Resolution of a cyclopalladated ferrocenylketimine

Article abstract of DOI:10.1039/a803739f

The cyclopalladated ferrocenylketimine, [{Pd[(η⁵-C₅C₅)Fe{η⁵-C ₅H₃C(CH₃)=N(C₆H₄CH ₃-4)}](μ-Cl)}₂] 1 was resolved into optically active diastereomers by using (S)-leucine as chiral auxiliary. The new optically active (S)-leucinato complexes of Pd^II containing ferrocenylketimine could be converted into optically active dimers with the same absolute configurations in the ferrocene moiety. The structure of the chiral dimer (R_p,R_p)-1 was determined by X-ray diffraction, on the basis of which the absolute configurations of all the optically active compounds studied were ascertained.

Full text of DOI:10.1039/a803739f

View Article Online / Journal Homepage / Table of Contents for this issue
Resolution of a cyclopalladated ferrocenylketimine
Yang Jie Wu,* Xiu Ling Cui, Chen Xia Du, Wen Ling Wang, Rui Yun Guo and Rong Feng Chen
Department of Chemistry, Zhengzhou University, Zhengzhou 450052, P.R. China.
E-mail: wyj@mail.zzu.edu.cn
Received 19th May 1998, Accepted 23rd September 1998
The cyclopalladated ferrocenylketimine, [{Pd[(η5-C H )Fe{η5-C H C(CH )᎐N(C H CH -4)}](µ-Cl)} ] 1 was
᎐
5
5
5
3
3
6
4
3
2
resolved into optically active diastereomers by using (S)-leucine as chiral auxiliary. The new optically active
(S)-leucinato complexes of PdII containing ferrocenylketimine could be converted into optically active dimers
with the same absolute configurations in the ferrocene moiety. The structure of the chiral dimer (Rp,Rp)-1 was
determined by X-ray diffraction, on the basis of which the absolute configurations of all the optically active
compounds studied were ascertained.
The diastereomers 2 shown in Scheme 1 were assumed to be
Introduction
the trans-N, N form, similar to ortho-palladated complexes.4,8
It was found that diastereomers 2 could be resolved both by
chromatography and fractional crystallization techniques and
the former was a most efficient method. Their isolation was
easily achieved by chromatography of the reaction mixture on a
silica gel plate developed with CH2Cl2–CH3COCH3 (1:1), since
the diastereomer (ϩ)-2 exhibited a higher Rf value than that
of the diastereomer (Ϫ)-2. Both of the compounds were
Cyclometallated compounds are important intermediates for
synthesizing ortho-disubstituted aromatic compounds as well as
heterocycles.1 Chiral cyclopalladated compounds are valuable
reagents for asymmetric reaction, resolution, the determination
of enantiomeric excess and absolute configuration of chiral
substrates.2 On the other hand, optically active ferrocene
derivatives are of increasing importance in the synthesis of
chiral ligands used in asymmetric catalysis and asymmetric
synthesis.3 Therefore much effort has gone into developing
practical methodologies for asymmetric synthesis and reso-
lution of cyclopalladated ferrocene derivatives, such as: (a)
enantiopure ferrocenes were mainly obtained by resolution
methods with a chiral amino acid;4 (b) Sokolov et al.5 have
developed useful methods to afford the planar chiral cyclo-
palladated ferrocene derivatives in the presence of the salts of
optically active amino acids as nucleophilic catalysts. However
most of the documented researches involving optically active
cyclopalladated ferrocene derivatives have focused on 1-ferro-
cenyl-N,N-dimethylethylamine and its analogues; there have
been few reports on other ligands.6 Although the cyclo-
palladation reaction of ferrocenylimines has been extensively
studied,7 the cyclopalladated ferrocenylimines have not been
resolved. In this paper will be reported the resolution and
structure of a cyclopalladated ferrocenylketimine.
1
characterized by elemental analysis, IR and H NMR spectra.
The infrared spectra of the imine showed a band at 1561 cmϪ1
.
Other IR bands were found at ca. 1000 and 1100 cmϪ1, which
indicated an unsubstituted cyclopentadienyl ring.7a The IR
features of the pair of diastereomers 2 were very similar. The
1H NMR spectrum of (ϩ)-2 showed signals of H-3 at δ 4.66 (d),
H-4 at δ 4.37 (t) and that of H-5 at δ 4.60 (d), while the other
(Ϫ)-2, showed peaks at δ 4.72 (d), 4.38 (t) and 4.61 (d), respect-
ively. The signal of H-3 was used as an indication of complete
separation of the diastereomers.
The complex (ϩ)-[Pd{C H FeC H C(CH )᎐N(C H CH -
᎐
5
5
5
3
3
6
4
3
4)}(S-LeuO)] (ϩ)-2 was mixed with LiCl in acetic acid and
stirred at room temperature for 10 min, giving (ϩ)-1 (Scheme 2)
with the same absolute configuration of the ferrocene moiety,
which was confirmed by CD spectra. The CD spectra of the
pair of diastereomers 2 are shown in Fig. 1 together with the
CD spectrum of (ϩ)-1. The CD spectra of the diastereomers 2
were nearly enantiomeric to each other and the CD spectrum
of (ϩ)-1 was similar to that of (ϩ)-2, which indicated that
compound (ϩ)-1 had the same absolute configuration in the
ferrocene moiety as that of (ϩ)-2. The chiral dimer (ϩ)-1 was
air stable, soluble in dicholoromethane, acetone, and other
common organic solvents. Moreover, it underwent a bridge-
splitting reaction with PPh3 to produce quantitatively the
Results and discussion
A useful candidate for this study was the complex 1 prepared by
the published method.7a Reaction of complex 1 with Na2CO3
and (S)-leucine gave the (S)-leucinato complex of PdII con-
taining ferrocenylketimine as a solid in 84% yield (Scheme 1).
Scheme 1
J. Chem. Soc., Dalton Trans., 1998, 3727–3730
3727

View Article Online
Scheme 2
Scheme 3
Table 1 Selected bond distances (Å) for complex (Rp,Rp)-1
Pd(1)–Cl(1)
2.328(3)
2.071(8)
2.490(3)
2.091(9)
2.04(1)
2.06(1)
2.06(1)
2.04(1)
2.08(1)
2.02(1)
2.05(1)
2.04(1)
2.09(1)
2.08(1)
1.30(1)
1.30(1)
1.40(2)
1.42(2)
1.44(2)
1.34(2)
1.36(2)
1.48(3)
1.42(2)
1.44(2)
1.38(2)
1.43(3)
1.42(3)
Pd(1)–Cl(2)
Pd(1)–C(1)
Pd(2)–Cl(2)
Pd(2)–C(20)
Fe(1)–C(2)
Fe(1)–C(4)
Fe(1)–C(6)
Fe(1)–C(8)
Fe(1)–C(10)
Fe(2)–C(21)
Fe(2)–C(23)
Fe(2)–C(25)
Fe(2)–C(27)
Fe(2)–C(29)
N(1)–C(13)
N(2)–C(32)
C(1)–C(5)
C(2)–C(11)
C(4)–C(5)
C(6)–C(10)
C(8)–C(9)
C(20)–C(21)
C(21)–C(22)
C(22)–C(23)
C(25)–C(26)
C(26)–C(27)
C(28)–C(29)
2.470(3)
1.969(9)
2.321(3)
1.96(1)
2.02(1)
2.04(1)
2.04(1)
2.04(1)
2.03(2)
2.06(1)
2.03(1)
2.06(2)
2.04(2)
2.05(2)
1.43(1)
1.42(1)
1.43(1)
1.48(2)
1.42(1)
1.41(3)
1.38(3)
1.40(2)
1.44(2)
1.44(2)
1.38(3)
1.43(2)
1.41(3)
Pd(1)–N(1)
Pd(2)–Cl(1)
Pd(2)–N(2)
Fe(1)–C(1)
Fe(1)–C(3)
Fe(1)–C(5)
Fe(1)–C(7)
Fe(1)–C(9)
Fe(2)–C(20)
Fe(2)–C(22)
Fe(2)–C(24)
Fe(2)–C(26)
Fe(2)–C(28)
N(1)–C(11)
N(2)–C(30)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(6)–C(7)
C(7)–C(8)
C(9)–C(10)
C(20)–C(24)
C(21)–C(30)
C(23)–C(24)
C(25)–C(29)
C(27)–C(28)
Fig. 1 The CD spectra of methanol solutions of (a) complexes (Rp,Rp)-
1, (b) (Rp,Sc)-2 and (c) (Sp,Sc)-2.
Fig. 2 The CD spectra of methanol solutions of complexes (a)
(Rp,Rp)-1 and (b) (Rp)-3.
converted into dimers with the same configuration in the ferro-
cene moiety, but their single crystals are difficult to obtain.
Therefore, the optically active dimer (ϩ)-1 was chosen to
determine the absolute configuration by X-ray diffraction. The
structure is shown in Fig. 3. Selected bond lengths and angles
are listed in Tables 1 and 2, respectively. The structure shows
clearly that (ϩ)-1 is a binuclear complex of palladium, and that
both the palladium atoms are linked to ortho positions of the
substituted ferrocenyl rings resulting in two five membered
metallocycles. The two metallocycles, which are nearly planar,
form a dihedral angle of 62.70Њ with each other. The plane
monomeric triphenylphosphine derivative (ϩ)-3, a typical reac-
tion of chloride-bridged binuclear complexes of palladium9
(Scheme 3). The CD spectrum of (ϩ)-3 is compared with that
of (ϩ)-1 in Fig. 2. The results also showed that the absolute
configuration of the ferrocene moiety in (ϩ)-3 was same as that
in (ϩ)-1, consistent with the addition of triphenylphosphine
leading only to cleavage of the di-µ-chloro bridges without
breaking of Pd–C and Pd–N bonds.
As has been previously described, the (S)-leucinato com-
plexes of cyclopalladated ferrocenylimines can be successfully
3728
J. Chem. Soc., Dalton Trans., 1998, 3727–3730

View Article Online
Fig. 3 Molecular structure of complex (Rp,Rp)-1.
Table 2 Selected bond angles (Њ) for complex (Rp,Rp)-1
identical planar chirality (R configuration).10 So the compound
(ϩ)-2 had the same absolute R configuration in the ferrocene
moiety, and (Ϫ)-2 had the S configuration, and (ϩ)-2, (Ϫ)-2,
(ϩ)-1 and (ϩ)-3 were assigned as (Rp,Sc)-2, (Sp,Sc)-2, (Rp,Rp)-1
and Rp-3, respectively.
Cl(1)–Pd(1)–Cl(2)
Cl(1)–Pd(1)–C(1)
Cl(2)–Pd(1)–C(1)
Cl(1)–Pd(2)–Cl(2)
Cl(1)–Pd(2)–C(20)
Cl(2)–Pd(2)–C(20)
Pd(1)–Cl(1)–Pd(2)
Pd(1)–N(1)–C(11)
C(11)–N(1)–C(13)
Pd(2)–N(2)–C(32)
Pd(1)–C(1)–Fe(1)
Pd(1)–C(1)–C(5)
C(1)–C(2)–C(11)
N(1)–C(11)–C(2)
C(2)–C(11)–C(12)
N(1)–C(13)–C(15)
Pd(2)–C(20)–C(21)
C(22)–C(21)–C(30)
N(2)–C(30)–C(31)
N(2)–C(32)–C(33)
87.0(1)
92.5(3)
177.2(3)
86.6(1)
179.2(4)
93.4(4)
81.96(9)
116.4(7)
120.9(9)
121.4(7)
119.9(5)
138.7(9)
116.8(10)
112.3(9)
118.9(10)
121.9(10)
114.1(9)
133(1)
Cl(1)–Pd(1)–N(1)
Cl(2)–Pd(1)–N(1)
N(1)–Pd(1)–C(1)
Cl(1)–Pd(2)–N(2)
Cl(2)–Pd(2)–N(2)
N(2)–Pd(2)–C(20)
Pd(1)–Cl(2)–Pd(2)
Pd(1)–N(1)–C(13)
Pd(2)–N(2)–C(30)
C(30)–N(2)–C(32)
Pd(1)–C(1)–C(2)
C(3)–C(2)–C(11)
N(1)–C(11)–C(12)
N(1)–C(13)–C(14)
Pd(2)–C(20)–Fe(2)
Pd(2)–C(20)–C(24)
C(20)–C(21)–C(30)
N(2)–C(30)–C(21)
C(21)–C(30)–C(31)
N(2)–C(32)–C(34)
168.7(3)
100.6(2)
80.4(4)
100.5(3)
169.7(2)
79.5(5)
82.55(9)
122.2(7)
115.6(8)
122(1)
113.5(7)
133(1)
128(1)
119.2(10)
124.1(6)
138(1)
116.7(10)
113(1)
Experimental
General
Melting points were measured on a WC-1 apparatus and are
uncorrected. Elemental analyses were determined with a Carlo
Erba 1160 elemental analyzer. Proton NMR spectra were
recorded on a Bruker DPX 400 spectrometer using Me2SO as
the solvent and SiMe4 as an internal standard, IR spectra on a
Perkin-Elmer FTIR 1750 spectrophotometer. Preparative TLC
was performed on dry silica gel plates developed with
dichloromethane–acetone (1:1). Optical rotations at 5890 Å
were determined by a Perkin-Elmer 341 polarimeter at 20 ЊC.
The CD spectra were recorded on GJASCO J-20C automatic
recording spectropolarimeter at 20 ЊC.
125(1)
120(1)
120(1)
121(1)
Pd(1)Cl(2)Pd(2) forms a dihedral angle of 129.67Њ with plane
Pd(2)Cl(1)Pd(1). Owing to the co-ordination between the
palladium atoms and the nitrogen atoms, the angles Pd(1)–
C(1)–C(2), C(1)–C(2)–C(11), Pd(2)–C(20)–C(21) and C(20)–
C(21)–C(30) are decreased to 113.5, 116.8, 114.1 and 116.7Њ,
respectively, compared with the normal value of 126Њ.7a The
Pd(1)–N(1) and Pd(2)–N(2) distances are 2.071(8) and 2.091(9)
Å, respectively, suggesting the formation of Pd–N bonds. The
two halves of the molecule are in a cis arrangement and exhibit
Syntheses
[Pd{C H FeC H C(CH )᎐N(C H CH -4)}(S-LeuO)] 2. To
᎐
5
5
5
3
3
6
4
3
a methanol suspension (10 ml) of complex 1 (1.0 g, 1.1 mmol)
was added a slight excess of (S)-leucine (0.16 g, 1.2 mmol) and
Na2CO3 (0.13 g, 1.2 mmol) and stirred for 6 h at room temper-
ature until the solution became clear. After evaporation of the
solvent in vacuo the crude residue was treated with CH2Cl2 in
order to remove the unchanged amino acid. Further evapor-
J. Chem. Soc., Dalton Trans., 1998, 3727–3730
3729

View Article Online
ation of the CH2Cl2 and treatment of the residue with CH2Cl2–
light petroleum (bp 60–90 ЊC) (1:3) afforded a 1:1 mixture
of diastereomers 2 in 84% yield. Their separation was easily
achieved by TLC of the mixture on a silica gel plate developed
with dichloromethane–acetone (1:1); the first band was
(Rp,Sc)-2, the second (Sp,Sc)-2.
exposed for 16.0 min. The crystal-to-detector distance was
110.00 mm with the detector at the zero swing position. The
data were corrected for Lorentz-polarization effects. The
structure was solved by direct methods11 and expanded using
Fourier techniques. The non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were included but not refined.
The final cycle of full-matrix least-squares refinement was
based on 3374 observed reflections [I > 3.00σ(I)] and 416
variable parameters. The function minimized was Σw(|Fo| Ϫ
|Fc|)2. The maximum and minimum peaks on the final Fourier-
difference map corresponded to 1.89 and Ϫ1.45 e ÅϪ3, respec-
tively. The absolute configuration of complex (Rp,Rp)-1 was
confirmed by the significance of the difference between the two
sigma weighted R factors, as judged by the Hamilton test.12 The
final R factors were 0.042 (RЈ = 0.062) and 0.043 (0.063) for the
R and S configuration in the ferrocene moiety, respectively. All
calculations were performed using the TEXSAN crystallo-
graphic software package.13
(R ,S )-(ϩ)-[Pd{C H FeC H C(CH )᎐N(C H CH -4)}(S-
᎐
p
c
5
5
5
3
3
6
4
3
LeuO)] (Rp,Sc)-2: red crystals, mp >250 ЊC (decomp.), [α]D20
ϩ2209.3 deg cm3 gϪ1 dmϪ1 (c 0.0086 g per 100 ml in CH3OH),
Rf 0.68 (Found: C, 54.32; H, 5.48; N, 5.15. Calc. for C25H30-
FeN2O2Pd: C, 54.32; H, 5.47; N, 5.07%). IR(KBr): 3287, 3091,
2955, 2867, 1619, 1561, 1508, 1474, 1106, 1001, 817, 722 and
669 cmϪ1. 1H NMR: δ 4.66 (d, 1 H, J = 2.0, H-3), 4.60 (d, 1 H,
J = 2.4, H-5), 4.37 (t, 1 H, J = 2.2, H-4), 4.32 (s, 5 H, H-1Ј), 7.17
(d, 2 H, J = 8.0, NC6H4), 7.00 (d, 2 H, J = 8.0, NC6H4), 2.05 (s,
3 H, CH3); 2.31 (s, 3 H, CH3), 1.53 [m, 1 H, CH(CH3)2], 1.66
(m), 1.85 (m, 2 H, CH2), 3.20 (m, 1 H, NH2CH), 0.88, 0.86 [d,
6 H, J = 6.6 Hz, (CH3)2CH].
(S ,S )-(Ϫ)-[Pd{C H FeC H C(CH )᎐N(C H CH -4)}(S-
CCDC reference number 186/1177.
᎐
p
c
5
5
5
3
3
6
4
3
LeuO)] (Sp,Sc)-2: red crystals, mp >250 ЊC (decomp.), [α]D20
Ϫ2344.8 deg cm3 gϪ1 dmϪ1 (c 0.0116 g per 100 ml in CH3OH),
Rf 0.58 (Found: C, 54.32; H, 5.42; N, 5.12. Calc. for C25H30-
FeN2O2Pd: C, 54.32; H, 5.47; N, 5.07%). IR(KBr): 3290, 3092,
2954, 2868, 1618, 1561, 1508, 1471, 1106, 1001, 815, 720 and
669 cmϪ1. 1H NMR: δ 4.72 (d, 1 H, J = 2.0, H-3), 4.61 (d, 1 H,
J = 2.4, H-5), 4.38 (t, 1 H, J = 2.2, H-4), 4.32 (s, 5 H, H-1Ј), 7.18
(d, 2 H, J = 8.0, NC6H4), 6.98 (d, 2 H, J = 8.0, NC6H4), 2.06 (s,
3 H, CH3), 2.32 (s, 3 H, CH3), 1.68 [m, 1 H, CH(CH3)2], 1.92,
1.78 (m, 2 H, CH2), 3.17 (m, 1 H, NH2CH), 0.95, 0.99 [2d, 6 H,
J = 6.4 Hz, (CH3)2CH].
See http://www.rsc.org/suppdata/dt/1998/3727/ for crystallo-
graphic files in .cif format.
Acknowledgements
We are grateful to the National Science Foundation of China
(Project 29592066) and the Natural Science Foundation of
Henan Province for financial support. We thank Professors
V. I. Sokolov, Weiwei Huang and Hongwen Hu for valuable
dicussion.
References
R ,R -(؉)-[{PdCl[C H FeC H C(CH )᎐N(C H CH -4)]} ]
᎐
p
p
5
5
5
3
3
6
4
3
2
1 M. I. Bruce, Angew. Chem., Int. Ed. Engl., 1977, 16, 73; C. H. Chao,
D. W. Hast, R. Bau and R. F. Heck, J. Organomet. Chem., 1979,
179, 301; N. Beydoun and M. Pfeffer, Synthesis, 1990, 729;
M. Pfeffer, J. P. Sutter, A. Decian and J. Fischer, Organometallics,
1993, 12, 1167.
2 S. Y. M. Chooi, P. H. Leung, C. C. Lim, K. F. Mok, G. H. Quek,
K. Y. Sim and M. K. Tam, Tetrahedron: Asymmetry, 1992, 3, 529;
S. Y. M. Chooi, S. Y. Siah, P. H. Leung and K. F. Mok, Inorg. Chem.,
1993, 32, 4812; J. L. Bookham and W. Mcfarlane, J. Chem. Soc.,
Chem. Commun., 1993, 1352; D. G. Allen, G. M. Mclaughlin,
G. B. Robertson, W. L. Steffen, G. Salem and S. B. Wild, Inorg.
Chem., 1982, 21, 1007; R. T Aplin, H. Doucet, M. W. Hooper and
J. M. Brown, Chem. Commun., 1997, 2097.
3 V. I. Sokolov, L. L. Troitskaya and O. A. Reatov, J. Organomet.
Chem., 1979, 182, 537; T. Hayashi and M. Kumada, Asymmetric
Synthesis, Academic Press, Inc., Orlando, FL, 1985, vol. 5, p. 147;
A. Togni and T. Hayashi, Ferrocenes: Homogeneous Catalysis,
Organic Synthesis and Materials Science, VCH, Weinheim, 1995,
p. 105 and refs. therein; K. H. Ahn, C. W. Cho, H. H. Baek, J. Park
and S. Lee, J. Org. Chem., 1995, 61, 4937.
4 T. Komatsu, M. Nonoyama and J. Fujita, Bull. Chem. Soc. Jpn.,
1981, 54, 184.
5 V. I. Sokolov, L. L. Troitskaya and O. A. Reatov, J. Organomet.
Chem., 1977, 133, C28.
6 A. Patti, D. Lambusta, M. Piattelli and G. Nicolosi, Tetrahedron,
1997, 53, 1361.
7 (a) S. Q. Huo, Y. J. Wu, C. X. Du, H. Z. Yuan and X. A. Mao,
J. Organomet. Chem., 1994, 483, 139; (b) Y. J. Wu, Y. H. Liu,
H. Z. Yuan and X. A. Mao, Polyhedron, 1996, 15, 3315; (c)
C. López, J. Sales, X. Solans and R. Zquiak, J. Chem. Soc., Dalton
Trans., 1992, 2321.
(Rp,Rp)-1. A methanol solution (1 ml) of 0.1 g of complex (Rp,Sc)-
2 and 2 mol of LiCl was mixed with acetic acid (6 ml). The
mixture was stirred at room temperature for about 10 min, then
filtered, and washed with light petroleum three times. The solid
obtained was recrystallized from CH2Cl2–light petroleum
(bp 60–90 ЊC) to produce compound (Rp,Rp)-1. Red crystals,
yield 92.4%, mp >210 ЊC (decomp.), [α]D20 ϩ3212.5 deg cm3 gϪ1
dmϪ1 (c 0.0080 g per 100 ml in CHCl3) (Found: C, 49.92; H,
3.91; N, 2.93. Calc. for C19H18ClFeNPd: C, 49.82; H, 3.96; N,
3.06%). IR(KBr): 3090, 2920, 1551, 1508, 1474, 1105, 999, 817,
721 and 693 cmϪ1. 1H NMR: δ 5.14 (2 H, H-3), 4.73 (2 H, H-5),
4.48 (2 H, H-4), 4.38 (s, 10 H, H-1Ј), 2.01 (s, 6 H, CH3), 2.31 (s,
6 H, CH3), 7.14 (d, 4 H, J = 8.0, NC6H4) and 6.94 (d, 4 H,
J = 6.8 Hz, NC6H4).
Compound (Rp)-3. This was prepared by the published
method.7a Red crystals, yield 79.2%. mp >220 ЊC (decomp.).
[α]D20 ϩ1704.5 deg cm3 gϪ1 dmϪ1 (c 0.0088 g per 100 ml in CHCl3)
(Found: C, 61.48; H, 4.67; N, 1.93. Calc. for C37H33ClFeNPPd:
C, 61.72; H, 4.62; N, 1.94%). IR(KBr): 3067, 3049, 2921, 1569,
1507, 1480, 1094, 998, 817, 758 and 700 cmϪ1. 1H NMR: δ 3.15
(1 H, H-3), 4.65 (1 H, H-5), 4.17 (1 H, H-4), 3.30 (s, 5 H, H-1Ј),
2.05 (s, 3 H, CH3); 2.31 (s, 3 H, CH3), 7.15 (d, 2 H, J = 7.6,
NC6H4), 6.89 (d, 2 H, J = 7.6 Hz, NC6H4), 7.48 m, 7.70 m
(15 H, PPh3).
Crystal structure determination of complex (Rp,Rp)-1
8 R. Navarro, J. Garcia, E. P. Urriolabeitia, C. Catviela and
M. D. Diaz-de-Villegas, J. Organomet. Chem., 1995, 490, 35.
9 J. C. Gaunt and B. L. Shaw, J. Organomet. Chem., 1975, 102, 511;
A. Kasahara, T. Izumi and M. Maemura, Bull. Chem. Soc. Jpn.,
1977, 50, 1878.
10 K. Schlögl, M. Fried and H. Falk, Monatsh. Chem., 1964, 95, 576.
11 SIR 92, A. Altomare, M. C. Burla, M. Camalli, M. Cascarano,
C. Giacovazzo, A. Guagliardi and G. Polidori, J. Appl. Crystallogr.,
1994, 27, 435.
Crystal data. C38H36Cl2N2Fe2Pd2, M = 916.12, red prismatic,
crystal size 2.70 × 0.10 × 1.00 mm, monoclinic, space group
P21 (no. 4), a = 11.64(1), b = 12.083(2), c = 13.004(2) Å,
β = 94.445(3)Њ, Z = 2, V = 1824.1 Å3, Dc = 1.668
g
cmϪ3
,
F(000) = 912, µ(Mo-Kα) = 19.25 cmϪ1
.
Data collection. All measurements were made on a Rigaku
RAXIS-IV imaging plate area detector with graphite mono-
chromated Mo-Kα radiation (λ = 0.71070 Å). The data were
collected at 15 1 ЊC to a maximum 2θ value of 55.0Њ. A total
of 45 images of 4.00Њ oscillation were collected, each being
12 W. C. Hamilton, Acta Crystallogr., 1965, 18, 502.
13 TEXSAN, Crystal Structure Analysis Package, Molecular Structure
Corporation, Houston, TX, 1985 and 1992.
Paper 8/03739F
3730
J. Chem. Soc., Dalton Trans., 1998, 3727–3730