Multiple ligand transfer reaction between [CpRu(L)(AN)2][PF6] (L = AN, CO, P(OMe)3; AN = acetonitrile) and CpFe(CO)L′X (L′ = CO, PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X = Cl, Br, I)

Article abstract of DOI:10.1016/S0022-328X(00)00370-3

Treatment of ruthenium complexes [CpRu(AN)₃][PF₆] (1a) (AN = acetonitrile) with iron complexes CpFe(CO)₂X (2a-2c) (X = Cl, Br, I) and CpFe(CO)L′X (6a-6g) (L′ = PMe₃, PMe₂Ph, PMePh₂, PPh₃, P(OPh)₃; X = Cl, Br, I) in refluxing CH₂Cl₂ for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)₂X (3a-3c) (X = Cl, Br, I) and CpRu(CO)L′X (7a-7g) (L′ = PMe₃, PMe₂Ph, PMePh₂, PPh₃, P(OPh)₃; X = Br, I), respectively. Similar reaction of [CpRu(L)(AN)₂][PF₆] (1b: L = CO, 1c: P(OMe)₃) causes double ligand transfer to yield complexes 3a-3c and 7a-7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)]₂ was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH₂Cl₂ at room temperature to give 3a, and transforms into 7a by the reaction with PMe₃.

Full text of DOI:10.1016/S0022-328X(00)00370-3

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 610 (2000) 31–37
Multiple ligand transfer reaction between [CpRu(L)(AN)2][PF6]
(L=AN, CO, P(OMe)3; AN=acetonitrile) and CpFe(CO)L%X
(L%=CO, PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Cl, Br, I)
Taku Katayama, Kiyotaka Onitsuka, Shigetoshi Takahashi *
The Institute of Scientific and Industrial Research, Osaka Uni6ersity, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan
Received 12 April 2000; received in revised form 8 May 2000; accepted 19 May 2000
Abstract
Treatment of ruthenium complexes [CpRu(AN)3][PF6] (1a) (AN=acetonitrile) with iron complexes CpFe(CO)2X (2a–2c)
(X=Cl, Br, I) and CpFe(CO)L%X (6a–6g) (L%=PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Cl, Br, I) in refluxing CH2Cl2 for
3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)2X (3a–3c)
(X=Cl, Br, I) and CpRu(CO)L%X (7a–7g) (L%=PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Br, I), respectively. Similar
reaction of [CpRu(L)(AN)2][PF6] (1b: L=CO, 1c: P(OMe)3) causes double ligand transfer to yield complexes 3a–3c and 7a–7h.
Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer
reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(m-I)]2 was isolated from the reaction of 1a with 6a at 0°C. Complex
11a slowly decomposes in CH2Cl2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe3. © 2000
Elsevier Science S.A. All rights reserved.
Keywords: Ligand transfer reactions; Half-sandwich ruthenium complexes; Crystal structures
the reaction of a coordinatively unsaturated complex
with an appropriate complex generates di- or multinu-
clear complexes [7]. Recently novel clusters have been
prepared by the reaction of 1a with anionic metal
carbonyl clusters [8]. Thus, we have examined the reac-
tivity of complex 1a with some transition metal com-
plexes and found that the reaction with iron complexes
CpFe(CO)L%X (2) (L%=CO, PR3, P(OR)3; X=Cl, Br,
I) resulted in a multiple ligand transfer reaction from
iron to ruthenium to give half-sandwich ruthenium
complexes CpRu(CO)L%X. In the present paper we wish
to report the scope and limitation of this multiple
ligand transfer from iron to ruthenium and discuss the
reaction mechanism.
1. Introduction
Much attention has recently focused on half-sand-
wich ruthenium complexes CpRuL2X with a three-
legged piano stool structure due to their potentials in
precise organic syntheses [1]. Although traditional syn-
thetic routes to such ruthenium complexes relied on
CpRu(CO)2Cl and CpRu(PPh3)2Cl as starting materials
[2], convenient routes have been developed by use of
ruthenium complexes with easily exchangeable ligands
[3–6]. Especially the tris(acetonitrile) complex
[CpRu(AN)3][PF6] (1a) (AN=CH3CN) is useful as a
precursor since it has three weak-coordinated ligands
which can be exchanged by various ligands stepwise to
give [CpRu(L)(AN)2][PF6], [CpRu(L)2(AN)][PF6] and
[CpRu(L)3][PF6] [3,4]. Therefore, complex 1a can be
regarded as a pseudo coordinatively unsaturated species
[CpRu]+. On the other hand, it has been reported that
2. Results and discussion
When [CpRu(AN)3](PF6) (1a) was treated with
CpFe(CO)2I (2a) in refluxing CH2Cl2 for
CpRu(CO)2I (3a) was isolated in 84% yield and 14% of
the starting iron complex 2a was recovered. The struc-
3 h,
* Corresponding author. Tel.: +81-6-879-8455; fax: +81-6-879-
8459.
E-mail address: takahashi@sanken.osaka-u.ac.jp (S. Takahashi).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00370-3

32
T. Katayama et al. / Journal of Organometallic Chemistry 610 (2000) 31–37
Table 1
Multiple ligand transfer reaction between [CpRu(AN)3][PF6] (1a) and CpFe(CO)(L%)X (2a–2d, 6a–6g)
Run Substrate
Fe complex
Yield of products (%) a
Recovery of Fe complex (%) a
L%
X
CpRu(CO)2X CpRu(CO)(L%)X
Cp2Ru 4 b Cp2Fe 5 b
1
2
3
4
5
6
7
8
9
2a
2b
2c
2d
6a
6b
6c
6d
6e
6f
CO
CO
CO
CO
PMe3
PMe2Ph
PMe2Ph
PPh3
P(OPh)3
PPh3
I
Br
Cl
CꢀCPh
I
I
I
I
I
Br
Br
84 3a
79 3b
35 3c
14
1
21
10
14
7
9
1
3
16
15
5
21
10
19
25
26
1
11
26
2
11 3a
18 3a
22 3a
27 3a
26 3a
30 3b
24 3b
44 7a
36 7b
32 7c
31 7d
34 7e
28 7f
18 7g
18
17
10
10
6
10
11
6g
P(OPh)3
11
a Isolated yields.
b Yields were estimated from the 1H-NMR spectrum of the mixture of 4 and 5.
The molecular structure of complex 9a was deter-
mined by X-ray crystallography. Selected bond dis-
tances and angles are listed in Table 2. As shown in
Fig. 1, complex 9a has a typical three-legged piano
stool structure. The Fe–P bond distances are 2.144(1)
ture of the resulting complex 3a suggested that two CO
ligands along with one iodide ligand were transferred
from iron to ruthenium. Though the ligand transfer
between transition metal complexes is often found in
organometallic chemistry, multiple transfer is quite rare
[9]. Thus, we investigated this ligand transfer reaction
in detail, and the results are summarized in Table 1.
Reactions of 1a with 2b (X=Br) and 2c (X=Cl) also
caused the ligand transfer to give 3b and 3c, respec-
tively (runs 2 and 3). In these reactions ruthenocene 4
and ferrocene 5 were also produced (Scheme 1). Al-
though the starting iron complexes 2b and 2c were
completely consumed, the fate of iron is not clear since
other identifiable iron complexes were not detected.
Yields of 3a–3c depend on the nature of the halide and
decrease in the order I\Br\Cl, whereas yields of
metallocenes 4 and 5 increase in the order IBBrBCl.
On the other hand, treatment of 1a with iron acetylide
2d (X=CꢀCPh) did not give CpRu(CO)2(CꢀCPh) but
small amounts of 4 and 5, suggesting that the halide
ligand on iron is essential to the present ligand transfer
reaction (run 4). Analogous iron complexes
CpFe(CO)(PR3)X (6a–6g) with phosphine or phosphite
ligands also reacted with 1a to give ruthenium phos-
phine or phosphite complexes CpRu(CO)(PR3)X (7a–
7g) and CpRu(CO)2X (3a–3b) along with metallocenes
4 and 5 (runs 5–11, Scheme 2). In these reactions yields
of 3a increase in the order PMe3BPMe2PhB
PMePh2BPPh3, while yields of 7a–7d decrease in the
order PMe3\PMe2Ph\PMePh2\PPh3. It should be
,
and 2.1653(9) A, which are slightly shorter than those
of [CpFe{P(OMe)3}2(AN)][PF6] (9b) (2.181(6) and
,
2.175(6) A) [10]. This is probably due to the difference
Scheme 1.
noted
that
no
ruthenium
complex
but
[CpFe{P(OPh)3}2(AN)][PF6] (9a) was isolated from the
reaction of 1a with bis(phosphite) complex
CpFe{P(OPh)3}2Br (8) (Scheme 3). This result suggests
that CO ligand on iron has an important role in the
ligand transfer reaction.
Scheme 2.

T. Katayama et al. / Journal of Organometallic Chemistry 610 (2000) 31–37
33
Table 3). Treatments of [CpRu(CO)(AN)2](PF6) (1b)
with CpFe(CO)2X (2a–2c) also gave CpRu(CO)2X
(3a–3c), respectively (runs 1–3). Conversions of iron
complexes 2a–2c, however, are lower than those in the
reactions
with
1a.
Reactions
of
1b
with
CpFe(CO)(PR3)X (6a–6g) produced complex 3a or 3b
as a major product, suggesting that the CO ligand
moves from iron to ruthenium in preference to phos-
phine and phosphite (runs 4–8). Formation of iron
complexes 9a and 9c indicates the phosphorus ligand
transfer between iron complexes which released the CO
and halide ligands. It may be of interest that the
reaction of 1b with 8 afforded 3b and 7g in low yields
(run 9). This result indicates that the carbonyl ligand on
ruthenium is effective for the ligand transfer. When
[CpRu{P(OMe)3}(AN)2](PF6) (1c) was treated with
CpFe(CO)2X (2a–2c), CpRu(CO){P(OMe)3}X (7h–7j)
were isolated as a sole ruthenium complex (runs 10–12,
Scheme 4). Reaction of 1c with 6a gave 7h in 90% yield
(run 13). In this reaction CpRu(PMe3){P(OMe)3}X (10)
could not be detected, suggesting that the phosphine
transfer did not occur at all. As observed in the reac-
tion of 1a with 8, treatment of 1c with 8 gave iron
complex 9a since there are no CO ligands on both
Scheme 3.
Table 2
Selected bond distances (A) and angles (°) for 9a
,
Fe(1)–P(1)
Fe(1)–N(1)
Fe(1)–C(2)
Fe(1)–C(4)
N(1)–C(6)
2.144(1)
1.918(3)
2.104(3)
2.123(3)
1.133(4)
Fe(1)–P(2)
Fe(1)–C(1)
Fe(1)–C(3)
Fe(1)–C(5)
2.1653(9)
2.102(3)
2.122(3)
2.092(3)
P(1)–Fe(1)–P(2)
P(2)–Fe(1)–N(1)
93.97(3)
95.46(8)
P(1)–Fe(1)–N(1)
Fe(1)–N(1)–C(6)
89.86(8)
173.7(3)
of p-acid character between P(OPh)3 and P(OMe)3.
Consequently the Fe–C(Cp) distances of 9a (average
distance 2.109 A) are slightly longer than those of 9b
,
,
(average distance: 2.092 A). In contrast, the Fe–N
,
distance of 9a (1.918(3) A) is consistent with that of 9b
,
(1.923(15) A). Although the cone angle of P(OPh)3 is
ruthenium
and
iron
(run
14).
Complexes
[CpRu(CO)2(AN)][PF6] (1d) and [CpRu{P(OMe)3}2-
(AN)][PF6] (1e) having one acetonitrile ligand did not
react with 2b at all, and an almost quantitative amount
of 2b was recovered (runs 15 and 16). These results
clearly show that at least two acetonitrile ligands are
larger than that of P(OMe)3 [10], no significant differ-
ences are found in the bond angles around iron between
complexes 9a and 9b.
Next we investigated the effect of the ligand on
ruthenium in the ligand transfer reaction (Scheme 4,
Fig. 1. Molecular structure of complex 9a. Hydrogen atoms and PF−6 have been omitted for clarity.

Table 3
Multiple ligand transfer reaction between [CpRu(AN)(L1)(L2)[PF6] (1b–1e) and CpFe(CO)(L%)X (2a–2d and 6a–6g) and CpFe(L)2X (8)
Run Substrate
Ru complex
Yield of products (%) a
Recovery of Fe complex (%)
L1
L2
Fe complex
CpRu(CO)2X
CpRu(CO)(L)X
Cp2Ru 4 b [CpFe(L)2(AN)][PF6]
Cp2Fe 5 b
/
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
1b
1b
1b
1b
1b
1b
1b
1b
1b
1c
1c
1c
1c
1c
1d
1e
AN
AN
AN
AN
AN
AN
AN
AN
AN
AN
AN
AN
AN
AN
CO
CO
CO
CO
CO
CO
CO
CO
CO
2a
2b
2c
6a
6d
6e
6f
6g
8
2a
2b
2c
6a
8
71 3a
43 3b
21 3c
62 3a
58 3a
75 3a
48 3b
59 3b
11 3b
26
53
73
12
21
20
10
10
5
1
7
6 7a
4 7d
5
28 9a
16 7f
2 7g
4
47 9c
22 9a
42 9a
4
30
CO
16 7g
87 7h
48 7i
23 7j
90 7h
P(OMe)3
P(OMe)3
P(OMe)3
P(OMe)3
P(OMe)3
CO
12
50
40
3
9
18
7
610
33 9a
(
2b
2b
97
96
P(OMe)3
P(OMe)3
3
a Isolated yields.
b Yields were estimated from the 1H-NMR spectrum of the mixture of 4 and 5.

T. Katayama et al. / Journal of Organometallic Chemistry 610 (2000) 31–37
35
ity, unequivocal identification was achieved by spectral
analyses. The FAB mass spectrum showed a molecular
ion peak of m/z=644, which corresponds to the dinu-
clear complex possessing two of each Cp, CO, and
iodide ligands. In the IR spectrum of 11a a strong
absorption was observed at 1953 cm−1, suggesting that
the CO ligands do not bridge two ruthenium atoms but
coordinate to ruthenium in an h1 fashion. One sharp
1
singlet signal appeared at l 4.50 in the H-NMR spec-
trum. These data strongly suggest 11a to be a dinuclear
ruthenium complex with two halogen bridges. Complex
11a was unstable in CH2Cl2 at room temperature and
slowly transformed into 3a and unidentified complexes.
However, treatment of 11a with PMe3 instantly gave 7a
in a quantitative yield (Scheme 6).
From the experimental results described above, req-
uisites for the present multiple ligand transfer reaction
may be concluded as follows: (1) halide ligands on iron,
(2) CO ligands on iron or ruthenium, (3) at least two
acetonitrile ligands on ruthenium. A proposed reaction
mechanism involving dinuclear complex 12 as a key
intermediate is illustrated in Scheme 7. Coordinatively
unsaturated ruthenium species provided by dissociation
of two acetonitrile ligands react with iron complexes to
generate complex 12 with both halide and carbonyl
bridges. When 1b or 1c is used as a starting material,
the ligand transfer from iron to ruthenium is achieved
by cleavage of Fe–X and Fe–CO bonds to give stable
ruthenium complexes 3a–3c and 7a–7j. Therefore,
yields of the products are fairly high on the basis of the
conversion of iron complexes in most of the cases
shown in Table 1. In contrast, the reactions of 1a
Scheme 4.
Scheme 5.
Scheme 6.
required on ruthenium for the present ligand transfer
reaction.
When the reaction of 1a with 6a was performed at
0°C, a new ruthenium complex 11a [CpRu(CO)(m-I)]2
along with small amounts of 3a and 7a was obtained
(Scheme 5). Although complex 11a could not be iso-
lated as an analytically pure sample due to low stabil-
Scheme 7.

36
T. Katayama et al. / Journal of Organometallic Chemistry 610 (2000) 31–37
CpFe(CO){P(OPh)3}Br (6g) [19], and CpFe{P-
(OPh)3}2Br (8) [20] were prepared according to the
literature methods.
Typical procedure for the ligand transfer reaction
between [CpRu(AN)2(L)]PF6 (1a–1c) (L=AN,
P(OMe)3, CO) and CpFe(CO)(L%)X (2a–2c, 6a–6g)
(L%=CO, PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3;
X=I, Br, Cl) is as follows.
produce labile ruthenium complex 13, which undergoes
a dimerization with the loss of acetonitrile to give
complex 11. Iron complex 14 with two acetonitrile
ligands is also produced as a result of the transfer of
halide and CO ligands followed by the coordination of
acetonitrile liberated from ruthenium. Complex 14
would be unstable to convert into other iron complexes
such as ferrocene with liberating free ligands L%. Reac-
tions of 11 with free ligands L% (CO, phosphine or
phosphite) provide stable ruthenium complexes 3a–3c
and 7a–7g while complexes 3a–3c are also produced
from decomposition of 11. Ligand exchange of acetoni-
trile on 14 with L% (phosphine or phosphite) gives stable
cationic iron complexes 9a and 9c. Metallocenes 4 and
5 may be produced by the reaction with a cyclopentadi-
enyl ligand released by decomposition of ruthenium
and iron complexes.
In conclusion, we have shown a novel multiple ligand
transfer reaction between ruthenium complexes
[CpRu(L)(AN)2][PF6] (1a–1c) and iron complexes
CpFe(CO)L%X (2a–2c and 6a–6g) to yield
CpRu(CO)LX or CpRu(CO)L%X (3a–3c and 7a–7h).
Such a multiple ligand transfer reaction between transi-
tion metal complexes is quite rare [9]. Although most of
the ruthenium complexes obtained in this study have
already been synthesized by other methods, the multiple
ligand transfer reaction may provide new chemistry of
Group 8 metal complexes and may be applicable to the
synthesis of new cyclopentadienyl–ruthenium com-
plexes.
A dichloromethane solution (30 ml) of [CpRu-
(MeCN)2(L)]PF6 (1.0 mmol) and CpFe(CO)(L%)X (1.0
mmol) was refluxed for 3 h. After removal of the
solvent under reduced pressure, the residue was purified
by column chromatography on silica gel using
dichloromethane or a mixture of dichloromethane–
ethyl acetate as an eluent followed by recrystallization.
All of the resulting ruthenium complexes were char-
acterized by spectral analyses. Spectroscopic data of
CpRu(CO)2X (3a: X=I, 3b: X=Br, 3c: X=Cl) [21],
CpRu(CO)(PMe3)Br (7a) [22], CpRu(CO)(L%)I (7b:
L%=PMe2Ph, 7c: L%=PMePh2, 7d: L%=PPh3, 7e: L%=
P(OPh)3) [23], CpRu(CO)(L%)Br (7f: L%=PPh3, 7g: L%=
P(OPh)3) [24], CpRu(CO){P(OMe)3}I (7h) [23],
CpRu(CO){P(OMe)3}X (7i: X=Br, 7j: X=Cl) [24],
and [CpFe(PPh3)2(AN)][PF6] (9c) [25] were identical to
those found in the literature. Spectroscopic data for a
new cationic iron complex [CpFe{P(OPh)3}2(AN)][PF6]
(9a) are as follows.
1
9a: H-NMR (acetone-d6): l 2.48 (3H, s, CH3CN),
4.33 (5H, s, Cp), 7.27 (6H, t, J=7.3 Hz, Ph), 7.33
(12H, d, J=8.1 Hz, Ph), 7.43 (12H, d, J=7.8 Hz, Ph).
13C-NMR (acetone-d6): l 6.35 (CH3CN), 81.56 (Cp),
122.29 (Ph), 126.63 (Ph), 131.26 (Ph), 137.65 (ipso-C of
Ph), 152.42 (CH3CN). FAB MS: m/z 783 (M+–PF6).
Anal. Calc. for C43H38F6FeNO6P3: C, 55.68; H, 4.13;
N, 1.51; P, 10.02; F, 12.29. Found: C, 55.87; H, 4.00;
N, 1.66; P, 9.93; F, 12.44%.
3. Experimental
All reactions were carried out under an atmosphere
of argon, but the workup was performed in air. 1H- and
13C-NMR spectra were measured in acetone-d6 using
SiMe4 as an internal standard and recorded on a JEOL
JNM-LA400 spectrometer. IR and mass spectra were
taken on a Perkin–Elmer system 2000 FTIR and JEOL
JMS-600H instrument, respectively. Elemental analyses
were performed by The Material Analysis Center, ISIR,
Osaka University.
Dichloromethane was dried over calcium hydride and
distilled before use. All other chemicals available from
commercial sources were used without further purifica-
tion. Ruthenium complexes [CpRu(L)(AN)2][PF6] (1a:
L=AN, 1b: L=CO, 1c: L=P(OMe)3) [3], [CpRu-
(CO)2(AN)][PF6] (1d) [11] and [CpRu{P(OMe)3}2(AN)]-
[PF6] (1e) [3] were prepared by published procedures.
Iron complexes CpFe(CO)2I (2a) [12], CpFe(CO)2Br
(2b) [13], CpFe(CO)2Cl (2c) [14], CpFe(CO)2(CꢀCPh)
(2d) [15], CpFe(CO)(PMe3)I (6a) [16], CpFe(CO)(L%)I
(6b: L%=PMe2Ph, 6c: L%=PMePh2, 6d: L%=PPh3, 6e:
L%=P(OPh)3) [17], CpFe(CO)(PPh3)Br (6f) [18],
3.1. X-ray crystallography of
[CpFe{P(OPh)3}2(AN)][PF6] (9a)
A single crystal suitable for X-ray diffraction was
obtained by recrystallization from dichloromethane–
hexane and mounted on a glass fiber with epoxy resin.
All measurements were performed on a Rigaku AFC7R
automated four-circle diffractometer using graphite
,
monochromated Mo–Ka radiation (u=0.71069 A) at
−50°C. Intensities were corrected for Lorentz and
polarization effects and for absorption using c-scan
technique. The structure was solved by Patterson meth-
ods (DIRDIF94). All non-hydrogen atoms were refined
anisotropically by full-matrix least-squares minimizing
Rw(ꢀFoꢀ−ꢀFcꢀ)2 (w=1/s2(Fo)). The hydrogen atoms
were included at the calculated positions (dC–H=0.95
,
A) and their parameters were not refined. The final

T. Katayama et al. / Journal of Organometallic Chemistry 610 (2000) 31–37
37
Table 4
Crystallographic data for 9a
References
[1] For reviews, see: (a) G. Consiglio and F. Morandini, Chem. Rev.
87 (1987) 761. (b) S.G. Davies, J.P. McNally, A.J. Smallridge,
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[2] For reviews, see: M.A. Bennett, M.I. Bruce, T.W. Matheson, in:
G. Wilkinson (Ed.), Comprehensive Organometallic Chemistry,
vol. 4, Pergamon, Oxford, 1982, p 775.
[3] T.P. Gill, K.R. Mann, Organometallics 1 (1982) 485.
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K. Mereiter, R. Schmid, K. Kirchner, Organometallics 18 (1999)
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3865.
[5] (a) M.O. Albers, D.J. Robinson, A. Shaver, E. Singleton,
Organometallics 5 (1986) 2199. (b) M.O. Albers, D.C. Liles, D.J.
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Chemical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
Unit cell parameters
C43H38F6FeNO6P3
912.50
0.65×0.40×0.25
Monoclinic
Cc (no. 9)
,
a (A)
10.644(2)
19.652(5)
20.249(4)
97.88(2)
4195(1)
4
1.468
5.49
5069
4849 (Rint=0.026)
4544 (I\3.0s(I))
542
0.028
0.041
,
b (A)
,
c (A)
i (°)
3
,
V (A )
Z
Dcalc (g cm−3
)
v (Mo–Ka) (cm−1
)
No. of reflections collected
No. of unique reflections
No. of observed reflections
No. of variables
R
[6] (a) T. Daniel, N. Mahr, T. Braum, H. Werner, Organometallics
12 (1993) 1475. (b) T. Braun, O. Gevert, H. Werner, J. Am.
Chem. Soc. 117 (1995) 7291.
Rw
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Goodness of fit
1.08
cycle of full-matrix least-squares refinement was
converged. All calculation was performed using the
TEXSAN crystallographic software package. Crystallo-
graphic data are listed in Table 4.
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4. Supplementary material
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
.
Data Centre, CCDC No. 142961 for complex 9a.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ UK (fax: +44-1223-336033; e-
mail: deposit@ccdc.cam.ac.uk. or www: http://www.
ccdc.cam.ac.uk).
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Acknowledgements
This work was supported by Grant-in-Aid for Scien-
tific Research from the Ministry of Education, Science,
Sports and Culture. We are grateful to The Material
Analysis Center, ISIR, Osaka University, for support
of spectral and X-ray measurements as well as
microanalyses.
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