Three new enantiomerically pure ferrocenylphosphole compounds

Article abstract of DOI:10.1107/S0108270106010833

The absolute configurations of three new enantiomerically pure ferrocenylphosphole compounds, namely (2S,4S,S_Fc)-4-methoxymethyl-2- [2-(9-thioxo-9λ⁵-phosphafluoren-9-yl)ferrocenyl]-1,3-dioxane, [Fe(C₅H₅)(C₂₃H₂₂O₃PS)], (III), (S_Fc)-[2-(9-thioxo-9λ⁵-phosphafluoren-9-yl) ferrocenyl]methanol, [Fe(C₅H₅)(C₁₈H ₁₄OPS)], (V), and (S_Fc)-diphenyl[2-(9-thioxo- 9λ⁵-phosphafluoren-9-yl]ferrocenylmethyl]phosphine, [Fe(C ₅H₅)(C₃₀H₂₃P₂)], (VIII), have been unambiguously established. All three ligands contain a planar chiral ferrocene group, bearing a dibenzophosphole and either a dioxane, a methanol or a diphenylphosphinomethane group on the same cyclopentadienyl. In compound (V), the occurrence of O - H...S and C - H...S hydrogen bonds results in the formation of a two-dimensional network parallel to (001). The geometry of the ferrocene frameworks agrees with related reported structures.

Full text of DOI:10.1107/S0108270106010833

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
et al., 2004) or Walphos-type ligands (Sturm et al., 2003).
Common characteristics of these ligands include the ferroce-
nylethyl backbone and the presence of both planar and central
chiralities. Little attention has been paid to ligands based on
the ferrocenylmethyl backbone or, more generally, to ferro-
cenes possessing planar chirality as their only element of
chirality. Thus, we have recently investigated the family of 1,2-
disubstituted planar chiral ferrocenes by the introduction of a
phosphole group, leading to planar chiral ferrocenylphosphole
ISSN 0108-2701
Three new enantiomerically pure
ferrocenylphosphole compounds
Â
amine ligands (Lopez Cortes et al., 2006). We report here the
a
b
Â
Â
Â
Jose Guadalupe Lopez Cortes, Sandrine Vincendeau,
Jean-Claude Daran,b* Eric Manouryb and Maryse
Gouygoub
structural characterization of three enantiomerically pure
ferrocenyl derivatives containing the dibenzophosphole
(9-phospha¯uorene) moiety, viz. (III), (V) and (VIII).
aInstituto de Quimica, UNAM, Circuito Exterior, Ciudad Universitaria, Coyoacan,
Mexico DF, Mexico, and bLaboratoire de Chimie de Coordination, UPR±CNRS
Â
8241, 205 Route de Narbonne, 31077 Toulouse Cedex, France
Correspondence e-mail: daran@lcc-toulouse.fr
Received 16 March 2006
Accepted 24 March 2006
Online 13 April 2006
The absolute con®gurations of three new enantiomerically
pure ferrocenylphosphole compounds, namely (2S,4S,SFc)-4-
methoxymethyl-2-[2-(9-thioxo-9ꢀ5-phospha¯uoren-9-yl)ferro-
cenyl]-1,3-dioxane, [Fe(C5H5)(C23H22O3PS)], (III), (SFc)-[2-
(9-thioxo-9ꢀ5-phospha¯uoren-9-yl)ferrocenyl]methanol, [Fe-
(C5H5)(C18H14OPS)], (V), and (SFc)-diphenyl[2-(9-thioxo-
9ꢀ5-phospha¯uoren-9-yl]ferrocenylmethyl]phosphine, [Fe-
(C5H5)(C30H23P2)], (VIII), have been unambiguously estab-
lished. All three ligands contain a planar chiral ferrocene
group, bearing a dibenzophosphole and either a dioxane,
a methanol or a diphenylphosphinomethane group on the
same cyclopentadienyl. In compound (V), the occurrence of
OÐHÁ Á ÁS and CÐHÁ Á ÁS hydrogen bonds results in the
formation of a two-dimensional network parallel to (001).
The geometry of the ferrocene frameworks agrees with related
reported structures.
A molecular view of compound (III) is shown in Fig. 1. As
expected, the phosphole ring is planar, with the largest
Ê
deviation being 0.068 (2) A for atom C112. Atom P1 deviates
Ê
slightly [by 0.204 (2) A] from the cyclopentadienyl (Cp) ring
to which it is attached, whereas atom S1 is endo with respect to
Ê
this Cp ring by 1.026 (3) A. The dibenzophosphole system and
Comment
Considerable efforts have been devoted to the development of
new chiral ligands owing to the growing importance of tran-
sition metal-catalysed asymmetric synthesis (Ojima, 2000;
Jacobsen et al., 1999; Noyori, 1994). Of these chiral ligands,
ferrocene-containing ligands are among the most interesting
because of their stability, the easy introduction of planar
chirality and the special electronic and stereoproperties of the
ferrocene skeleton (Togni & Hayashi, 1995; Borman, 1996;
Togni, 1996; Atkinson et al., 2004). Of the chiral ferrocene-
based ligands, enantiopure 1,2-disubstituted ferrocene deri-
vatives, especially ferrocenyldiphosphine ligands, have played
a dominant role (Colacot, 2003; Tang et al., 2003; Barbaro et
al., 2004). Typical examples are TRAP ligands (Sawamura et
al., 1996; Kuwano et al., 1999, 2000) and the diphosphine
Josiphos ligands (Blaser et al., 2002, and references therein), in
particular the industrially important Xyliphos (Blaser, 2002,
and references therein), Taniaphos (Lotz et al., 2002; Spindler
Figure 1
The molecular structure of compound (III), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level.
H atoms have been omitted for clarity.
m188 # 2006 International Union of Crystallography
DOI: 10.1107/S0108270106010833
Acta Cryst. (2006). C62, m188±m191

metal-organic compounds
the Cp rings are nearly perpendicular, making a dihedral angle
of 88.21 (5)ꢀ. The dioxane ring is distorted and the puckering
parameters (Cremer & Pople, 1975) show that its conforma-
tion is close to that of a chair: the ꢁ and ' angles calculated for
the atom sequence C21±O21±C22±C23±C24±O22 are
175.4 (2) and 133 (2)ꢀ, respectively. Owing to steric hindrance,
the dioxane ring is twisted with respect to the Cp ring, with
C3ÐC2ÐC21ÐO21 and C3ÐC2ÐC21ÐO22 torsion angles
of 5.0 (3) and 115.8 (2)ꢀ, respectively. The two Cp rings are
nearly eclipsed, with a twist angle of only 3.5ꢀ.
A molecular view of alcohol (V) is shown in Fig. 2. As noted
previously, the dibenzophosphole system is roughly planar,
Ê
with the largest deviation being 0.109 (2) A for atom C14, and
it makes a dihedral angle of 87.34 (7)ꢀ with the Cp ring to
which it is attached. Atom P1 is nearly coplanar with the Cp
Ê
ring, deviating by only 0.088 (2) A. Atom S1 is endo by
Ê
1.333 (3) A with respect to this Cp ring. An interesting feature
is the occurrence of an intermolecular OÐHÁ Á ÁS hydrogen
bond linking the molecules to form a chain developing parallel
to the a axis. It is worth pointing out that, in the related
compound (SFc)-[2-(3,4-dimethyl-1-thio-1H-1ꢀ5-phosphol-1-
yl)ferrocenyl]methanol (Mourgues et al., 2003), the OÐHÁ Á ÁS
interaction is only intramolecular. Moreover, in (V) the chains
are interconnected by weak CÐHÁ Á ÁS hydrogen bonds to
form a two-dimensional network parallel to (001) (Table 1 and
Fig. 3). The two Cp rings are twisted with respect to one
another by 13.9ꢀ. This larger value compared with compound
(III) might be related to the occurrence of the hydrogen bond.
The alcohol group is twisted with respect to the Cp plane, with
a C3ÐC2ÐC21ÐO21 torsion angle of 103.1 (3)ꢀ. A similar
conformation of the alcohol group has been found in the
related compound rac-2-(diphenylthiophosphoryl)ferrocenyl-
Â
Â
methanol (Stepnicka & Cõsarova, 2002). However, the OÐ
HÁ Á ÁS hydrogen bonds in that compound resulted in the
formation of a pseudo-dimer through an inversion centre.
A molecular view of complex (VIII) is shown in Fig. 4. As
already observed in free phosphole ligands (Tissot et al., 2000;
Ogasawara et al., 2001; Hydrio et al., 2002; Melaimi et al.,
2002), the P atom is located slightly above the butadiene
Figure 2
The molecular structure of compound (V), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level.
H atoms have been omitted for clarity.
Ê
fragment [0.129 (5) A]. Atom P1 is roughly in the plane of the
Ê
Cp ring, with a deviation from the mean plane of 0.09 (1) A.
Atom P2 is oriented exo with respect to the Cp ring and is
Ê
located 1.62 (1) A above it. The two Cp rings are perfectly
eclipsed, with a twist angle of 0.5ꢀ. The two phenyl rings make
a dihedral angle of 65.7 (2)ꢀ. It is interesting to note that the
lone pairs of the two P atoms are in the correct arrangement
for chelating to a metal precursor.
In all three compounds, the geometry within the ferrocene
framework is roughly identical (Table 2) and agrees with that
of related compounds found in the Cambridge Structural
Figure 3
Figure 4
A packing view for compound (V), showing the OÐHÁ Á ÁS and CÐHÁ Á ÁS
hydrogen-bonding interactions (dashed lines) resulting in the formation
of a two-dimensional network parallel to (001). [Symmetry codes: (i)
The molecular structure of compound (VIII), showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level.
H atoms have been omitted for clarity.
x
1, y, z; (ii) x + 2, y + 12, z + 1.]
ꢁ
Acta Cryst. (2006). C62, m188±m191
Cortes et al.
[Fe(C5H5)(C23H22O3PS)], [Fe(C5H5)(C18H14OPS)] and [Fe(C5H5)(C30H23P2)] m189

metal-organic compounds
Table 1
Hydrogen-bond geometry (A, ) for (V).
Database (Version 5.27; Allen, 2002). For these three
compounds, re®nement of the Flack parameter (Flack, 1983;
Bernardinelli & Flack, 1985) allowed the determination of the
absolute con®guration.
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O21ÐH21Á Á ÁS1i
0.82
0.93
2.73
2.78
3.426 (2)
3.633 (3)
144
153
C114ÐH114Á Á ÁS1ii
Experimental
Symmetry codes: (i) x 1; y; z; (ii) x ‡ 2; y ‡ 12; z ‡ 1.
Compounds (III), (V) and (VIII) were synthesized according to the
Â
procedure reported by Lopez Cortes et al. (2006) (see scheme).
Compound (VIII)
Intermediate products (IV), (VI) and (VII) were obtained as oils,
whereas crystals of (III), (V) and (VIII) suitable for X-ray analyses
were obtained by slow diffusion of pentane into dichloromethane
solutions.
Crystal data
[Fe(C5H5)(C30H23P2)]
Mr = 566.36
Orthorhombic, P212121
a = 10.9693 (10) A
Ê
b = 11.0436 (10) A
Z = 4
Dx = 1.369 Mg m
Mo Kꢃ radiation
ꢄ = 0.69 mm
T = 180 (2) K
Prism, yellow
0.2 Â 0.12 Â 0.1 mm
3
1
Ê
Compound (III)
Ê
c = 22.678 (2) A
Ê
V = 2747.2 (4) A
Crystal data
3
[Fe(C5H5)(C23H22O3PS)]
Mr = 530.38
Monoclinic, P21
Z = 2
Dx = 1.470 Mg m
Mo Kꢃ radiation
ꢄ = 0.81 mm
T = 180 (2) K
Prism, yellow
0.36 Â 0.28 Â 0.22 mm
3
Data collection
Stoe IPDS diffractometer
' scans
Absorption correction: multi-scan
(Blessing, 1995)
Tmin = 0.852, Tmax = 0.894
22007 measured re¯ections
5395 independent re¯ections
3205 re¯ections with I > 2ꢅ(I)
Rint = 0.145
1
Ê
a = 7.4885 (7) A
Ê
b = 9.5175 (8) A
Ê
c = 16.8193 (13) A
ꢂ = 91.067 (7)ꢀ
V = 1198.53 (18) A
ꢁmax = 26.1ꢀ
3
Ê
Re®nement
Data collection
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.057
wR(F2) = 0.126
S = 0.93
5395 re¯ections
w = 1/[ꢅ2(Fo2) + (0.0476P)2]
2
where P = (Fo + 2Fc2)/3
Oxford Xcalibur diffractometer
! and ' scans
10617 measured re¯ections
4383 independent re¯ections
4045 re¯ections with I > 2ꢅ(I)
Rint = 0.023
ꢁmax = 28.3ꢀ
(Á/ꢅ)max = 0.004
3
Ê
Áꢆmax = 0.97 e A
3
Ê
0.47 e A
Áꢆmin
=
343 parameters
H-atom parameters constrained
Absolute structure: Flack (1983),
with 2333 Friedel pairs
Flack parameter: 0.01 (3)
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.027
wR(F2) = 0.066
S = 1.07
4383 re¯ections
w = 1/[ꢅ2(Fo2) + (0.0401P)2
+ 0.0522P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max = 0.002
Table 2
Selected distances (A) within the three title compounds.
Ê
3
Ê
Áꢆmax = 0.33 e A
3
Cg1 and Cg2 are the centroids of rings C1±C5 and C6±C10, respectively.
Ê
0.33 e A
308 parameters
H-atom parameters constrained
Áꢆmin
=
Absolute structure: Flack (1983),
with 1249 Friedel pairs
Flack parameter: 0.00 (1)
Compound
Fe1ÐCg1
Fe1ÐCg2
C1ÐP1
P1ÐS1
C2ÐC21
(III)
a
(V)
1.639 (5)
1.645 (9)
1.636 (2)
1.636 (8)
1.633 (2)
1.6337 (8)
1.6392 (4)
1.6375 (8)
1.6443 (7)
1.653 (5)
1.660 (10)
1.651 (2)
1.646 (8)
1.652 (2)
1.6503 (8)
1.6588 (4)
1.656 (1)
1.6596 (7)
1.796 (2)
1.790 (3)
1.785 (2)
1.7901 (18)
1.7885 (14)
1.803 (6)
1.809 (3)
1.790 (2)
1.795 (3)
1.9384 (7)
1.9487 (11)
1.9555 (9)
1.9677 (6)
1.9645 (6)
1.503 (3)
1.504 (4)
1.490 (4)
1.505 (3)
1.489 (2)
1.496 (8)
1.515 (5)
1.485 (2)
1.505 (2)
Compound (V)
a
Crystal data
b
(VIII)
a
c
[Fe(C5H5)(C18H14OPS)]
Mr = 430.26
Monoclinic, P21
Z = 2
Dx = 1.539 Mg m
3
1.9567 (6)
1.9561 (5)
Mo Kꢃ radiation
1
Ê
d
a = 7.1110 (13) A
Ê
ꢄ = 1.02 mm
T = 180 (2) K
b = 12.862 (3) A
Â
References: (a) Lopez Cortes et al. (2006); (b) Mourgues et al. (2003); (c) Stepnicka &
Cõsarova (2002); (d) Stepnicka & Cõsarova (2003).
Ê
c = 10.223 (2) A
Needle, yellow
0.48 Â 0.13 Â 0.12 mm
Â
Â
Â
Â
ꢂ = 96.73 (2)ꢀ
V = 928.6 (3) A
3
Ê
All H atoms were positioned geometrically and treated as riding
Ê
on their parent atoms, with CÐH = 0.93 (aromatic C) or 0.96 A
Ê
(methyl C) and OÐH = 0.82 A, and with Uiso(H) = 1.2Ueq(aromatic
C,O) or 1.5Ueq(methyl C).
Data collection
Stoe IPDS diffractometer
' scans
Absorption correction: multi-scan
(Blessing, 1995)
Tmin = 0.598, Tmax = 0.873
9253 measured re¯ections
3619 independent re¯ections
3380 re¯ections with I > 2ꢅ(I)
Rint = 0.050
Data collection: CrysAlis CCD (Oxford Diffraction, 2003) for
(III); IPDS Software (Stoe & Cie, 2000) for (V) and (VIII). Cell
re®nement: CrysAlis RED (Oxford Diffraction, 2003) for (III); IPDS
Software for (V) and (VIII). Data reduction: CrysAlis RED for (III);
X-RED (Stoe & Cie, 1996) for (V) and (VIII). For all compounds,
program(s) used to solve structure: SIR97 (Altomare et al., 1999);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997).
Molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) for (III)
and (VIII); ORTEP-3 for Windows (Farrugia, 1997) and PLATON
(Spek, 2003) for (V). For all compounds, software used to prepare
material for publication: WinGX (Farrugia, 1999).
ꢁmax = 26.1ꢀ
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.026
wR(F2) = 0.061
S = 0.98
3619 re¯ections
w = 1/[ꢅ2(Fo2) + (0.0359P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max = 0.001
3
Ê
Áꢆmax = 0.36 e A
3
Ê
0.25 e A
Áꢆmin
=
245 parameters
H-atom parameters constrained
Absolute structure: Flack (1983),
with 1722 Friedel pairs
Flack parameter: 0.015 (12)
ꢁ
m190 Cortes et al. [Fe(C5H5)(C23H22O3PS)], [Fe(C5H5)(C18H14OPS)] and [Fe(C5H5)(C30H23P2)]
Acta Cryst. (2006). C62, m188±m191

metal-organic compounds
Â
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ꢁ
Acta Cryst. (2006). C62, m188±m191
Cortes et al.
[Fe(C5H5)(C23H22O3PS)], [Fe(C5H5)(C18H14OPS)] and [Fe(C5H5)(C30H23P2)] m191