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Inorganica Chimica Acta 352 (2003) 188 /200

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Dangling or tethering the side chain:


(h -(R)-3-phenylbutanol)Ru(II) complexes.
Chiral arene ruthenium complexes: Part 5
6

Guido Marconi a, Holger Baier a, Frank W. Heinemann a, Patrcia Pinto a,


Hans Pritzkow b, Ulrich Zenneck a,*
a
b

Institut fu
r Anorganische Chemie, Universita
t Erlangen-Nu
rnberg, Egerlandstrasse 1, D-91058 Erlangen, Germany
Anorganisch-Chemisches Institut, Universita
t Heidelberg, Im Neuenheimer Feld 276, D-69121 Heidelberg, Germany
Received 23 September 2002; accepted 30 December 2002
Dedicated to Prof. Martin A. Bennett

Abstract
The preparation of optically pure ((R )-3-phenylbutanol)Ru(II) complexes is described. Depending on the reaction conditions and
the co-ligands, the chiral alcohol side chain may dangle free at the periphery of the h6-co-ordinated arene ligand or be co-ordinated
to the metal to result in a h6:h1-chelate ligand system. A key molecule is the dimeric complex [(h6-(R )-3-phenylbutanol)RuCl2]2 (2)
with dangling side chains. It is accessible in good yield either by oxidation and COD ligand exchange of the Ru(0) species
[(COD)(h6-(R )-3-phenylbutanol)Ru] (1) (COD /1,5-cyclooctadiene) or by complexation and dehydrogenation of (R )-3-cyclohexa(1,4-dien-1-yl)-butanol (5). 5 is thus accessible in good yield in two steps from a commercially available starting material. Dimer 2
can be split into mononuclear complexes by heating alcohol solutions to afford tethered [(h6:h1-(R )-3-phenylbutanol)RuCl2] (6), or
by reaction with an additional ligand L (L /PR3, P(OR)3, pyridine) to furnish [(h6-(R )-3-phenylbutanol)(L)RuCl2] (7a /f). If 7a /d
are reacted with silver salts, the side chain is strapped through chloride elimination to form the diastereomeric salts [(h6:h1-(R )-3phenylbutanol)(L)RuCl]  X  (8X) (X /BF4, PF6). The absolute molecular structures of the complexes have been determined in the
solid state. Especially the side chains exhibit interesting conformational features. The CD spectra of 2, 6, and 7a are reported.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Chiral complexes; Arene complexes; Alcohol complexes; Ruthenium complexes; Crystal structures

1. Introduction
First examples of configurationally stable chiral-atmetal arene ruthenium half-sandwich complexes have
been created by Brunner in 1978 [2,3]. Several studies
about synthesis and application of asymmetric arene
ruthenium complexes followed thereafter [4 /7]. One
reason for a still increasing interest in this class of
compounds is their importance in catalysis. Arene
ruthenium complexes can be used in catalytic Diels-

For Part 4, see [1].


* Corresponding author. Tel.: /49-9131-852 7464; fax: /49-9131852 7376.
E-mail address: zenneck@chemie.uni-erlangen.de (U. Zenneck).

Alder [8], alkene metathesis [9], and enantioselective


hydrogen transfer catalyst for carbonyl or imine group
reduction [10,11], for example. These stimulating results
attracted our interest. With the idea of controlling the
stereochemistry and increasing the stability of arene
ruthenium complexes at the same time, we added chiral
side chains to the arene ligand with a donor function in a
suitable distance to the ring. First results of this project
have been already reported [1,12,13]. We introduce
preferably such donor groups, which contain protic
hydrogen atoms, to allow them to play an active role in
the hydrogen transfer [10,11]. In this paper we report
about the ruthenium(II) complex chemistry of enantiopure (R )-3-phenylbutanol, which fulfils these conditions. The ruthenium(II) complex chemistry of the
achiral ligand analogue, 3-phenylpropanol has been

0020-1693/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(03)00136-1

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

investigated lately by Kurosawa and co-workers [14].


They found a free dangling propanol chain as well as a
tethered h6:h1-ligand constellation, depending on the
co-ligands and the chemical conditions.

2. Results and discussion


2.1. Preparation of dimeric [(h6-(R )-3phenylbutanol)RuCl2]2 (2)
We have recently reported about the preparation of
the enantiopure (arene)Ru(0) complex [(COD)(h6-(R )3-phenylbutanol)Ru] (1) (COD /1,5-cyclooctadiene)
[12] by arene metathesis. The related [(COD)(h6-hexamethylbenzene)Ru] has been oxidized successfully by
hydrochloric acid to form the (arene)Ru(II) complex
dimer [(h6-hexamethylbenzene)RuCl2]2 [15]. In the same
manner, the treatment of a acetone solution of 1 with
concentrated hydrochloric acid gave the target product
[(h6-(R )-3-phenylbutanol)RuCl2]2 (2) as a poorly soluble bright orange powder in 85% isolated yield (Scheme
1).
Other polar organic solvents like CH2Cl2, or THF
cannot be used in this reaction, as they cause a loss of
the arene ligand. The crucial point seems to be the coligand substitution of COD by the two chlorides when
the oxidation of the central metal takes place. As the
oxidizing agent has not been identified for the hexamethylbenzene complex to date, we investigated this point
for the transformation 1 0/2. According to gas chromatography, only cyclooctene is formed by the process. No
cyclooctane or COD is observable in the reaction
mixture after completion. This leads to the clue that
two solvated protons oxidize the central metal of 1 and
the in situ formed hydrogen atoms are added to one of
the two C /C double bonds of the COD ligand directly,
thus eliminating its bonding interaction with the metal
and thereby initiating its substitution by chloride ions.
The identity of 2 results from its analytical and
spectroscopic data. Due to its dimeric nature, it is only
sparingly soluble in common organic solvents. Highly
co-ordinating media like acetonitrile or DMSO cleave
the dichloro bridge and enhance the solubility of the
material to allow its NMR-spectroscopic identification.
The NMR spectra obtained from the solutions of 2 in

189

acetonitrile-d3 are slightly broadened in parts, but give


unambiguous evidence for the chiral (h6-(R )-3-phenylbutanol)Ru fragment of 2. As the spectra are identical
with those, obtained from acetonitrile-d3 solutions of
the mononuclear and tethered species [(h6:h1-(R )-3phenylbutanol)RuCl2] (6) (vide infra), the signals must
have been generated by a mononuclear acetonitrile
derivative. Unlike acetonitrile solutions of [(arene)RuCl2]-dimers with non co-ordinating side chains [16], we
cannot identify any trace of a co-ordinated deuteroacetonitrile ligand in the 13C NMR spectra of 2 or 6.
Therefore, we believe in a rapid ligand exchange which
causes the observed broadening effect by interconverting
the mononuclear complexes [(CD3CN)(h6-(R )-3-phenylbutanol)RuCl2] (2a) and strapped 6. On the other
hand, IR spectroscopy of solid 2 proves its dimeric
nature in the solid state. Two bridging (273 and 247
cm 1) Ru /Cl valence modes are observed together with
one terminal (302 cm 1) Ru /Cl mode [17]. The dimer is
present in FD mass spectra as well, however, the basis
peak at m /z /536 represents a species [(areneH)2Ru2Cl] . The loss of two HCl molecules is most
probably due to the formation of alkoxide ligands upon
evaporation, which favor a bridging mode between two
(h6-arene)ruthenium(II) moieties [18]. As we investigated the cationic part of the MS spectra, the loss of
another chloride ion is electrostatically favored in this
case.
On the basis of RuCl3, five steps are necessary to
prepare the enantiopure starting complex 1 [12], thus
this preparative route to 2 is pretty long. To get it more
effectively, we tried an alternative access via Birchreduction, as well [19], which works fine for the achiral

Scheme 1.

Scheme 2.

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G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

phenylpropanol ligand [14]. Basis of this approach is the


commercially available enantiopure ester 3 (Scheme 2).
3 is reduced by LiAlH4 to form the ligand (R )-3phenylbutanol (4) in 98% yield with no effect on its
optical purity [20]. Birch-reduction of 4 leads to 1,4cyclohexadiene derivative 5 which is p-complexed then
to form 2, as designed. This complex reaction includes a
regeneration of 4 by dehydrogenation of 5 and the
reduction of the metal at the same time. The Birchreduction of the arene ring of 4 proceeds with good yield
(92%), but the complexation step requires a threefold
excess of 5 [14,21] to afford 2 in 80% yield in a decent
time, however, flash chromatography of the organic
part of the reaction mixture allows to recover around
90% of the excess of ligand 5. All properties, including
the chiroptical ones of complex 2 obtained by both
methods did not show any relevant difference. Thus, the
stereochemical effectiveness of both routes is identical.

2.2. Mononuclear (h6-(R)-3-phenylbutanol)Ru(II)


complexes
As outlined above for donor solvents, addition of
suitable ligands splits arene ruthenium dichloride dimers
effectively. Alcohols as ligands, however, are not strong
enough, to lead to isolable [(alcohol)(arene)RuCl2]
complexes. In spite of this fact, we suspended 2 in
alcoholic media and heated the mixture until a clear red
solution was formed. Slow cooling led to the precipitation of red crystalline [(h6:h1-(R )-3-phenylbutanol)RuCl2] (6) (65% yield in methanol), thus the ligand
function of the side chain OH group can be activated by
hot alcohols (Scheme 3).
Further evidence for the postulated equilibrium
between the solvent complex [(CD3CN)(h6-(R )-3-phenylbutanol)RuCl2] and tethered 6 was found, when
adding diethyl ether to an acetonitrile solution of 2,
which results in the precipitation of 6. In contrast to the
isolable acetonitrile complexes [(CH3CN)(h6-benzene)RuCl2] [22] and [(CH3CN)(h6-toluene)RuCl2] [16],
this proves a labile bond between the acetonitrile and
the ruthenium atom of 6.

The 1H NMR spectra of the dynamic mixture of


mononuclear complexes which results from 2 or 6 in
acetonitrile solution and 6 in non-co-ordinating solvents, indicate the structural differences of both bonding
modes of the side chain. The multiplet at 3.68 /3.58
ppm, for example, which is assigned to the diastereotopic terminal CH2O group of the free dangling chains,
splits into two clearly separated signals at 3.95 and 3.78
ppm for 6.
The crystal structure of 6 (Fig. 1) consists of two
symmetrically independent molecules of the same enantiomer in the asymmetric unit, in which the sixmembered chelate ring of the tether exhibit chair- (6?)
and boat- (6??) like conformations, respectively.
The absolute configurations of the stereogenic centers
are identical with the starting material and the structure
has been determined three times with different crystals,
obtaining always identical stereochemical results, within
the margin of the experimental error. Since all O /Ru /
Cl and Cl /Ru /Cl angles are close to rectangular, the
ruthenium atom can be considered bearing a pseudooctahedral geometry with the arene occupying three
adjacent sites of the octahedron. Treatment of 2 with a
stoichiometric amount of P-ligands (trimethylphosphite
or various phosphanes) in solutions of acetonitrile or
CH2Cl2 at room temperature, afforded the monomeric
species [(h6-(R )-3-phenylbutanol)Ru(L)Cl2] 7a /d with
good to excellent yields.
With respect to N-ligands, only pyridine and bpicoline were introduced successfully (7e/f). a-Picoline
and other N-heterocycles like imidazole and N -methylimidazole did not form the expected complexes in pure
form, as well as primary amines such as n-BuNH2.
Multicomponent mixtures are formed, instead. A synopsis of these results is reported in Table 1.
7a /f can be treated with hot ethanol to give crystals
suitable for X-ray analysis in all cases.
We report the crystal structures of 7a, 7b and 7e to
elucidate the structural details of the class of compounds
in the solid state (Fig. 2).
In the case of 7a, two symmetrically independent
molecules with remarkably different orientation of the
dangling alcohol side chain and an ethanol molecule are

Scheme 3.

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

191

154.40(19)8; P1 /Ru1 /C6, 159.09(19)8); 7a?? (C41/Ru2 /


P2, 157.1(2)8; C46 /Ru2 /P2, 155.12(18)8); 7b (P1/Ru1 /
C1, 161.57(19)8; P1 /Ru1 /C6, 151.36(19)8). The related
Ru /Carene bond distances are indeed longer than the
mean values of the other four Ru /C interactions. 7a?:
; mean value
Ru1 /C5 /2.231(7); Ru1 /C6 /2.274(4) A

of Ru1 /C(1/4) /2.181 A. 7a??: Ru2 /C41 /2.257(7);


; mean value of Ru2 /C(42/
Ru2 /C46 /2.299(6) A

45) /2.191 A. 7b: Ru1 /C1 /2.272(6); Ru1 /C6 /


; mean value of Ru1 /C(2/5) /2.182 A

2.274(4) A
(Fig. 3).
The crystal structure of 7e consists of two independent molecules in the unity cell. Since they show similar
features, only one is described here. The pyridine ligand
is situated almost opposite to the bond C1 /C2 (N1 /
Ru1 /C1, 152.2(3)8; N1 /Ru1 /C2, 157.0(3)8). As assumed, there is no significant trans elongation for the
Ru /Carene bonds (Fig. 4).
2.3. Tethering the side chain by chloride elimination

Fig. 1. Bottom view of the molecular structure of conformers 6? (a)


and 6?? (b) of [(h6:h1-(R )-3-phenylbutanol)RuCl2] (6) in the solid state.
Hydrogen atoms have been omitted, with the exception of H1B and
H2B, for clarity. Selected bond distances are given in Table 4.

present in the asymmetric unit. The three molecules are


connected by O /H /O hydrogen bridges between the
alcohol functions, which most probably cause the
structural diversity on the molecular level. In the case
of 7a? the dangling chain points away from the metal,
whereas for 7a?? it is the methyl group, which occupies
the sterically unhindered outside position. Corresponding to that, the terminal group O2 /H2O of 7a?? is
somewhat directed to the metal, however, the distances
between the hydrogen atom and the chloride ligands Cl3
and Cl4 are far too long, to assume another hydrogen
bridge. The characteristics of the molecular structure of
7b, resemble the ones of 7a.
As phosphine ligands are well-known for their trans
effect [23], we investigated this point for 7a and 7b,
however, not a ring carbon atom, but a C /C bond of
the arene ring is trans located to the phosphorus atom.
The bond angles Pligand /Ru /Cring characterize the
geometrical constellation best. The angles exceed 1508
for the two carbon atoms, which are influenced by the
effect, but always smaller than 1508 for all the other ring
carbon atoms. The relevant data: 7a? (P1 /Ru1 /C5,

Treatment of 7a /d with 1 equiv. of AgX (X /BF4 or


PF6) in MeOH/CH2Cl2 at room temperature proceeds in
the loss of a chloride anion and the co-ordination of the
dangling hydroxyl group to the ruthenium center. It
affords the formation of complex salts [(h6:h1-(R )-3phenylbutanol)(L)RuCl]X  (8a /dX). Complex salts
8c /dX have not been fully characterized, but prepared
only for a differential reactivity study to determine the
d.e. of the chlorine substitution reaction (Scheme 4).
Cations 8a/d form a pair of NMR-spectroscopic
distinguishable diastereomers each. Due to the single
line absorption of both diastereomers, 31P{1H} NMR is
the method of choice to determine the influence of the
side chain stereogenic center on the stereochemistry of
the ruthenium atom (Table 2).
The diastereoselectivity obtained for complex cations
8a (triphenylphosphane, d.e. /17%) and 8d (trimethylphosphite, 22%) is significantly lower then for 8b
(triethylphosphane, 56%) and 8c (trimethylphosphane,
56%). These values are unexplained in the moment.
Crystals of 8aBF4 could be obtained from a cold
methanol solution. The molecular structure of the
complex cation 8a in the solid state consists of two
diastereomers, 8a? and 8a??, which are both present in
the asymmetric unit. The molecular structure of cation
8a? is presented in Fig. 5.
A view along the molecular axis for both diastereomers is depicted in Fig. 6. Both 8a? and 8a?? exhibit the
defined R -configuration of the enantiopure side chain
stereogenic center, but opposite configurations of the
central metal.
According to the Cahn /Ingold /Prelog rules, 8a?
represents the (SRu,RC) and 8a?? the (RRu,RC) case.
There is no evidence from the molecular structures of 8a?
and 8a?? for a significant stereochemical interaction

192

Table 1
Analytical and spectroscopic data for compounds [(h6-(R )-3-phenylbutanol)(L)RuCl2] (7a /f)
Compound
(L)

a
[a]RT
D /
(8)

Elemental analysis b (%)

NMR data c
31

HL

5.70 (d, 1H, J/5.69); 5.30 /5.28 (br, 1H,


J/5.80); 5.19 (t, 1H, J/5.80); 4.71 /4.68
(dt, 1H, J/19.72, 2.61); 4.48 /4.44 (dt, 1H,
J/5.31, 2.96)
5.63 (d, 1H, J/5.5 Hz); 5.27 /5.18 (m, 2H);
5.18 /5.10 (m, 2H)

4.06 (m, 1H, CH H /O); 3.74 (m, 1H, CHH /O); 3.25
(pseudosext, 1H, CHbenzyl, J/7.04); 2.52 (s, 1H, OH ); 2.19 /
2.09 (m, 1H, CH /CH H); 1.87 /1.75 (m, 1H, CH /CHH );
1.34 (d, 3H, CH3, J/7.0)
4.08 /3.95 (m, 1H, CHH /O); 3.75 /3.61 (m, 1H, CH H /O);
3.19 /3.03 (m, 1H, CHbenzyl); 2.12 /1.90 (m, 1H, CH /CH H);
1.85 /1.69 (m, 1H, CH/CHH ); 1.29 (d, 3H, CH3, J/7.0)
4.07 /3.87 (m, 1H, CHH /O); 3.78 /3.60 (m, 1H, CH H /O);
3.12 /2.95 (m, 1H, CHbenzyl); 2.42 (s, 1H, OH ); 2.01 /1.90 (m,
1H, CH/CH H); 1.85 /1.69 (m, 1H, CH/CHH ); 1.29 (d, 3H,
CH3, J/6.8)
3.90 /375 (m, 1H, CHH /O); 3.78 /3.60 (m, 1H, CH H /O);
3.03 /2.85 (m, 1H, CHbenzyl); 2.17 (s, 1H, OH ); 1.97 /1.85 (m,
1H, CH/CH H); 1.81 /1.75 (m, 1H, CH/CHH ); 1.32 (d, 3H,
CH3, J/7.0)
3.87 (m, 1H, CHH /O); 3.69 (br, 1H, CH H/O); 3.08
(pseudosext, 1H, CHbenzyl, J/6.4); 2.12 /1.97 (m, 1H, CH /
CH H); 1.81 /1.68 (m, 1H, CH/CHH ); 1.56 (s, 1H, OH ); 1.33
(d, 3H, CH3, J/7.0)
3.87 (br, 1H, CHH /O); 3.69 (br, 1H, CH H/O); 3.08
(pseudosext, 1H, CHbenzyl, J/6.1); 2.11 /1.99 (m, 1H, CH /
CH H); 1.78 /1.73 (m, 1H, CH /CHH ); 1.33 (d, 3H, CH3, J/
7.0)

Harene

a (PPh3)

/10.0

C: 57.46 (57.54); H: 28.5 (s)


5.31 (5.00)

7.72 /7.37 (m, 15H)

b (PEt3)

/43.0

C: 43.63 (43.64); H: 29.9 (s)


6.87 (6.64)

2.12 /1.90 (m, 6H); 1.14 /0.98


(m, 9H)

c (PMe3)

/37.0

C: 38.88 (39.21); H: 8.0 (s)


6.13 (5.82)

1.58 (d, 9H, J /12.0)

5.60 (d, 1H, J/5.6); 5.30 /5.18 (m, 2H);


5.15 (d, 1H, J/5.6); 5.10 (m, 1H)

d (P(OMe)3) /36.7

C: 35.01 (34.99);
H:5.57 (5.19)

3.73 (d, 9H, J /12.0)

5.65 /5.45 (m, 5H)

e (py)

/34.1

C: 44.71 (44.90); H: /
4.91 (4.77); N: 3.27
(3.49)

9.04 /9.00 (m, 2H, Ha); 7.82 /


5.58 /5.54 (m, 1H); 5.50 /5.37 (m, 4H)
7.75 (m, 1H, Hg); 7.37 /7.32 (m,
2H, Hb)

f (b-pic)

/30.0

C: 45.99 (46.27); H: /
5.35 (5.10); N: 3.16
(3.37)

8.85 /8.83 (m, 2H, Ha); 7.59 (d, 5.57 /5.37 (m, 5H)
2H, Hg, J/8.0); 7.25 /7.22 (dd,
1H, Hb, J/6.1, 7.6); 2.35 (s,
3H, CH3)

a
b
c

123.6 (s)

Measurements performed in CH2Cl2 (c :/0.1).


Calculated values are given in parentheses.
Measurements performed in CD2Cl2 (7e, 7f), CDCl3 (7a, 7b, 7c) and CD3OD (7d). J/3JHH (Hz).

Hchain

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

P{1H}L

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

193

Fig. 3. Molecular structure of [(h6-(R )-3-phenylbutanol)(PEt3)RuCl2]


(7b) in the solid state. Hydrogen atoms have been omitted, with the
exception of H1A. Selected bond distances are given in Table 4.

Fig. 2. Molecular structures of the two rotamers of [(h6-(R )-3phenylbutanol)(PPh3)RuCl2] 7a? (a) and 7a?? (b) in the solid state.
Solvent molecules are omitted for clarity. Hydrogen atoms have been
also omitted, with the exception of H1O and H2O. Selected bond
distances are given in Table 4.

between the chiral tether and the co-ordination sphere


of the ruthenium atom. As for 7a?, 7a?? a comparable
influence of the co-ordinated phosphorus atom on the
trans -located Ru /Carene bonds is observed for 8a? and
8a?? as well.
When looking down the axis that connects the
centroid of the arene ligand and the metal atom (Fig.
6), one can observe an almost parallel (8a?) or only
slightly twisted (8a??) orientation of the tether, which
spans the distance between ring ligand and metal.
Within the chain there is no significant distortion with
respect to ideal sp3 hybridization of the chain carbon
atoms (vide supra). As a consequence, the two diastereotopic positions at the ruthenium atom opposite to the
coordinated hydroxyl group are not significantly differentiated by the chiral tether.
Single crystals of 8bX could be obtained by crystallization from a mixture ethyl acetate /hexane. Due to
partial hydrolysis of the introduced hexafluoropho-

Fig. 4. Molecular structure of one of the two rotamers of [(h6-(R )-3phenylbutanol)(py)RuCl2] (7e) in the solid state. Hydrogen atoms have
been omitted, with the exception of H1A. Selected bond distances are
given in Table 4.

sphate anion, the unity cell results more complicated


than the one of 8aBF4. From the stereochemical point of
view, the configuration of cation 8b (Fig. 7) shows
essentially the same features of 8a.

2.4. Chiroptical properties


Circular dichroism spectra of solvated 2, 6, and 7a
have been measured (Fig. 8).
The defined complexes 6 and 7a exhibit detailed and
intense CD curves, but a broad and weak signal is
recorded from the acetonitrile solution of dimer 2. In
spite of an identical stereochemistry of the side chain,
the extreme values of the curves for 6 and 7a appear at
different wavelengths. Even the change of the direction
of the effect is observed in the short wavelength region.

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

194

Scheme 4.
Table 2
Diastereomeric excesses of tethered complexes
Compound

31

P{1H} (d )

Integral ratio

d.e. (%)

8a
8b
8c
8d

33.20; 32.95
33.22; 31.44
11.02; 8.99
120.42; 120.02

1:1.40
1:3.57
1:3.57
1:1.58

17
56
56
22

Fig. 5. Molecular structure of the cationic diastereomer 8a? (SRu,RC).


Hydrogen atoms have been omitted, with the exception of H2O.
Selected bond distances are given in Table 4.

As 2 is the starting material for the preparation of 7a


and 6, the weakness of its CD spectrum cannot be
related to a smaller optical purity, but rather to a
compensation effect. The postulated acetonitrile complex 2a and tethered 6 should be comparably different in
their CD spectra as 7a and 6. If so, this finding is
another hint on a dynamic mixture of 2a and 6 in this
solvent.

3. Conclusions
As demonstrated in this paper, chiral ((R )-3-phenylbutanol)Ru(II) complexes are accessible as optically
pure compounds by different routes. Depending on

Fig. 6. Top view of the molecular structure of the diastereomeric


cations 8a? (SRu,RC) (a) and 8a?? (RRu,RC) (b). Counterions, hydrogen
atoms, phenyl substituents of PPh3 and solvent molecules are omitted
for clarity.

reaction conditions and the co-ligands, the donor


substituted side chain may dangle free at the periphery
of the arene ligand [(h6-(R )-3-phenylbutanol)(L)RuCl2]
(7a /f); [(h6-(R )-3-phenylbutanol)RuCl2]2 (2) or
strapped to the central metal. ([(h6:h1-(R )-3-phenylbutanol)RuCl2] (6); [(h6:h1-(R )-3-phenylbutanol)(L)RuCl]X  (8X)).

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

Fig. 7. Molecular structure of the cationic diastereomer 8b (SRu,RC).


Hydrogen atoms have been omitted, with the exception of H1. Selected
bond distances are given in Table 4.

Salts 8X form diastereomers, where a defined side


chain stereogenic center is combined with a chiral metal
co-ordination sphere. The diastereomeric excess values
between 17 and 56% obtained with the combination of
various P-ligands and (R )-3-phenylbutanol are unexplained at the moment, but X-ray structure data indicate
an only weak interaction of the side chain stereogenic
center and the ligands of the central metal atom. This
interaction should be increased if the chiral information
is positioned closer to the donor function. On the other
hand, if the donor center is changed from oxygen to
nitrogen or phosphorus, the second substituents of the
hetero atom should enhance the diastereoselectivity,
too, because of their extra sterical demand. Chiral
systems of that sort are under current investigation.

4. Experimental details
All reactions involving organometallic compounds
were carried out under a dry nitrogen or argon atmosphere, using conventional Schlenk-tube techniques.

195

The areneruthenium(II) complexes are fully air-stable


in the solid state and only slightly air-sensitive in
solution. Solvents were dried and degassed prior to
use. NMR spectra were recorded at room temperature
on JEOL FT-JNM-EX 270 and JEOL FT-JNM-LA
400, spectrometers, using dimethylpolysiloxane and
solvent signals as internal standards. Mass spectra
were recorded on a Varian MAT 212 spectrometer.
Microanalyses were performed using a Carlo Erba
Elemental Analyser Model 1106. Circular dichroism
spectra were recorded on a JASCO J-710 spectropolarimeter, and polarimetric measurements were performed on a Perkin /Elmer 241 polarimeter. IR spectra
were recorded with a Perkin/Elmer 983 spectrophotometer. Compounds 1 [12] and 4 [20] have been
prepared as reported in literature. Analytical data for
compounds 7a/d are reported in Table 1.

4.1. (R )-3-cyclohexa-(1,4-diene-1-yl)-butanol (5)


Approximately, 1 l of liquid ammonia was condensed
in a 2 l flask at /78 8C. A solution of 4 (15.3 g, 0.10
mol) in 80 ml of EtOH and 2.8 g (0.40 mol) of small
freshly cut pieces of lithium were added portionwise at
the same temperature. After 3 h the reaction was
quenched by EtOH (20 ml) and solid NH4Cl (25 g,
0.46 mol). The mixture was then allowed to warm up
slowly by removing the cooling bath. After evaporation
of the ammonia, it was treated with water, extracted
with diethyl ether and dried over anhydrous MgSO4.
Evaporation of the solvent in vacuo gave 5 as a colorless
viscous liquid (13.2 g, 85%) which was used without
further purification.
1
H NMR (399.7 MHz, C6D6, d ): 5.68 /5.59 (m, 2H,
H4/H5); 5.40 (br, 1H, H2); 3.66 (br, 1H, OH); 3.52 (t,
2H, H9, 3JHH /6.83 Hz); 2.60 /2.56 (m, 2H, H3 or H4);
2.51 /2.45 (m, 2H, H3 or H4); 2.20 (pseudosext, 1H, H7,
3
JHH /7.07 Hz); 1.68 /1.57 (m, 1H, H8); 1.51 /1.43 (m,
1H, H8?); 0.95 (d, 3H, H10, 3JHH /6.79 Hz).

Fig. 8. CD spectra of 2 (MeCN, 1/10 4 M), 6 (MeOH, 3/10 4 M), and 7 (MeOH, 1/10 4 M).

196

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

13

C NMR (100.4 MHz, C6D6, d ): 139.3 (C1) 124.9


and 124.7 (C4/C5); 118.6 (C2); 61.2 (C9); 38.1 (C8); 38.0
and 27.3 (C3/C6); 26.1 (C7); 19.8 (C10).
RT
/[a]
D / //12.68 (neat)
4.2. [(h6-(R )-3-phenylbutanol)RuCl2]2 (2)
Method a: To a solution of 350 mg of [(COD)(h6-(R )3-phenylbutanol)Ru] (1) (0.97 mmol) in dry acetone (4
ml) 0.2 ml of concentrated aqueous HCl (2.34 mmol)
was added at room temperature. Complex 2 precipitated
immediately as an orange powder. After stirring for 20
min, the powder was decanted, washed with acetone and
ether, and dried in vacuo (265 mg, 85%).
Method b: RuCl3 /3H2O (5.47 g, ca. 26.4 mmol Ru)
and (R )-3-cyclohexa-(1,4-diene-1-yl)-butanol (5) (17.9 g,
118 mmol) were suspended in ethanol (150 ml). The
mixture was refluxed and stirred for 7 h. On standing
overnight at /30 8C, a dark orange powder of 2
precipitated. It was washed with ethanol, diethyl ether
and dried in vacuo (6.74 g, 79%). All liquid phases were
collected and mixed with the mother liquor. After
removal of the solvents, flash chromatography of the
remaining brown oil (silica; hexane/ethyl acetate, 8:2)
afforded 12.1 g (ca. 90% of the excess) of 5.
1
H NMR (300.1 MHz, CD3CN, d ): 5.64 /5.55 (m,
3Harom); 5.54 /5.49 (m, 2Harom); 3.68 /3.58 (m, 2H,
CH2O); 2.95 /2.87 (pseudosext, 1H, CHbenzyl, 3JHH :/
7.0 Hz); 1.77 /1.66 (m, 1H, CH /CHH /CH2); 1.58 /1.47
(m, 1H, CH /CHH /CH2); 1.12 (d, 3H, CH3, 3JHH /
6.96 Hz).
13
C NMR (67.8 MHz, CD3CN, d ): 104.8 (br, Carene,
ipso ); 84.0 (Carene); 82.7 (Carene); 81.8 (Carene); 59.7
(C H2OH); 38.6 (C H2CH2OH); 33.1 (ArC H(CH3));
19.0 (C H3).
Elemental analysis: Anal. Found: C, 37.90; H, 4.88.
Calc. for C10H14Cl2ORu: C, 37.28; H, 4.38%.
IR (CsI): n[RuCl] (cm1): 302 (terminal), 273 (sh,
chloro bridge), 249 (sh, chloro bridge).
RT
/[a]
D / //37.08 (DMSO, c /0.2).
MS (FD, 2 kV, m /z ): 536 (100%, [(areneH)2Ru2Cl]).
4.3. [(h6:h1-(R )-3-phenylbutanol)RuCl2] (6)
A suspension of 2 (1.37 g, 4.24 mmol) in methanol (10
ml) was refluxed until a deep red solution was obtained.
By slow cooling to room temperature, red crystals of 6
settled down. The crystals were washed with cold
methanol, diethyl ether and dried in vacuo (890 mg,
65%).
1
H NMR (399.7 MHz, CD2Cl2, d): 5.85 (t, 1H,
CHmeta, 3JHH /5.60 Hz); 5.73 (t, 1H, CHmeta,
3
JHH /5.60 Hz); 5.48 (d, 1H, CHortho, 3JHH /6.10
Hz); 5.41 (d, 1H, CHortho, 3JHH /5.60 Hz); 5.33 (t, 1H,
CHpara, 3JHH /5.60 Hz); 3.99 /3.94 (m, 1H, CH H/O);

3.81 /3.76 (m, 1H, CHH /O); 3.00 (s, 1H, OH ); 2.47 /
2.40 (pseudosext, 1H, CHbenzyl, 3JHH /6.96 Hz); 2.18 /
2.02 (m, 2H, CH /CH2); 1.34 (d, 3H, CH3, 3JHH /6.95
Hz).
13
C NMR (67.8 MHz, CD2Cl2, d): 99.41 (Carene, ipso );
89.5 (Carene); 86.2 (Carene); 82.0 (Carene); 77.0 (Carene);
72.21 (Carene); 66.0 (C H2O); 36.4 and 36.0 (ArC HCH2/
ArCHC H2); 21.6 (C H3).
Elemental analysis: Anal. Found: C, 37.56; H, 5.01.
Calc. for C10H14Cl2ORu: C, 37.28; H, 4.38%.
MS (FD, 2 kV, m /z): 536 (100%, [(areneH)2Ru2Cl] ).
RT
/[a]
D / //1.88 (MeOH, c /0.1).
4.4. [(h6-(R )-3-phenylbutanol)(PPh3)RuCl2] (7a)
To a suspension of 2 (359 mg, 1.1 mmol) in
acetonitrile (10 ml), a solution of triphenylphosphane
(299 mg, 1.1 mmol) in 5 ml of the same solvent was
added and the mixture was stirred overnight at room
temperature. After that, the solvent was evaporated and
the residue was washed several times with hexane and
diethyl ether to give 7 as a red powder (636 mg, 98%).
Recrystallization from hot ethanol gave crystals suitable
for X-ray analysis.
13
C NMR (67.8 MHz, CDCl3, d ): 134.1 (d, JCP /9.3
Hz, Cphenyl); 133.3 (d, JCP /47.8 Hz, Cphenyl, ipso); 130.4
(d, JCP /2.5 Hz, Cphenyl); 128.1 (d, JCP /10.5 Hz,
Cphenyl); 118.3 (d, JCP /9.3 Hz, Carene, ipso); 90.3 (d,
JCP /7.5 Hz, Carene); 86.7 (d, JCP /2.4 Hz, Carene);
85.8 (Carene); 85.7 (Carene); 82.6 (Carene); 59.5 (C H2O);
37.7 (C HCH2); 32.0 (CHC H2); 21.8 (C H3).
MS (FD, 2 kV, m /z): 584 [M ]; 536 [(areneH)2Ru2Cl ]; 262 (100%, PPh3). For more data see
Table 1.
4.5. [(h6-(R )-3-phenylbutanol)(PEt3)RuCl2] (7b)
Prepared as 7a, yield 72%, for data see Table 1.
C NMR (75.5 MHz, CDCl3, d): 118.5; 90.1; 85.0;
83.4; 81.6; 77.4; 59.1; 37.5; 31.8; 21.7; 17.8 (d); 7.7.
13

4.6. [(h6-(R )-3-phenylbutanol)(PMe3)RuCl2] (7c)


Prepared as 7a, yield 94%, for data see Table 1.
C NMR (75.5 MHz, CDCl3, d): 119.4; 89.0; 84.9;
84.1; 82.8; 77.8; 59.0; 37.6; 31.9; 21.4; 16.6.
13

4.7. [(h6-(R )-3-phenylbutanol)(P(OMe)3)RuCl2]


(7d)
Prepared as 7a, yield 91%, for data see Table 1.
C NMR (75.5 MHz, CD3OD, d ): 120.7; 92.3; 90.8;
90.7; 87.4; 82.6; 54.4; 59.9; 39.7; 33.5; 19.8.
13

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

4.8. [(h6-(R )-3-phenylbutanol)(pyridine)RuCl2] (7e)


Prepared as 7a but dichloromethane as a reaction
solvent; yield 87%; for data see Table 1.
13
C NMR (67.8 MHz, CD2Cl2, d): 155.3; 138.0;
124.7; 107.1; 84.7; 84.3; 81.8; 81.7; 59.7; 38.8; 32.6; 20.5.
4.9. [(h6-(R )-3-phenylbutanol)(b-picoline)RuCl2] (7f)
Prepared as 7a but dichloromethane as a reaction
solvent; yield 91%; for data see Table 1.
13
C NMR (67.8 MHz, CD2Cl2, d): 155.6; 152.6;
138.7; 135.0; 107.1; 84.5 (d); 81.9 (d); 59.8; 38,9; 32.7;
20.6; 18.4.
4.10. [(h6:h1-(R )-3phenylbutanol)(PPh3)RuCl]BF4 (8aBF4)
To a solution of 7a (558 mg, 0.95 mmol) in
dichloromethane (15 ml), a solution of AgBF4 (185
mg, 0.95 mmol) in 3 ml of methanol was added and the
mixture was stirred at room temperature for 30 min. The
suspension was filtered and the solvent was evaporated.
Recrystallization from MeOH gave (532 mg, 86%) of
8aBF4 as orange crystals.
Spectroscopic data are given for the diastereomeric
mixture.
1
H NMR (399.7 MHz, CD2Cl2, d ): 7.50 /7.35 (m,
30H, phosphane); 6.31 (br, 2H); 6.15 (d, 1H, 3JHH /
5.63 Hz); 5.68 (d, 1H, 3JHH /6.31 Hz); 5.65 (t, 1H,
3
JHH /5.35 Hz); 5.10 /5.07 (m, 1H); 5.01 /4.97 (m,
2H); 4.62 (d, 2H, 3JHH /5.39 Hz); 4.48 /4.44 (m, 1H);
4.24 /4.22 (m, 1H); 3.77 /3.73 (m, 3H); 2.84 /2.76 (m,
1H); 2.74 /2.65 (m, 1H); 2.29 /2.24 (m, 1H); 2.16 /2.05
(m, 2H,); 1.93 /1.85 (m, 2H); 1.33 (d, 3H, CH3, 3JHH /
6.8 Hz); 1.31 (d, 3H, CH3, 3JHH /6.8 Hz).
13
C NMR (67.8 MHz, CD2Cl2, d ): 134.5 (d, JCP /
9.8 Hz); 134.3 (d, JCP /9.8 Hz); 131.8 (d, JCP /2.5
Hz); 131.7 (d, JCP /3.3 Hz); 130.3 (d, JCP /2.4 Hz);
129.8 (d, JCP /2.5 Hz); 129.2 (d, JCP /9.9 Hz); 129.2
(d, JCP /10.7 Hz); 109.3 (d, JCP /5.8 Hz); 106.5;
101.6 (d, JCP /5.8 Hz); 97.5 (d, JCP /11.5 Hz); 91.9;
89.6 (d, JCP /11.5 Hz); 87.0; 85.9; 85.5; 76.0; 66.3;
73.6; 66.3; 36.6; 35.9; 35.7; 34.9; 21.6; 21.5.
31
P NMR (161.7 MHz, CD2Cl2, d ); 33.20; 32.95.
Elemental analysis: Anal. Found: C, 52.41; H, 4.88.
Calc. for C28H29BClF4OPRu: C, 52.89; H, 4.60%.
MS (FD, 2 kV, m /z): 548 [M ]; 536 (100%, [(areneH)2Ru2Cl]).
4.11. [(h6:h1-(R )-3phenylbutanol)(PEt3)RuCl]PF6 (8bPF6)
To a solution of [(h6-(R )-3-phenylbutanol)(PEt3)RuCl2] 7b (250 mg, 0.57 mmol) in dichloromethane
(10 ml), a solution of AgPF6 (144 mg, 0.57 mmol) in 2

197

ml of methanol was added and the mixture was stirred at


room temperature for 15 min. The suspension was
filtered and the solvent was evaporated. The oily residue
was washed with diethyl ether and dried in vacuum to
give 312 mg (98%) of 8bPF6 as an orange microcrystalline solid.
Spectroscopic data are given for the major diastereomer.
1
H NMR (399.7 MHz, CD3OD, d ): 5.63 (d, 1H,
arene, 3JHH /5.5 Hz); 5.27 /5.18 (m, 2H, arene); 5.18 /
5.10 (m, 2H, arene); 4.08 /3.95 (m, 1H, CHH /O); 3.75 /
3.61 (m, 1H, CHH /O); 3.19 /3.03 (m, 1H, CHbenzyl);
2.12 /1.90 (dt/m, 1H, CH /CHH/6H, P /CH2); 1.85 /
1.69 (dt, 1H, CH /CHH ); 1.29 (d, 3H, CH3, 3JHH /7.0
Hz); 1.14 /0.98 (m, 9H, PCH2CH3).
13
C NMR (67.8 MHz, CD3OD, d): 106.7; 104.2 (d,
JCP /6.6 Hz); 91.9; 90.5 (d, JCP /12.3 Hz); 86.2; 80.1;
70.8; 65.8; 37.4; 36.9; 21.9; 17.4 (d, JCP /28.9 Hz); 8.0
(d, JCP /4.1 Hz).
31
P NMR (161.7 MHz, CD2Cl2, d); 33.22; 31.44.
MS (FD, 2 kV, m /z): 405 (100%, [M ]).
4.12. [(h6:h1-(R )-3phenylbutanol)(PMe3)RuCl]BF4 (8cBF4) and
[(h6:h1-(R )-3-phenylbutanol)(P(OMe)3)RuCl]BF4
(8dBF4)
These complexes have been prepared by reacting
solutions of approximately 0.1 mmol of 7c or 7d,
respectively, in 5 ml of dichloromethane with 1.0 equiv.
of silver tetrafluoroborate which is dissolved in 5 ml of
MeOH. The suspension was stirred for 20 min, filtered
and the solvent was removed in vacuo to form an orange
solid. The material was washed with diethyl ether. The
ratio of the diastereomer concentrations was determined
by 31P NMR (see Table 2).
4.13. Crystal structure determination
Crystal data for compounds for 6, 7a /0.5EtOH, 7b,
7c, 8aBF4 /MeOH, and 8b(PF6)0.5(H2PO4)0.5 are given in
Table 3. Selected bond distances and angles are listed in
Table 4. Suitable crystals of the compounds were taken
from the mother liquor. Data were collected on a
Siemens P4 diffractometer using Mo Ka radiation
) and a graphite monochromator. All
(l/0.71073 A
structures were solved by direct methods and refined on
F2 by full-matrix least-squares procedures (SHELXTL 5.03
[24] or SHELXTL 5.10 [25]). All non-hydrogen atoms were
refined anisotropically. Treatment of hydrogen atoms:
Compound 6: All hydrogen atom positions were
obtained from a difference Fourier synthesis, their
positional parameters were refined, while a common
isotropic displacement parameter was kept constant
during refinement. Compounds 7b and 8aBF4 /MeOH:
All hydrogen atom positions were obtained from a

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

198

Table 3
Crystallographic data for 6, 7a /0.5EtOH, 7b, 7e, 8aBF4 /MeOH, 8b(PF6)0.5(H2PO4)0.5

Empirical formula
Formula weight
Color, form
Crystal size (mm)
Crystal system
Space group
)
a (A
)
b (A
)
c (A
a (8)
b (8)
g (8)
3)
V (A
Z
rcalc (g cm3)
m (mm 1)
T (K)
Absorption correction
Tmin; Tmax
No. of refined parameters
F (0 0 0)
Reflections measured
Independent reflections
Observed reflections a
Goodness-of-fit on F2
R1a
wR2 (all data)
Max.; min. residual den 3)
sity (e A
Absolute structural
parameter [26]
a

7a/0.5EtOH

7b

7e

8aBF4 /MeOH

8b(PF6)0.5(H2PO4)0.5

C10H14Cl2ORu
322.18
red, irregular
0.55 /0.45 /
0.18
triclinic
P1
7.563(1)
8.747(1)
9.075(1)
106.37(1)
102.04(1)
97.15(1)
552.5(1)
2
1.937
1.865
210
psi-scan
0.257; 0.345
337

C29H32Cl2O1.5PRu
607.49
red, plates
0.74/0.68/0.06

C15H19Cl2NORu
401.28
yellow, plates
0.56/0.26/
0.08
orthorhombic
P 212121
7.259(1)
13.065(2)
31.719(4)
90.0
90.0
90.0
3008.2(7)
8
1.772
1.392
200
psi-scan
0.284; 0.333
365

C30H37BClF4O3PRu
699.90
orange, prism
0.68/0.52/0.36

C16H30ClF3O3P2Ru
525.86
red, prism
0.46/0.44/0.22

monoclinic
P 21
12.416(1)
13.553(1)
16.766(2)
90.0
107.54(1)
90.0
2690.1(4)
4
1.500
0.864
210
none
/
627

C16H29Cl2OPRu
440.33
red, irregular
0.28/0.20/
0.14
monoclinic
P 21
7.436(1)
10.868(1)
11.909(2)
90.0
104.02(1)
90.0
933.7(2)
2
1.566
1.208
210
none
/
190

monoclinic
P 21
12.680(1)
19.287(1)
13.002(1)
90
93.34(1)
90
3174.4(4)
4
1.464
0.681
210
none
/
768

triclinic
P1
8.437(1)
15.801(2)
16.377(2)
83.08(1)
88.56(1)
86.24(1)
2162.4(5)
4
1.615
1.035
200
psi-scan
0.336; 0.390
999

320
5211
5210
4979
1.078
0.0217
0.0534
0.627; /0.894

1244
12791
11766
9750
1.023
0.0508
0.1303
0.962; /0.990

452
4123
3612
3282
1.058
0.0384
0.0981
1.079; /0.892

1616
7471
6567
5113
1.018
0.0510
0.1164
0.864; /0.552

1432
14910
13889
12713
1.057
0.0345
0.0815
0.554; /0.512

1072
18864
18864
13986
1.018
0.0542
0.1137
0.691; /0.575

0.01(4)

/0.02(4)

0.04(5)

/0.05(7)

0.00(2)

0.01(4)

F0 ]/4s (F ).

difference Fourier synthesis, and both positional and


common isotropic displacement parameters were kept
constant during refinement. Compounds 7a /0.5EtOH,
7c, and 8b(PF6)0.5(H2PO4)0.5: The hydrogen atoms were
geometrically positioned and allowed to ride on their
carrier atoms during refinement; their isotropic displacement parameters were tied to those of the adjacent C
and O atoms by a factor of either 1.2 or 1.5.
Other remarks: The sample of 7b contained only one
single crystal suitable for X-ray diffraction. During the
intensity measurement of the outer shell reflections
(428B/2u B/588) the capillary containing the crystal
broke. The completeness of the data set in this shell
amounts to only about 54%, and is about 75% for the
whole data set. Therefore, no subsequent absorption
correction was possible, but all significant residual
electron density maxima are localized close to the Ru
atoms.

The two independent H2PO4 anions of the unit cell


of 8b(PF6)0.5(H2PO4)0.5 are disordered around one P /O
vector. The BF4 anion of 8aBF4 /MeOH is disordered
around one B /F vector.

5. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC numbers 193800, 193801, 199541,
199543, 193802 and 199542 for compounds 6, 7a, 7b, 7e,
(8aBF4 /MeOH), and (8b(PF6)0.5(H2PO4)0.5), respectively. Copies of this information may be obtained free
of charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: /44-1233-336-033; email deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).

Table 4
) and angles (8) for 6, 7a/0.5EtOH, 7b, 7e, 8aBF4 /MeOH, 8b(PF6)0.5(H2PO4)0.5
Selected bond distances (A
7a/0.5EtOH

7b

8aBF4 /MeOH

7e

8b(PF6)0.5(H2PO4)0.5

2.130(6)
2.148(6)
2.160(6)
2.200(6)
2.169(5)
2.138(5)
2.163(4)
2.3903(14)
2.4198(16)
2.195(5)
2.158(6)
2.151(7)
2.167(6)
2.175(6)
2.139(5)
2.173(4)
2.3876(15)
2.4216(16)

Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/P1
Ru1/Cl1
Ru1/Cl2
Ru2/C41
Ru2/C42
Ru2/C43
Ru2/C44
Ru2/C45
Ru2/C46
Ru2/P2
Ru2/Cl3
Ru2/Cl4

2.173(6)
2.208(7)
2.176(7)
2.167(7)
2.231(7)
2.264 (6)
2.3392(13)
2.405(2)
2.4367(17)
2.257(7)
2.173(8)
2.201(7)
2.198(8)
2.192(7)
2.299(6)
2.3502(14)
2.4116(17)
2.398(2)

Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/P1
Ru1/Cl1
Ru1/Cl2

2.272(6)
2.166(6)
2.199(8)
2.183(7)
2.178(6)
2.274(4)
2.3392(13)
2.4206(15)
2.4148(16)

Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/N1
Ru1/Cl1
Ru1/Cl2

2.183(8)
2.211(8)
2.166(7)
2.167(8)
2.187(7)
2.215 (7)
2.118(6)
2.4158(19)
2.4250(19)

Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/P1
Ru1/O1
Ru1/Cl1
Ru2/C41
Ru2/C42
Ru2/C43
Ru2/C44
Ru2/C45
Ru2/C46
Ru2/P2
Ru2/O2
Ru2/Cl2

2.192(4)
2.213(4)
2.189(4)
2.162(5)
2.218(4)
2.236(3)
2.3649(9)
2.152(3)
2.3863(11)
2.239(4)
2.229(5)
2.177(4)
2.175(4)
2.210(4)
2.200(4)
2.3623(9)
2.136(3)
2.3826(11)

Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/P1
Ru1/O1
Ru1/Cl1

2.193(9)
2.159(9)
2.165(10)
2.230(9)
2.250(9)
2.191(9)
2.344(2)
2.154(8)
2.395(2)

Angles
O1/Ru1/Cl1
O1/Ru1/Cl2
Cl1/Ru1/Cl2
O2/Ru2/Cl3
O2/Ru2/Cl4
Cl3/Ru2/Cl4

83.11(12)
83.26(13)
89.02(6)
84.22(13)
82.62(13)
88.65(6)

P1/Ru1/Cl1
P1/Ru1/Cl2
Cl1/Ru1/Cl2
P2/Ru2/Cl3
P2/Ru2/Cl4
Cl3/Ru2/Cl4

86.66(6)
90.43(5)
88.46(7)
87.33(6)
89.39(6)
87.44(7)

P1/Ru1/Cl1
P1/Ru1/Cl2
Cl1/Ru1/Cl2

86.37(5)
86.44(6)
89.55(6)

N1/Ru1/Cl1
N1/Ru1/Cl2
Cl1 /Ru1/Cl2

86.30(18)
87.76(19)
85.78(7)

P1/Ru1/Cl1
O1/Ru1/Cl1
O1/Ru1/P1
P2/Ru2/Cl2
O2/Ru2/Cl2
O2/Ru2/P2

87.30(4)
83.59(8)
89.83(8)
86.38(4)
84.28(8)
87.26(8)

P1/Ru1/Cl1
O1/Ru1/Cl1
O1/Ru1/P1

87.72(9)
83.4(2)
87.1(2)

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

Distances
Ru1/C1
Ru1/C2
Ru1/C3
Ru1/C4
Ru1/C5
Ru1/C6
Ru1/O1
Ru1/Cl1
Ru1/Cl2
Ru2/C11
Ru2/C12
Ru2/C13
Ru2/C14
Ru2/C15
Ru2/C16
Ru2/O2
Ru2/Cl3
Ru2/Cl4

199

200

G. Marconi et al. / Inorganica Chimica Acta 352 (2003) 188 /200

Acknowledgements
We thank the Deutsche Forschungsgemeinschaft
(SFB 583) and the Fonds der Chemischen Industrie
for financial support. Prof. Dr. P. Gmeiner (E. Fischer
Zentrum-Lehrstuhl fur Pharmazeutische Chemie und
Lebensmittelchemie, Erlangen) is thanked for providing
CD spectroscopic facilities.

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