Dichlorido[(S,R S)-1-diphenylphosphino-2-(ethylsulfanylmethyl)- ferrocene]palladium(II)

Article abstract of DOI:10.1107/S0108270107052742

The reaction of enantio-merically pure planar chiral ferrocene phosphine thio-ether with bis-(aceto-nitrile)-dichlorido-palla-dium yields the title square-planar mononuclear palladium complex as an enantio-merically pure single diastereoisomer, [PdFe(C5H5

Full text of DOI:10.1107/S0108270107052742

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Manoury et al., 2006; Malacea, Daran et al., 2006; Malacea et
al., 2007). These ligands, in enantiomerically pure forms, have
been successfully applied to some asymmetric catalytic reac-
tions, namely palladium-catalysed allylic substitution (Routa-
boul et al., 2005, 2007) and iridium-catalysed ketone hydro-
genation (Le Roux et al., 2007).
ISSN 0108-2701
Dichlorido[(S,RS)-1-diphenyl-
phosphino-2-(ethylsulfanylmethyl)-
ferrocene]palladium(II)
The reaction of the planar chiral ligand (S)-(III) with one
equivalent of (acetonitrile)dichloridobispalladium (see
scheme) quantitatively yields the title square-planar mono-
nuclear palladium complex, (I), as a single diastereoisomer, as
shown by NMR data (1H, 31P and 13C).
Lisa Diab,a Jean-Claude Daran,a* Maryse Gouygou,a Eric
Compound (I) adopts a mononuclear square-planar
geometry, with the phosphine and thioether functions in
relative cis positions. The largest deviation from the square
plane is 0.0857 (4) for atom Cl1. This plane makes a dihedral
angle of 37.08 (7)ꢀ with the plane containing the substituted
cyclopentadienyl (Cp) ring and atoms P1 and C21. As
observed in the racemic compound and in related Pd
complexes (Malacea et al., 2007), the S substituent is located
on the opposite side (anti) of the SÐCÐCÐCÐP chelate,
relative to the FeCp group. Thus, the Pd atom has been
selectively coordinated by one of the two lone pairs of the S
atom; after coordination, the remaining lone pair is oriented
syn to the unsubstituted Cp ring. Owing to the synthetic
pathway, compound (I) is an enantiomerically pure single
diastereoisomer with the con®guration for planar chirality
being S, and the con®guration of the S atom being R. This
stereochemistry has been unequivocally determined by the
structural analysis, with a value of 0.01 (2) for the enantiopole
parameter (Flack, 1983). The planar chirality of the ligand is
then retained in the complex and fully controls the central
chirality on the S atom.
Manourya and Martine Urrutigoõtyb
È
aLaboratoire de Chimie de Coordination du CNRS, UPR 8241, 205 Route de
Narbonne, 31077 Toulouse Cedex 4, France, and bLaboratoire de Chimie de
Coordination du CNRS, UPR 8241, ComposanteENSIACET±INP, 118 route de
Narbonne, 31077 Toulouse Cedex, France
Correspondence e-mail: daran@lcc-toulouse.fr
Received 28 September 2007
Accepted 24 October 2007
Online 24 November 2007
The reaction of enantiomerically pure planar chiral ferrocene
phosphine thioether with bis(acetonitrile)dichloridopalladium
yields the title square-planar mononuclear palladium complex
as an enantiomerically pure single diastereoisomer,
[PdFe(C5H5)(C20H20PS)Cl2]. The planar chirality of the ligand
is retained in the complex and fully controls the central
chirality on the S atom. The absolute con®guration, viz. S for
the planar chirality and R for the S atom, is unequivocally
determined by re®nement of the Flack parameter.
As shown in Table 1, there are no signi®cant differences in
the relevant structural parameters between compound (I) and
its racemic equivalent (II) (Table 1; Malacea et al., 2007).
Although their crystal systems are different, orthorhombic for
(I) and monoclinic for (II) (Table 1), their packings are
Comment
Owing to the huge importance of asymmetric catalysis for
academic and industrial research, considerable efforts have
been devoted to the development of new chiral ligands for
transition metal-catalysed asymmetric catalysis (Noyori, 1994;
Jacobsen et al., 1999; Ojima 2000). Chiral ferrocene-based
ligands have proved to be of particular interest (Colacot, 2003;
Atkinson et al., 2004; Gomez Arrayas et al., 2006) because of
their stability, easy introduction of planar chirality (Togni,
1996; Riant & Kagan, 1997; Balavoine et al., 1998; Richards &
Locke, 1998) and special stereoelectronic properties of the
ferrocene skeleton.
We have recently developed new chiral ferrocene-based
phosphine thioether ligands having only planar chirality, in
both racemic and enantiomerically pure forms (R or S
con®guration) (Routaboul et al., 2005; Mateus et al., 2006) and
brie¯y reported on their coordination chemistry (Malacea,
Figure 1
A molecular view of compound (I), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level and H
atoms have been omitted for clarity.
m586 # 2007 International Union of Crystallography
DOI: 10.1107/S0108270107052742
Acta Cryst. (2007). C63, m586±m588

metal-organic compounds
roughly similar, with four molecules within the unit cell (Figs. 2
and 3) and weak CÐHÁ Á ÁCl interactions (Steiner, 1998)
(Table 2). It may be noted that only atom Cl1 is involved in
these hydrogen bonds in both compounds, which re¯ects the
electronic trans effect of the P atom.
When comparing the structure of the title compound with
Â
related structures (Malacea et al., 2007; Garcõa ManchenÄo et
al., 2005) (Table 1), it can indeed be noted that the PdÐS bond
is longer than the PdÐP bond, and the PdÐCl bond trans to P
is longer than the PdÐCl bond trans to S, in agreement with
the stronger trans effect of phosphine donors compared with
thioethers (Table 1). The PdÐP distances are within the
Ê
previously established range (2.228±2.237 A) for relevant
compounds found in the Cambridge Structural Database
(Version 5.28; Allen, 2002), whereas the PdÐS distances are
slightly longer with respect to the reported range of 2.257±
Ê
2.296 A. In compounds (I), (II), (III) and (IV), the PÐPdÐS,
PÐPdÐCl and SÐPdÐCl angles (Table 1) seem to be in¯u-
enced by the growing steric repulsion between the S substi-
tuent and the pseudo-axial phosphine phenyl group. Indeed,
the largest differences are observed for compound (IV), where
the S atom bears a bulky tert-butyl substituent. In compound
(V), where the S atom is directly bonded to the Cp ring
Â
(Garcõa ManchenÄo et al., 2005), the square-planar framework
is nearly perfect, with all angles close to 90 or 180ꢀ.
Experimental
Thioether (S)-(III) (88 mg, 0.225 mmol) and [PdCl2(CH3CN)2]
(58 mg, 0.225 mmol) were dissolved in dry dichloromethane (15 ml)
under argon. After stirring for 2 h at room temperature, the solvent
was evaporated and the resulting red solid was washed with dry
pentane (yield 113 mg, 81%). Single crystals of complex (I) suitable
for X-ray diffraction analysis were obtained by slow evaporation of a
methanol solution. 1H NMR (500 MHz, CDCl3): ꢀ 7.72±7.53 (6H, m,
Ph), 751±7.41 (4H, m, Ph), 4.63 (5H, s, Cp), 4.56 (1H, s large, subst.
Cp), 4.41 (1H, s large, subst. Cp), 3.78 [1H, d(AB), JHH = 12 Hz,
Figure 2
A partial packing view of compound (I), showing the CÐHÁ Á ÁCl
interactions as dashed lines. H atoms not involved in hydrogen bonding
have been omitted for clarity. [Symmetry codes: (i) 1 x, 12 + y, 21 z;
1
2
1
2
3
2
(ii) 2 x,
+ y, 12 z; (iii) + x,
y, 1 z.]
CH2ÐCp], 3.53 (1H, s large, subst. Cp), 3.29 [1H, d(AB), JHH
=
12 Hz, CH2ÐCp], 3.24 (2H, q, JHH = 7 Hz, CH2ÐCH3), 1.38 (3H, t,
JHH = 7 Hz, CH2ÐCH3). 31P NMR (500 MHz, CDCl3): ꢀ 21.2.
Crystal data
3
Ê
[PdFe(C5H5)(C20H20PS)Cl2]
Mr = 621.63
Orthorhombic, P212121
V = 2460.6 (4) A
Z = 4
Mo Kꢁ radiation
1
Ê
a = 9.7644 (7) A
b = 14.8595 (15) A
ꢂ = 1.70 mm
T = 180 (2) K
Ê
Ê
c = 16.9586 (12) A
0.58 Â 0.31 Â 0.1 mm
Data collection
Stoe IPDS diffractometer
Absorption correction: multi-scan
(Blessing, 1995)
24267 measured re¯ections
4771 independent re¯ections
4539 re¯ections with I > 2ꢃ(I)
Rint = 0.045
Tmin = 0.565, Tmax = 0.856
Re®nement
3
R[F2 > 2ꢃ(F2)] = 0.024
wR(F2) = 0.059
S = 1.03
4771 re¯ections
281 parameters
H-atom parameters constrained
Áꢄmax = 0.51 e A
Ê
3
Ê
0.53 e A
Áꢄmin
=
Absolute structure: Flack (1983),
with 2048 Friedel pairs
Flack parameter: 0.008 (17)
Figure 3
A partial packing view of compound (II) (Malacea et al., 2007), the
related racemate of (I). Hydrogen bonds are shown as dashed lines and H
atoms not involved in hydrogen bonding have been omitted for clarity.
[Symmetry codes: (i) x, 1 y, 12 + z; (ii) x, y, 1 + z; (iii) 21 + x, 12 y,
All H atoms were ®xed geometrically and treated as riding, with
Ê
CÐH = 0.93 (aromatic), 0.96 (methyl) or 0.97 A (methylene), and
with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).
1
+ z.]
2
ꢁ
Acta Cryst. (2007). C63, m586±m588
Diab et al.
[PdFe(C5H5)(C20H20PS)Cl2] m587

metal-organic compounds
Table 1
Comparison of selected geometric parameters (A, ) for the title compound and related
ꢀ
Ê
t
CpFe[1,2-C5H3(PPh2){(CH2)nSR}]PdCl2 structures, where R = Et, Ph or Bu.
Cg1 and Cg2 are the centroids of the Cp rings and ꢀ is the twist angle between the two Cp rings.
Parameter
(I)²
(II)³
(III)§
(IV)}
(V)²²
Space group
Pd1ÐP1
Pd1ÐS2
Pd1ÐCl2
Pd1ÐCl1
P1ÐPd1ÐS2
P1ÐPd1ÐCl2
P1ÐPd1ÐCl1
S2ÐPd1ÐCl1
S2ÐPd1ÐCl2
Cl1ÐPd1ÐCl2
Fe1ÐCg1
Fe1ÐCg2
Cg1ÐFe1ÐCg2
ꢀ
P212121
Cc
P21/c
P21/c
P212121
2.2302 (7)
2.2962 (8)
2.2971 (8)
2.3708 (7)
94.72 (3)
89.96 (3)
174.74 (3)
83.71 (3)
174.47 (3)
91.89 (3)
1.6463 (4)
1.6539 (4)
176.03 (7)
8.4 (3)
2.2253 (16)
2.3078 (18)
2.3139 (18)
2.3621 (17)
93.93 (6)
89.78 (6)
176.50 (7)
83.73 (6)
176.28 (6)
92.55 (7)
1.643 (7)
1.662 (6)
174.8 (11)
5.6 (5)
2.2311 (10)
2.3074 (9)
2.3102 (9)
2.3683 (10)
95.08 (4)
90.20 (3)
175.56 (3)
83.41 (3)
173.14 (3)
91.65 (4)
1.6523 (6)
1.6651 (6)
175.67 (3)
6.8 (3)
2.2251 (8)
2.3215 (8)
2.3006 (8)
2.3588 (8)
96.08 (3)
88.99 (3)
163.68 (3)
86.73 (3)
169.98 (3)
90.82 (3)
1.6581 (4)
1.6657 (4)
176.96 (3)
11.8 (2)
2.2427 (9)
2.3137 (9)
2.3022 (11)
2.3461 (11)
90.83 (3)
88.26 (4)
176.95 (4)
89.39 (4)
176.23 (4)
91.72 (5)
² For compound (I), n = 1, R = C2H5 (this work). ³ For compound (II), n = 1, R = C2H5; data from Malacea
et al. (2007). § For compound (III), n = 1, R = C6H5; data from Malacea et al. (2007). } For compound
(IV), n = 1, R = C(CH3)3; data from Malacea et al. (2007). ²² For compound (V), n = 0, R = C(CH3)3; data
Â
from Garcõa ManchenÄo et al. (2005).
Blessing, R. H. (1995). Acta Cryst. A51, 33±38.
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak
Ridge National Laboratory, Tennessee, USA.
Table 2
Comparison of CÐHÁ Á ÁCl hydrogen-bond interactions (A, ꢀ) between
Ê
compound (I) and its racemate (II).
Colacot, T. J. (2003). Chem. Rev. 103, 3101±3118.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838.
Flack, H. D. (1983). Acta Cryst. A39, 876±881.
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
(I)
C4ÐH4Á Á ÁCl1i
0.93
0.93
0.93
0.95
0.95
0.95
2.68
2.79
2.72
2.78
2.82
2.69
3.603 (3)
3.704 (4)
3.554 (4)
3.474 (8)
3.499 (7)
3.560 (9)
174.0
168.2
149.0
131.0
129.2
152.2
C115ÐH115Á Á ÁCl1ii
C125ÐH125Á Á ÁCl1iii
C113ÐH113Á Á ÁCl1iv
C114ÐH114Á Á ÁCl1v
C123ÐH123Á Á ÁCl1vi
Â
Â
Â
Garcõa ManchenÄo, O., Gomez Arrayas, R. & Carretero, J. C. (2005).
Organometallics, 24, 557±561.
(II)²
Gomez Arrayas, R., Adrio, J. & Carretero, J. C. (2006). Angew. Chem. Int. Ed.
45, 7674±7715.
Jacobsen, E. N., Pfaltz, A. & Yamamoto, H. (1999). Comprehensive
Asymmetric Catalysis. Berlin: Springer-Verlag.
Le Roux, E., Malacea, R., Manoury, E., Poli, R., Gonsalvi, L. & Peruzzini, M.
(2007). Adv. Synth. Catal. 349, 1064±1073.
1
1
2
Symmetry codes: (i) 1 x;
‡ y; 12 z; (ii) 2 x;
‡ y; 12 z; (iii) 21 ‡ x; 32 y; 1 z;
2
(iv) x; 1 y; 12 z; (v) x; y; 1 ‡ z; (vi)
‡ x; 12 y;
‡ z. ² Data for compound
1
2
1
2
(II) taken from Malacea et al. (2007).
Malacea, R., Daran, J.-C., Duckett, S. B., Dunne, J. P., Manoury, E., Poli, R. &
Withwood, A. C. (2006). Dalton Trans. pp. 3350±3359.
Malacea, R., Manoury, E., Routaboul, L., Daran, J.-C., Poli, R., Dunne, J. P.,
Withwood, A. C., Godard, C. & Duckett, S. B. (2006). Eur. J. Inorg. Chem.
pp. 1803±1816.
Malacea, R., Routaboul, L., Manoury, E., Daran, J.-C. & Poli, R. (2007). J.
Organomet. Chem. doi:10.1016/jorganchem.2007.08.021.
Mateus, N., Routaboul, L., Daran, J.-C. & Manoury, E. (2006). J. Organomet.
Chem. 691, 2297±2310.
Data collection: IPDS Software (Stoe & Cie, 2000); cell re®ne-
ment: IPDS Software; data reduction: X-RED (Stoe & Cie, 1996);
program(s) used to solve structure: SIR97 (Altomare et al., 1999);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);
molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and
ORTEP-3 for Windows (Farrugia, 1997); software used to prepare
material for publication: WinGX (Farrugia, 1999).
Noyori, R. (1994). In Asymmetric Catalysis in Organic Synthesis. New York:
Wiley-VCH.
Ojima, I. (2000) In Catalytic Asymmetric Synthesis, 2nd ed. New York: Wiley-
VCH.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: HJ3055). Services for accessing these data are
described at the back of the journal.
Riant, O. & Kagan, H. B. (1997). Advances in Asymmetric Synthesis, edited by
A. Hassner, Vol. 2, pp. 189±235. Greenwich: JAI Press.
Richards, C. J. & Locke, A. J. (1998). Tetrahedron Asymmetry, 9, 2377±2407.
Routaboul, L., Vincendeau, S., Daran, J.-C. & Manoury, E. (2005). Tetra-
hedron Asymmetry, 16, 2685±2690.
Routaboul, L., Vincendeau, S., Turrin, C.-O., Caminade, A.-M., Majoral, J.-P.,
Daran, J.-C. & Manoury, E. (2007). J. Organomet. Chem. 692, 1064±1073.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
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ꢁ
m588 Diab et al. [PdFe(C5H5)(C20H20PS)Cl2]
Acta Cryst. (2007). C63, m586±m588