Structure Determinations: A single crystal of each compound
was mounted under inert perfluoropolyether at the tip of a glass
fibre and cooled in the cryostream of a Stoe IPDS diffractometer
for 3b, 8b and 9b or an Oxford Diffraction XCALIBUR CCD dif-
fractometer for 5b. Data were collected using monochromatic Mo-
Kα radiation (λ = 0.71073). The structures were solved by direct
methods (SIR97[31]) and refined by least-squares procedures on F2
using SHELXL-97.[32] All H atoms were introduced in the calcula-
tion in idealised positions and treated as riding on their parent
atoms. The absolute configuration was confirmed by refinement of
the Flack’s enantiopole parameter[33] and careful examination of
sensitive reflections. Molecules were drawn with the help of OR-
7.1 Hz, subst. Cp), 70.7 (s, Cp), 71.5 (d, JC,P1 = 5.7 Hz, subst. Cp),
73.0 (dd, JC,P1 = 6.7 Hz, JC,P2 = 4.7 Hz, subst. Cp), 85.8 (br. d,
JC,P1 = 18 Hz, quat. Cp), 128.9 (d, JC,P2 = 11.1 Hz, PPh2), 129.15
(s, CCH3 β phosphole), 129.22 (s, CCH3 β phosphole), 129.23 (d,
JC,P2 = 11.3 Hz, PPh2), 129.7 (d, JC,P2 = 55.8 Hz, quat. PPh2), 130.8
(d, JC,P2 = 55.3 Hz, quat. PPh2), 131.8 (d, JC,P2 = 2.7 Hz, PPh2),
132.2 (d, JC,P2 = 3.0 Hz, PPh2), 133.9 (d, JC,P2 = 10.4 Hz, PPh2),
134.7 (d, JC,P2 = 10.9 Hz, PPh2), 146.9 (d, JC,P1 = 17.8 Hz, CCH3
α phosphole), 148.7 (d, JC,P1 = 18.2 Hz, CCH3 α phosphole) ppm.
31P NMR (CDCl3): δ = 36.2 (P1, phosphole), 46.8 (P2, PPh2) ppm.
MS (FAB, MNBA): m/z (%) = 663 (100) [M – Cl]+.
General Procedure for Palladium-Catalysed Allylic Substitution: A TEP32.[34] Crystal data and refinement parameters are shown in
mixture of ligand 8, 1,3-diphenylprop-2-enyl acetate (10) (0.454 g,
Table 1. CCDC-605992 to -605995 contain the supplementary crys-
Table 1. Crystal data and structure refinement.
3b
5b
8b
9b
Empirical formula
Formula mass
Temperature [K]
Wavelength [Å]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
α [°]
C24H31FeO3PS
486.37
180(2)
0.71073
monoclinic
P21
8.4215(16)
11.1878(16)
12.490(2)
90
C19H23FeOPS
386.25
180(2)
0.71073
monoclinic
P21
8.1583(6)
11.0794(7)
10.0725(7)
90
C31H32FeP2
522.36
180(2)
0.71073
orthorhombic
P212121
11.0468(7)
14.4359(12)
16.6373(13)
90
C33H34Cl8FeP2Pd
938.39
180(2)
0.71073
monoclinic
P21
9.7972(9)
18.2870(13)
21.391(3)
90
β [°]
95.92(2)
90
1170.5(3)
2
1.380
0.824
102.266(6)
90
889.66(11)
2
1.442
1.056
90
90
2653.2(3)
4
1.308
98.487(13)
90
3790.5(6)
4
1.644
1.530
γ [°]
V [Å3]
Z
Dcalcd. [Mg/m3]
µ [mm–1]
0.707
F(000)
Crystal size [mm]
θ [°]
276
404
1096
1880
0.76ϫ0.34ϫ0.16
2.43–26.11
11372
4109 (0.0321)
99.2
multiscan
0.9247/0.8729
F2
4374/3/313
1.118
0.64ϫ0.54ϫ0.31
3.46–28.28
6780
4105 (0.0200)
99.3
multiscan
0.731/0.522
F2
4105/1/213
1.053
0.38ϫ0.31ϫ0.28
2.21–26.04
26463
5206 (0.0536)
99.3
empirical
0.835/0.735
F2
5206/0/311
1.047
0.4ϫ0.32ϫ0.12
2.22–24.05
30390
11238 (0.0526)
93.9
multiscan
0.689/0.622
F2
11238/741/820
1.109
Reflections collected
Unique reflections [R(int)]
Completeness [%]
Absorption correction
Max./min. transmission
Refinement method
Data/restraints/parameters
Gof on F2
R1, wR2 [I Ͼ 2σ(I)]
R1, wR2 (all data)
0.0293, 0.0792
0.0306, 0.0804
0.0238, 0.0605
0.0246, 0.0613
0.000(10)
0.293/–0.318
0.0381, 0.0937
0.0500, 0.0985
–0.006(19)
0.999/–0.271
0.0637, 0.1560
0.0692, 0.1590
0.06(3)
Absolute structure parameter –0.06(5)
Largest diff. peak/hole [e/Å3]
0.326/–0.237
2.409/–1.177
Eur. J. Inorg. Chem. 2006, 5148–5157
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5155

E. Manoury, M. Gouygou et al.
FULL PAPER
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Received: August 18, 2006
Published Online: October 27, 2006
Eur. J. Inorg. Chem. 2006, 5148–5157
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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