Halogen atoms as reactive centers for the introduction of functional side chains into (arene)ruthenium(0) complexes

Article abstract of DOI:10.1002/ejic.200390038

Substitution of the naphthalene ligand of [(COD) (η⁶-naphthalene)Ru] (2) (COD = 1,5-cyclooctadiene) by suitable haloarenes (halogen = F, Cl, Br, I) affords several new mono- and dihaloarene(cyclooctadiene)ruthenium complexes. Depending on the number and position of the halogen and organyl substituents, the haloarenes form achiral or planarchiral π-ligands; [η⁶-bromoarene)(COD)Ru] complexes are prone to rapid bromine/lithium exchange with nBuLi at low temperatures, while the chloro and fluoro derivatives undergo ortho-metalation under the same conditions. The lithiated species react readily with chiral or achiral electrophiles such as chlorodiorganophosphanes, carbonyl chlorides, aldehydes, lactones, ketones, and epoxides to yield substituted [η⁶-arene)(COD)Ru] complexes with donor functions in their side chains, inaccessible by other routes. Enantiopure complexes are obtained when achiral lithioarene complexes are combined with chiral electrophiles, but pairs of diastereomers are formed if the lithioarene ligand is a planar-chiral species. Dinuclear ruthenium complexes [1,1-bis{(COD)(η⁶phenyl)Ru}-1,4-butanediol] (28) and [1,1-bis{(COD)(η6-4-fluorophenyl)Ru}-1,4-butanediol] (30) with two (η⁶-aryl)-(COD)Ru units linked by a common 1,4-butanediol side chain are formed through the reactions between the appropriate lithioarene complexes and γ-butyrolactone. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2003).

Full text of DOI:10.1002/ejic.200390038

FULL PAPER
Halogen Atoms as Reactive Centers for the Introduction of Functional Side
Chains into (Arene)ruthenium(0) Complexes[‡]
Gregor Bodes,[a] Frank W. Heinemann,[a] Günter Jobi,[a] Jens Klodwig,[a] Stefan Neumann,[a]
and Ulrich Zenneck*[a]
Dedicated to Professor Horst Kisch on the occasion of his 60th birthday
Keywords: Arene complexes / Electrophilic substitution / Lithiation / Ruthenium
Substitution of the naphthalene ligand of [(COD)(η6-naph-
thalene)Ru] (2) (COD 1,5-cyclooctadiene) by suitable
haloarenes (halogen = F, Cl, Br, I) affords several new mono-
stituted [(η6-arene)(COD)Ru] complexes with donor functions
in their side chains, inaccessible by other routes. Enantiopure
complexes are obtained when achiral lithioarene complexes
=
and dihaloarene(cyclooctadiene)ruthenium complexes. De- are combined with chiral electrophiles, but pairs of diastereo-
pending on the number and position of the halogen and or-
ganyl substituents, the haloarenes form achiral or planar-
chiral π-ligands; [(η6-bromoarene)(COD)Ru] complexes are
prone to rapid bromine/lithium exchange with nBuLi at low
temperatures, while the chloro and fluoro derivatives un-
dergo ortho-metalation under the same conditions. The
lithiated species react readily with chiral or achiral elec-
trophiles such as chlorodiorganophosphanes, carbonyl chlor-
ides, aldehydes, lactones, ketones, and epoxides to yield sub-
mers are formed if the lithioarene ligand is a planar-chiral
species. Dinuclear ruthenium complexes [1,1-bis{(COD)(η6-
phenyl)Ru}-1,4-butanediol] (28) and [1,1-bis{(COD)(η6-4-
fluorophenyl)Ru}-1,4-butanediol] (30) with two (η6-aryl)-
(COD)Ru units linked by a common 1,4-butanediol side
chain are formed through the reactions between the appro-
priate lithioarene complexes and γ-butyrolactone.
( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
2003)
Introduction
1,3,5-cyclooctatriene)Ru] (1) and [(COD)(η6-naphtha-
lene)Ru] (2) as suitable starting materials (Scheme 1).
(Arene)ruthenium(0) complexes are useful catalysts for
hydrogenation,[2,3] isomerization,[4] and dimerization[5,6] re-
actions of alkenes. Their (arene)ruthenium() counterparts
catalyze enantioselective hydrogen transfer to ketones[7,8]
and imines[9] in the presence of enantiomerically pure chiral
β-amino alcohols[7] or 1,2-diamines,[8,9] affording high
yields and high ees at the same time. Thanks to the particu-
lar stability of the areneϪmetal bond,[10] (arene)ruthenium
complexes may be converted from Ru0 into RuII without the
loss of the arene ligand, simply by addition of hydrochloric
acid.[2] Only the co-ligands that complete the coordination
sphere are exchanged in parallel with the redox process. Of
course, it would be very promising to perform the catalytic
reactions of (arene)ruthenium complexes in both redox
states with enantiopure species whose chirality was con-
nected with the arene ligand. The preparation of [(η6-arene)-
(COD)Ru] complexes is well known since the work of Ben-
nett, Vitulli, and Pertici,[3,11,12] who introduced [(COD)(η6-
Scheme 1. Synthesis of [(η6-arene)(COD)Ru] complexes by ligand
exchange
[‡]
Chiral Arene Ruthenium Complexes, 4. Part 3: Ref.[1]
[a]
However, bulky, polar, or highly substituted arenes can-
not be introduced in this way. An alternative route to such
complexes utilizes bromine/lithium exchange between [(η6-
bromoarene)(COD)Ru] complexes and n-butyllithium at
Institut für Anorganische Chemie der Universität Erlangen-
Nürnberg,
Egerlandstr. 1, 91058 Erlangen, Germany
Fax: (internat.) ϩ 49-(0)9131/852-7367
E-mail: Zenneck@chemie.uni-erlangen.de
Eur. J. Inorg. Chem. 2003, 281Ϫ292  2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0102Ϫ0281 $ 20.00ϩ.50/0
281

G. Bodes, F. W. Heinemann, G. Jobi, J. Klodwig, S. Neumann, U. Zenneck
FULL PAPER
low temperatures.[13] The lithiated species can be treated
with alkyl chloroformates to form ester-substituted [(η6-ar-
ene)(COD)Ru] compounds. Through the introduction of
chiral alkyl chloroformates [alkyl ϭ (Ϫ)-menthyl], this dir-
ectly affords enantiopure asymmetric complexes. To de-
velop the high potential of this approach, we investigated
the preparation and reactivity of (mono- and dihaloar-
ene)ruthenium() complexes systematically. These allow the
introduction of many electrophiles of choice. Examples are
provided for chlorodiorganophosphanes, carbonyl chlor-
ides, aldehydes, lactones, ketones, and epoxides. Novel (ar-
ene)ruthenium() complexes with donor functions such as
PR2 and OH in the side chain are of interest, as these func-
tions should offer the potential to control the reactivity of
the different types of (arene)ruthenium catalysts.
Results and Discussion
Preparation of [(COD)(η6-haloarene)Ru] Complexes
Mono- or dihaloarenes (fluorobenzene, 1,3-difluoroben-
zene, 3-fluorotoluene, 3-chlorotoluene, 1,4-dichlorobenzene,
2-bromo-1,4-xylene,
1,3-dibromobenzene,
1-bromo-4-
fluorobenzene, 1-bromo-4-iodobenzene, and 4,4Ј-difluoro-
1,1Ј-biphenyl) replace the naphthalene ligand of
[(COD)(η6-naphthalene)Ru] (2) in the presence of aceto-
nitrile at room temperature in moderate to excellent yield
(Scheme 2). The reaction fails with the triply substituted ar-
enes 3,5-dibromotoluene, 1,2,3- and 1,3,5-tribromobenzene,
and 1,2,3-trichlorobenzene.
Two different tendencies are exemplified by the experi-
mental results. If one halogen atom of an incoming arene
ligand is accompanied by one or two organyl substituents,
the yield increases, but it is reduced with a second halogen
atom. So far, no trihalobenzenes have been coordinated
successfully. The only dihalobenzene that gives yields of
more than 50% is 1,4-dibromobenzene;[13] in all other cases
it is between 10 and 21%. As the minimum yield is obtained
with 1,4-dichlorobenzene, there must be more than one
reason for the diminishing effect, but electronegativity is
most probably one of them. The electron-donating effects
of the alkyl substituents favor π-complexation directly. As
a consequence, even multiply alkyl-substituted arenes can
be introduced. Not only 1,2,4-trimethylbenzene, but also
1,2,3,4-tetramethylbenzene, are prone to this type of reac-
tion.[3] Two of the (dihalobenzene)ruthenium complexes
have been characterized by X-ray diffraction: [(η6-1-bromo-
4-fluorobenzene)(COD)Ru] (10) and [(η6-1-bromo-4-iodo-
benzene)(COD)Ru] (11) (Figure 1). Thanks to the pro-
nounced chemical differences between their halogen atoms,
10 and 11 are both suitable for stepwise substitution reac-
tions.
Scheme 2. Preparation of [(COD)(η6-haloarene)Ru] complexes
Figure 1. Molecular structures of 10 (left) and 11 (right) in the solid state; selected bond lengths [pm] for 10: Ru(1)ϪC(11) 225.4(6),
Ru(1)ϪC(12) 219.6(7), Ru(1)ϪC(13) 226.4(7), Ru(1)ϪC(14) 224.2(7), Ru(1)ϪC(15) 220.4(7), Ru(1)ϪC(16) 224.6(7); selected bond lengths
[pm] for 11: Ru(1)ϪC(11) 217.1(9), Ru(1)ϪC(12) 226.8(9), Ru(1)ϪC(13) 226.5(9), Ru(1)ϪC(14) 219.4(9), Ru(1)ϪC(15) 227.8(9),
Ru(1)ϪC(16) 226.4(9)
282
Eur. J. Inorg. Chem. 2003, 281Ϫ292

Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes
FULL PAPER
The coordinated arene ring is boat-like and distorted in 1,4-xylene)(COD)Ru] (8), [(η6-1-bromo-4-fluorobenzene)-
(COD)Ru] (10), [(η6-bromobenzene)(COD)Ru] (13), [(η6-2-
both cases, as two para-positioned ring carbon atoms are
situated significantly closer to the central metal atom than
bromotoluene)(COD)Ru] (14),[13] and n-butyllithium as the
the other four. In the case of 10 the average value is 220 pm
for Ru(1)ϪC(12) and Ru(1)ϪC(15), but 225 pm for the
other RuϪCring distances. The corresponding values for 11
are 218 pm for Ru(1)ϪC(11)/(14) versus 226 pm. This devi-
ation from planarity is a known effect in [(η6-arene)(CO-
D)Ru] complexes.[13,14] Its observation, undisturbed in the
case of [(COD)(η6-1,4-dihalobenzene)Ru] complexes, pro-
vides evidence for the interligand influence of COD and
arene ligands even in the case of electronegative 1,4-disub-
stitution of the arene.
metalation agent. In all cases, the bromine/lithium exchange
is accomplished within a few minutes in THF as the solvent
at Ϫ80 °C, and the electrophiles are added at the same tem-
perature immediately after its completion. In the case of
OH-group formation, the reaction sequence finishes with a
hydrolysis. We tested this type of reaction with chlorodi-
organophosphanes, carbonyl chlorides, ketones, epoxides,
aldehydes, and lactones as electrophiles. (Scheme 3, Table 1)
The reaction sequence proceeds very well, and so the in-
troduction of side chains with phosphanyl, ester, oxo, and
hydroxy groups, including phenolic hydroxy functions, is a
favorable preparative route. The mononuclear and dinuclear
complexes 15Ϫ34 are accessible in this way. We had previ-
ously attempted the direct preparation of some related com-
plexes by ligand exchange as an alternative and straightfor-
ward approach and had failed in several interesting cases.
Acidic hydrogen atoms, phosphanyl groups, and bulky sub-
stituents on incoming arene ligands block the arene ligand
exchange reaction of ruthenium().[1] Neither the NMR
spectra, nor other experimental observations point to direct
interactions between the donor centers of the side chains
and the ruthenium atoms in 15Ϫ34. As [(η6-arene)(COD)-
Ru] complexes are closed-shell 18-valence electron species,
there is no driving force for such an effect. The potential
interaction will come into play when an electron-deficient
situation is created for the ruthenium atom by oxidation or
COD ligand displacement, through a catalytic application
of the complexes.[16]
Electrophilic Substitution of [(η6-bromoarene)(COD)Ru]
Complexes
Metalation and subsequent reactions of organometallic
compounds are standard derivatization methods.[15] The
electrophilic substitution of [(η6-bromoarene)(COD)Ru]
complexes is initiated by a rapid bromine/lithium exchange
at low temperatures. Examples are given for [(η6-2-bromo-
Scheme 3. Electrophilic substitution reaction of [(η6-bromoarene)-
(COD)Ru] complexes
Table 1. Products of electrophilic substitution of [(η6-bromoarene)(COD)Ru] complexes
Starting
material
Electrophile
E
Product
Yield
(%)
13
14
13
14
14
13
14
13
13
14
13
13
13
ClP(iPr)2
ClP(iPr)2
ClP(tBu)2
ClPPh2
acetyl chloride
pivalyl chloride
pivalyl chloride
ClCOPhtBu
(1S)-(Ϫ)-camphanic chloride
(R)-(ϩ)-styrene epoxide
acetone
[(COD)(diisopropyl-η6-phenylphosphane)Ru] (15)
[(COD)(diisopropyl-η6-2-tolylphosphane)Ru] (16)
[(COD)(di-tert-butyl-η6-phenylphosphane)Ru] (17)
[(COD)(diphenyl-η6-2-tolylphosphane)Ru] (18)
[(COD)(η6-2-methylacetophenone)Ru] (19)
83
86
78
73
90
94
91
67
43
31
65
69
21
45
40
16
44
48
[(COD)(tert-butyl η6-phenyl ketone)Ru] (20)
[(COD)(tert-butyl η6-2-tolyl ketone)Ru] (21)
[(COD)(4-tert-butylphenyl η6-phenyl ketone)Ru] (22)
(Ϫ)-[(COD)(camphanoyl η6-phenyl ketone)Ru] (23)
[(COD){1-phenyl-2-(η6-2-tolyl)ethanol}Ru] (24a, 24b)
[(COD){dimethyl(η6-phenyl)methanol}Ru] (25)
[(COD)(η6-phenylcyclohexanol)Ru] (26)
cyclohexanone
γ-butyrolactone
[(COD)(3-hydroxypropyl η6-phenyl ketone)Ru] (27)
[1,1-bis-{(COD)(η6-phenyl)Ru}-1,4-butanediol] (28)
[(COD)(η6-4-fluorophenyl 3-hydroxypropyl ketone)Ru] (29)
[1,1-bis-{(COD)(η6-4-fluorophenyl)Ru}-1,4-butanediol] (30)
[(COD)(3-hydroxypropyl η6-2-tolyl ketone)Ru] (31)
[(COD){(6-methoxy-2,2-dimethyltetrahydrofuro[2,3-d]-
[1,3]dioxol-5-yl)(η6-phenyl)methanol}Ru] (32a, 32b)
10
γ-butyrolactone
14
13
γ-butyrolactone
1,2-O isopropylidene-3-O-
methyl-α--xylopento-
dialdofuranose-(1,4)
(Ϫ)-menthyl chloroformate
o-acetylsalicoyl chloride
8
14
[(COD)(menthyl η6-1,4-xylene-2-carboxylate)Ru] (33a, 33b)
[(COD)(o-hydroxyphenyl η6-2-tolyl ketone)Ru] (34)
42
60
Eur. J. Inorg. Chem. 2003, 281Ϫ292
283

G. Bodes, F. W. Heinemann, G. Jobi, J. Klodwig, S. Neumann, U. Zenneck
FULL PAPER
Scheme 4. Electrophilic substitution reactions of [(η6-2-bromotoluene)(COD)Ru] (14)
[(η6-bromobenzene)(COD)Ru] (13) is an achiral starting
material and the same is true for its lithium exchange prod-
uct [(η6-lithiobenzene)(COD)Ru] (13a). Treatment with op-
tically pure (1S)-(Ϫ)-camphanoyl chloride therefore directly
affords enantiopure (Ϫ)-[(COD)(camphanoyl η6-phenyl ke-
tone)Ru] (23). The electrophilic substitution reaction does
not affect the stereogenic centers of the incoming elec-
trophile. Because of the planar chirality of their arene li-
gands, 8 and 14 consist of racemic mixtures of asymmetric
compounds, and so a subsequent reaction with enantiopure
electrophiles produces pairs of diastereomers. An example
is the combination of 14 with (R)-(ϩ)-styrene epoxide. The
two C1-symmetric diastereomers 24a and 24b are formed in
this way (Scheme 4).
Diastereomers 32a and 32b are also obtained by treat-
ment of achiral 13 with 2-O isopropylidene-3-O-methyl-α-
-xylopentodialdofuranose-(1,4), as the transformation of
its aldehyde function into a secondary benzyl alcohol by
addition to the (arene)ruthenium fragment is not diastereo-
selective (Scheme 5).
Scheme 5. Preparation of diastereomeric furanose-substituted com-
plexes 32a and 32b
To our surprise, electrophilic substitution of 14 with o-
acetylsalicoyl chloride causes a spontaneous cleavage of the was treated with γ-butyrolactone. Not only was the de-
ester group, which was replaced by a phenolic OH group in signed ring-opening/addition product [(COD)(3-hydroxy-
the end product. Lithiated 14a thus yields [(3-hydroxy- propyl η6-phenyl ketone)Ru] (27) formed (in moderate
phenyl η6-2-tolyl ketone)(COD)Ru] (34) as the only isolable yield), but dinuclear [1,1-bis{(COD)(η6-phenyl)Ru}-1,4-bu-
product. (Scheme 4) Complex 34 was our target product tanediol] (28) was isolated as the main product. The results
from the beginning, as it contains an OH group at a suitable obtained from the combination of the 1-bromo-4-fluoro-
distance from the metal atom, but the experimental finding benzene complex 10 and γ-butyrolactone are very similar,
represents a nice shortcut in the right direction. As in the except that the yield of mononuclear product [(COD)(η6-4-
case of the (bromoarene)ruthenium complexes, the hand- fluorophenyl 3-hydroxypropyl ketone)Ru] (29) exceeds that
ling of the novel compounds 15 to 34 causes no problems. of dinuclear [1,1-bis{(COD)(η6-4-fluorophenyl)Ru}-1,4-bu-
All are stable in the solid state, show no sign of hydrolysis, tanediol] (30).
and are only slightly air-sensitive in solution.
The first addition intermediate 27a, most probably due
Another surprising result occurred when the bromine/li- to a high ketone reactivity,[1] couples with its lithiobenzene
thium exchange product 13a of bromobenzene complex 13 precursor complex 13a to form a 1,4-butanediolate interme-
284
Eur. J. Inorg. Chem. 2003, 281Ϫ292

Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes
FULL PAPER
Scheme 6. Formation of dinuclear (arene)ruthenium complex 28
diate. Both branches of the reaction sequence are termin- side chain per {(η6-aryl)(COD)Ru}2 unit, and the absence
ated by hydrolysis, the lithium ions being replaced by hydro- of ketone functions. The molecular structures of 28 and 30
gen atoms. (Scheme 6)
in the solid state represent different rotamers. This applies
This route represents a new and effective pathway to to the relative orientation of the (η6-aryl)(COD)Ru complex
benzyl carbon atom linked (bisarene)diruthenium com- units as well as for the 1,4-butanediol chains. In the case of
plexes. A special property is the bifunctionalization of the 28 the two (COD)Ru fragments are located opposite to the
common 1,4-butanediol side chain. Both dinuclear com- C116ϪC117ϪC214 bond angle of the bridging benzyl car-
plexes 28 and 30 have been characterized by X-ray diffrac- bon atom C117. Its reduction to 106.3° is a consequence
tion: their molecular structures are depicted in Figure 2.
of that arrangement. In contrast to that, the (COD)Ru(2)
The X-ray results are in full accordance with the analyt- fragment of 30 interacts directly with the arene ligand of
ical and spectroscopic findings on the complexes, which Ru(1) and the corresponding C116ϪC117ϪC216 benzyl
confirm their dinuclear nature, the introduction of only one carbon bond angle of 30 is increased significantly. The
Figure 2. Molecular structures of [1,1-bis{(COD)(η6-phenyl)Ru}-1,4-butanediol] (28, left) and [1,1-bis{(COD)(η6-4-fluorophenyl)Ru}-
1,4-butanediol] (30, right) in the solid state; hydrogen atoms have been omitted for clarity; selected bond lengths [ppm] of 28:
Ru(1)ϪC(111) 227.6(7), Ru(1)ϪC(112) 220.0(8), Ru(1)ϪC(113) 225.9(7), Ru(1)ϪC(114) 225.3(7), Ru(1)ϪC(115) 222.0(6), Ru(1)ϪC(116)
231.1(6); bond angle [°]: C(116)ϪC(117)ϪC(214) ϭ 106.3(5); selected bond lengths [ppm] of 30: Ru(1)ϪC(111) 223.7(3), Ru(1)ϪC(112)
219.3(3), Ru(1)ϪC(113) 225.9(2), Ru(1)ϪC(114) 228.0(3), Ru(1)ϪC(115) 220.7(3), Ru(1)ϪC(116) 229.4(2); bond angle [°]:
C(116)ϪC(117)ϪC(216) ϭ 112.19(19)
Eur. J. Inorg. Chem. 2003, 281Ϫ292
285

G. Bodes, F. W. Heinemann, G. Jobi, J. Klodwig, S. Neumann, U. Zenneck
FULL PAPER
RuϪCaryl bond lengths of both species cover a range from exchange, but ortho-metalation is observed instead.[17] This
220 to 231 pm. As in the case of the dihaloarene complexes, type of reactivity was tested by treatment of nBuLi with
the arene ligands are slightly boat-like distorted.
[(COD)(η6-3-fluorotoluene)Ru]
(5)
and
[(η6-3-
The molecular packing of the dinuclear complexes in the chlorotoluene)(COD)Ru] (6). o-Acetylsalicoyl chloride was
solid state is dominated by the formation of infinite zigzag treated with metalated fluoro derivative 5a, and α-phenyl-
chains of the 1,4-butanediol substituents by intermolecular cinnamoyl chloride with the corresponding chloro complex
OϪHϪO bridges. (Figure 3).
6a. (Scheme 7)
As in the case of the bromine/lithium exchange products,
the ortho-metalation intermediates 5a and 6a allow effective
introduction of electrophiles. The metalation takes place se-
lectively at the less sterically hindered o-position with re-
spect to the halogen substituent. As the chlorine and fluor-
ine atoms remain in the complexes they might be usable a
second time for subsequent modification of complexes 35
and 36. In analogy to phenol complex 34, the ester function
of o-acetylsalicoyl chloride is again split spontaneously in
the reaction and the target phenolic side chain OH group
is formed directly.
Figure 3. Molecular packing of 28 in the solid state; OϪHϪO
bridges are indicated by the dotted lines between the stacks
Conclusions
[(COD)(η6-haloarene)Ru] complexes are easily accessible
by arene ligand substitution of [(COD)(η6-naphthalene)Ru]
(2) by suitable mono- and dihaloarenes. The reaction works
with F, Cl, Br, and I as arene ring substituents, and the in-
coming haloarene may have one or two halogen atoms and
a maximum number of three substituents. Depending on the
number and position of the halogen atom(s) and organyl
substituent(s), the haloarenes form achiral or planar-chiral
π-ligands. [(COD)(η6-haloarene)Ru] complexes are valuable
starting materials for the introduction of arene ligand side
chains with functional groups that would otherwise block the
π-complexation of arene ligands to Ru0 or RuII. The bromine
atom of [(η6-bromoarene)(COD)Ru] complexes is rapidly ex-
Interestingly, a single o-methyl group is a steric protector
sufficiently powerful to disfavor the formation of dinuclear
1,4-butanediol complexes in the γ-butyrolactone reactions
almost completely. 2-Bromotoluene complex 14 therefore
forms [(COD)(3-hydroxypropyl η6-2-tolyl ketone)Ru] (31)
as the isolable main product. A dinuclear analogue to 28
and 30 can only be detected by mass spectrometry, as a
small side product.
Electrophilic Substitution through ortho-Metalation of
(Chloro- and fluoroarene)ruthenium Complexes
(Chloro- and fluoroarene)metal complexes follow a differ- changed for a lithium atom when they are treated with nBuLi
ent reaction pathway when they are attacked by organoli- at low temperatures, but the chloro and fluoro derivatives
thium agents. The main route is no longer halogen/lithium undergo ortho-metalation under the same conditions. The re-
Scheme 7. Electrophilic substitution reaction by ortho-metalation
286
Eur. J. Inorg. Chem. 2003, 281Ϫ292

Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes
FULL PAPER
ene and the combined liquids were filtered through Al2O3/5%H2O.
If necessary, the product was purified by column chromatography
on Al2O3/5%H2O with n-hexane as the mobile phase.
sulting lithiobenzene species react effectively with a great
variety of chiral or achiral electrophiles to yield substituted
[(η6-arene)(COD)Ru] complexes with donor functions such
as OH or PR2 groups in the side chains. Enantiopure com-
plexes are obtained when achiral lithioarene complexes are
combined with chiral electrophiles, but pairs of diastereo-
mers are formed if the lithioarene ligand is a planar chiral
species. Because of the high reactivity of the primary prod-
ucts, the combination of sterically unhindered lithiobenzene
complexes and γ-butyrolactone results in the formation of
dinuclear [1,1-bis{(η6-aryl)(COD)Ru}-1,4-butanediol] com-
plexes, each with two [(η6-aryl)(COD)Ru] units linked by a
common 1,4-butanediol side chain.
The new reaction sequences allow a completely new means
of ligand design for (arene)ruthenium catalysts of interest,
the selectivity and reactivity of which may now be controlled
by highly variable side chains with σ-ligand properties of
choice. This point is currently under investigation. In a sub-
sequent paper we will report on the oxidation of some of the
(η6-arene)Ru0 complexes with the donor side chains reported
here to form corresponding (η6-arene)RuII species, the
tethering of the donor function to the metal atom, and first
insights into their potential as hydrogen-transfer catalysts.[16]
o-Lithiation and Electrophilic Substitution Reactions of (η6-Chloro-
and η6-fluoroarene)ruthenium Complexes (General Procedure): The
chloro- or fluoroarene complex was dissolved in THF and cooled
to Ϫ80 °C, and a solution of n-butyllithium in hexane was added
by syringe. After 5 min, a solution of the electrophile in THF was
added at the same temperature, and the mixture was allowed to
come to room temp. over 2 h. All volatile components were re-
moved in vacuo. The residue was extracted with n-hexane and tolu-
ene and the product was purified by column chromatography on
Al2O3/5%H2O with n-hexane as the mobile phase.
[(COD)(η6-fluorobenzene)Ru] (3): Reaction mixture: [(COD)(η6-
naphthalene)Ru] (2) (1300 mg, 3.84 mmol), fluorobenzene (10 mL,
106.6 mmol) in 20 mL of THF and 1 mL of acetonitrile. Yield
650 mg (2.12 mmol, 55%) of 3. MS (FDϩ): m/z ϭ 306 [Mϩ]. 1H
NMR (269.7 MHz, C6D6):
δ ϭ ϭ 5.5,
5.14 (dd,3J{HoHm}
3J{HoF} ϭ 2.7 Hz, 2 H, Ho); 4.74 (td, 3J{HH} ϭ 5, 4J{HmF} ϭ
2.7 Hz, 2 H, Hm); 4.20 (td, 3J{HpHm} ϭ 5, 3J{HpF} ϭ 3.8 Hz, 1 H,
Hp); 3.60 (m, 4 H, olefin. COD); 2.39 (m, 8 H, aliphat. COD) ppm.
13C{1H} NMR (100.4 MHz, C6D6): δ ϭ 138.0 (d, 1J{CF} ϭ
Ϫ271 Hz, ipso-C); 86.1 (s, Cp); 81.1 (d, 4J{CF} ϭ 6 Hz, Cm); 80.6 (d,
3J{CF} ϭ 22.4 Hz, Co); 61.6 (C olefin. COD); 33.0 (C aliphat. COD)
ppm. C14H17FRu (305.2): calcd. C 55.1, H 5.6; found C 54.6, H 6.3.
[(COD)(η6-1,3-difluorobenzene)Ru] (4): Reaction mixture:
2
Experimental Section
(1300 mg, 3.84 mmol), 1,3-difluorobenzene (10 mL, 101.4 mmol) in
20 mL of THF and 1 mL of acetonitrile. Yield 510 mg (1.57 mmol,
41%) of 4. 1H NMR (399.65 MHz, C6D6): δ ϭ 5.61 (s, 1 H, aromat.
H); 4.76 (m, 1 H, aromat. H); 4.48 (m, 2 H, aromat. H); 3.57 (m,
4 H, olefin. COD); 2.24 (m, 8 H, aliphat. COD) ppm. C14H16F2Ru
(233.2): calcd. C 52.01, H 4.99; found C 52.19, H 5.35.
General: All reactions were carried out under dry, oxygen-free ni-
trogen. Solvents were purified by conventional methods, distilled,
and stored under nitrogen. NMR spectra were recorded at close to
room temperature with Jeol JNM-PMX 60, FT-JNM-EX 270, and
FT-JNM-GX 270 spectrometers, with dimethylpolysiloxane and
the solvent signals as internal standards. Mass spectra were re-
corded with a Varian MAT 212 spectrometer. Microanalyses were
performed at the analytical department of the institute, on Carlo
Erba Elemental Analyzers Mod. 1106 and Mod. 1108, for crystal-
line products only. Column chromatography (15 ϫ 1 cm) was ac-
complished on neutral degassed alumina (Merck), deactivated with
5% degassed water. The starting materials [(COD)(η6-naph-
thalene)Ru] (2),[12] [(η6-bromobenzene)(COD)Ru] (13),[13] and [(η6-
2-bromotoluene)(COD)Ru] (14)[13] were prepared as reported in
the literature.
[(COD (η6-3-fluorotoluene))Ru] (5): Reaction mixture: 2 (1300 mg,
3.84 mmol), 3-fluorotoluene (10 mL, 90.5 mmol) in 30 mL of THF
and 1 mL of acetonitrile. Yield 930 mg (2.76 mmol, 72%) of 5. MS
(FDϩ): m/z ϭ 320 [Mϩ]. 1H NMR (399.65 MHz, C6D6): δ ϭ 5.12
3
3
(s, 1 H, H1); 5.00 (d, J{H2H3} ϭ 5 Hz, 1 H, H2); 4.96 (td, J{H2/
4H3} ϭ 5, 4J{H3F} ϭ 3 Hz, 1 H, H3); 4.00 (dd, 3J{H4H3} ϭ 5,
3J{H4F} ϭ 4.5 Hz, 1 H, H4); 3.38 (m, 4 H, olefin. COD); 2.28
(m, 8 H, aliphat. COD); 1.57 (s, 3 H, CH3) ppm. 13C{1H} NMR
(100.4 MHz, C6D6): δ ϭ 138.0 (d, J{CF} ϭ Ϫ271 Hz, C6); 98.0
1
(d, 3J{CF} ϭ 6 Hz, C4); 87.3 (C3); 80.6 (d, 3J{CF} ϭ 6 Hz, C2);
77.3 (d, 2J{CF} ϭ 22 Hz, C1/5); 76.5 (d, 2J{CF} ϭ 22 Hz), C1/5
;
Preparation of [(COD)(η6-haloarene)Ru] Complexes (General Pro-
cedure): [(COD)(η6-naphthalene)Ru] (2) and an excess of the
haloarene were dissolved in THF and acetonitrile. After the mix-
ture had been stirred at room temperature (room temp.) for 3 d, all
volatile components were removed in vacuo at 45 °C. Filtering of
the obtained oils through alumina/5%H2O and recrystallization (if
possible) yielded the products.
63.9, 63.4 (C olefin. COD); 34.5, 33.8 (C aliphat. COD); 17.9 (C-
methyl) ppm. C15H19FRu (319.2): calcd. C 56.4, H 6.0; found C
56.3, H 6.2.
Bromine/Lithium Exchange and Electrophilic Substitution Reactions
of [(η6-Bromoarene) (COD)Ru] Complexes (General Procedure):
The bromoarene complex was dissolved in THF and cooled to Ϫ80
°C, and a solution of n-butyllithium in hexane was added by syr-
inge. The reaction mixture was stirred for 10 min and a solution of
the electrophile in THF was added at the same temperature. The
mixture was then allowed to warm slowly to room temp. over 2 h. [(η6-3-Chlorotoluene)(COD)Ru] (6): Reaction mixture: 2 (1200 mg,
In the case of Li alkoxide intermediates, a small portion of de-
gassed water was added by syringe to produce the OH groups. The
mixture was stirred for a few minutes and the solvents were re-
moved in vacuo. The residue was extracted with n-hexane and tolu-
3.55 mmol), 3-chlorotoluene (10 mL, 84.6 mmol) in 10 mL of THF
and 1 mL of acetonitrile. Yield 540 mg (1.61 mmol, 45%) of 6. MS
1
(FDϩ): m/z ϭ 336 [Mϩ]. H NMR (399.65 MHz, C6D6): δ ϭ 5.36
3
3
(s, 1 H, H1); 5.31 (d, J{H4H3} ϭ 5 Hz), 1 H, H4; 4.96 (t, J{H2/
Eur. J. Inorg. Chem. 2003, 281Ϫ292
287

G. Bodes, F. W. Heinemann, G. Jobi, J. Klodwig, S. Neumann, U. Zenneck
4H3} ϭ 5 Hz, 1 H, H3); 4.03 (d, J{H2H3} ϭ 5 Hz, 1 H, H2); 3.44 [(η6-1-Bromo-4-iodobenzene)(COD)Ru] (11): Reaction mixture: 2
FULL PAPER
3
(m, 4 H, olefin. COD); 2.37 (m, 8 H, aliphat. COD); 1.67 (s, 3 H,
(1400 mg, 4.1 mmol), 1-bromo-4-iodobenzene (10 g, 35.3 mmol) in
CH3) ppm. 13C{1H} NMR (100.4 MHz, C6D6): δ ϭ 125.7, 101.4,
20 mL of THF and 1 mL of acetonitrile. Yield 420 mg (0.85 mmol,
100.4 (aromat. C), 88.7 (d, C-Cl), 84.7, 83.3 (aromat. C); 65.6, 64.8 21%) of 11. MS (FDϩ): m/z ϭ 494 [M]ϩ. H NMR (399.65 MHz,
1
(C olefin. COD); 34.2, 33.5 (C aliphat. COD); 17.9 (C-methyl) ppm.
C6D6): δ ϭ 5.22 (d, 3J ϭ 5 Hz, 2 H, aromat. H); 5,12 (d, 3J ϭ
5 Hz, 2 H, aromat. H); 3.39 (s, 4 H, olefin. COD); 2.29 (m, 8 H,
aliphat. COD) ppm. 13C{1H} NMR (100.4 MHz, C6D6): δ ϭ 97.0,
96.2, 92.8, 91.9, 88.7 (aromat. C); 70.3 (C olefin. COD); 34.7 (C
aliphat. COD) ppm. C14H16BrIRu (492.2): calcd. C 34.2, H 3.3;
found C 34.4, H 3.1.
[(COD)(η6-4,4Ј-difluoro-1,1Ј-biphenyl)Ru] (12): Reaction mixture: 2
(960 mg,
2.84 mmol),
4,4Ј-difluoro-1,1Ј-biphenyl
(2,03 g,
10,7 mmol) in 50 mL of THF and 1.5 mL of acetonitrile. Yield
1035 mg (2.59 mmol, 91%) of 12. MS (FDϩ): m/z ϭ 399 [Mϩ]. 1H
NMR (269.7 MHz, C6D6): δ ϭ 6.99 (m, 4 H, free aromat. H); 4.95
(dd, 2 H, coord. aromat. H, CHCF); 4.72 (dd, 2 H, coord. aromat.
H); 3.35 (s, 4 H, olefin. COD); 2.28 (m, 8 H, aliphat. COD) ppm.
[(COD)(η6-1,4-dichlorobenzene)Ru] (7): Reaction mixture:
2
(180 mg, 0.53 mmol), 1,4-dichlorobenzene (735 mg, 5 mmol) in
10 mL of THF and 1 mL of acetonitrile. Yield 20 mg (0.06 mmol,
10%) of 7. MS (EI, 70 eV): m/z ϭ 356 [Mϩ]. 1H NMR (269.6 MHz,
C6D6): δ ϭ 5.05 (s, 4 H, aromat. H); 3.50 (m, 4 H, olefin. COD);
2.30 (m, 8 H, aliphat. COD) ppm. C14H16Cl2Ru (356.2): calcd. C
47.2, H 4.52; found C 46.06, H 4.38.
[(COD)(diisopropyl-η6-phenylphosphane)Ru] (15): Reaction mix-
ture: [(η6-bromobenzene)(COD)Ru] (13) (150 mg, 0.41 mmol) in
25 mL of Et2O, n-butyllithium (0.24 mL, 0.6 mmol), and chlorodi-
isopropylphosphane (0.095 mL, 0.6 mmol). Yield 137 mg
(0.34 mmol, 83%) of 15. MS (EI, 70 eV): m/z ϭ 404 [Mϩ]. 1H NMR
[(η6-2-Bromo-1,4-xylene)(COD)Ru] (8): Reaction mixture:
2
(500 mg, 1.5 mmol), 2-bromo-1,4-xylene (5 g, 27 mmol) in 25 mL
of THF and 1 mL of acetonitrile. Yield 380 mg (0.96 mmol, 64%)
3
(269.6 MHz, C6D6): δ ϭ 5.45 (t, 1 H, Hp); 4.63 (ddo, J{HoHm} ϭ
6, 3J{HoP} ϭ 5 Hz, 2 H, H); 4.45 (t, 2 H, Hm); 3.67 (s, 4 H, olefin.
COD); 2.15Ϫ2.40 (m, 8 H, aliphat. COD), 1.81 (dh, 2J{HP} ϭ 1.5,
3J{HH} ϭ 10.7 Hz, 2 H, CH isoprop.); 1.17 (dd, 3J{HP} ϭ 9.2,
1
of 8. MS (FDϩ): m/z ϭ 394 [Mϩ]. H NMR (269.6 MHz, C6D6):
3
δ ϭ 5.36 (s, 1 H, aromat. H); 4.34 (d, J ϭ 8 Hz, 1 H, arom-H);
3
4.04 (d, J ϭ 8 Hz, 1 H, aromat. H); 3.35 (m, 2 H, olefin. COD);
3
3J{HH} ϭ 6.7 Hz, 6 H, CH3 isoprop.); 0.95 (dd, J{HP} ϭ 15.6,
3.03 (m, 2 H, olefin. COD); 2.2Ϫ2.4 (m, 8 H, aliphat. COD); 1.95,
1.60 (s, 3 H, CH3) ppm. 13C{1H} NMR (67.7 MHz, C6D6): δ ϭ
104.0, 102.9, 92.4, 90.2, 86.0, 83.6 (aromat. C); 68.5, 66.6 (C olefin.
COD); 35.0, 33.6 (C aliphat. COD); 19.1,17.8 (CH3) ppm.
3J{HH} ϭ 6.7 H, 6 H, CH3 isoprop.) ppm. 13C{1H} NMR
(100.4 MHz, C6D6): δ ϭ 98.1 (d, 1J{CP} ϭ 29.72 Hz, C-ipso); 89.4
2
3
(C4), 88.3 (d, J{CP} ϭ 17.4 Hz, C2/6); 84.4 (d, J{CP} ϭ 4.9 Hz,
C3/5); 62.5 (C olefin. COD); 33.9 (C aliphat. COD); 22.6 (d,
J{CP} ϭ 14.8 Hz, C isoprop.); 19.9 (d, J{CP} ϭ 16.6 Hz, C iso-
prop.); 19.4 (d, J{CP} ϭ 9 Hz, C isoprop.) ppm. 31P NMR
(109.6 MHz, C6D6): δ ϭ 4.75 (s) ppm.
[(COD)(η6-1,3-Dibromobenzene)Ru] (9): Reaction mixture:
2
(950 mg, 2.81 mmol), 1,3-dibromobenzene (10 mL, 82.8 mmol) in
50 mL of THF and 1 mL of acetonitrile. Yield 310 mg (0.7 mmol,
1
20%) of 9. MS (FDϩ): m/z ϭ 444 [Mϩ]. H NMR (399.65 MHz,
[(COD)(diisopropyl-η6-2-tolylphosphane)Ru] (16): Reaction mix-
ture: [(η6-2-bromotoluene)(COD)Ru] (14) (185 mg, 0.48 mmol) in
25 mL of Et2O, n-butyllithium (0.26 mL, 0.65 mmol), and chlorodi-
isopropylphosphane (0.10 mL, 0.65 mmol). Yield 174 mg
(0.42 mmol, 86%) of 16. MS (EI, 70 eV): m/z ϭ 417 [Mϩ]. 1H NMR
C6D6): δ ϭ 5.91 (s, 1 H, H1); 4.77 (t, 3J{H2/4H3} ϭ 6 Hz, 1 H, H3);
4.68 (d, 3J{H2/4H3} ϭ 6 Hz, 2 H, H2/4); 3.49 (m, 4 H, olefin. COD);
2.26 (m, 8H, aliphat. COD) ppm. 13C{1H} NMR (100.4 MHz,
C6D6): δ ϭ 93.0, 89.2, 87.5, 86.3 (aromat. C); 69.8 (C olefin. COD);
34.6, 33.8 (C aliphat. COD) ppm. C14H16Br2Ru (445.1): calcd. C
37.77, H 3.62; found C 38.37, H 3.71.
3
(269.6 MHz, C6D6): δ ϭ 5.51 (t, J{HpHm} ϭ {HpHmЈ} ϭ 6 Hz, 1
H, Hp/m); 5.11 (d, 3J{HmЈHp} ϭ 6 Hz, 1 H, HmЈ); 5.10 (dd,
3
3
3J{HoHm} ϭ 6, J{HoP} ϭ 5 Hz, 1 H, Ho); 3.82 (t, J{HmHp} ϭ
3J{HmHo} ϭ 6 Hz, 1 H, Hm/p); 3.43 (s, 4 H, H olefin. COD);
2.00Ϫ2.40 (m, 10 H, H aliphat. COD, H isoprop.); 1.75 (s, 3 H,
3
CH3); 1.57 (dd, J{HH} ϭ 10.7, 3J{HP} ϭ 18.8 Hz, 3 H, H iso-
3
3
prop. CH3); 1.13 (dd, J{HH} ϭ 10.7, J{HP} ϭ 14.8 Hz, 3 H, H
isoprop. CH3); 0.94 (dd, J{HH} ϭ 10.7, J{HP} ϭ 14.8 Hz, 3 H,
3
3
3
3
H isoprop. CH3); 0.86 (dd, J{HH} ϭ 10.7, J{HP} ϭ 10.3 Hz, 3
H, H isoprop. CH3) ppm. 13C{1H} NMR (67.7 MHz, C6D6): δ ϭ
98.9 (d, 1J{CP} ϭ 32.11 Hz, C-ipso); 96.5 (d, J{CP} ϭ 26.2 Hz,
aromat. C); 92.8 (d, J{CP} ϭ 2.78 Hz, aromat. C); 91.6 (d,
J{CP} ϭ 2.71 Hz, aromat. C); 87.3, 79.7 (aromat. C); 62.9, 61.7 (C
olefin. COD); 34.3; 33.5 (C aliphat. COD); 25.2 (d, J{CP} ϭ
17.9 Hz, C isoprop.); 22.3 (d, J{CP} ϭ 13.7 Hz, C isoprop.); 22.1
(d, J{CP} ϭ 20.6 Hz), C isoprop.; 20.2 (d, J{CP} ϭ 15.2 Hz, C
isoprop.); 19.8 (d, J{CP} ϭ 16.6 Hz, C isoprop.); 18.7 (d, 3J{CP} ϭ
5.6 Hz, CH3 tolyl.); 18.3 (d, J{CP} ϭ 22.1 Hz, C isoprop.) ppm.
31P NMR (109.6 MHz, C6D6): δ ϭ Ϫ6.8 (s).
[(η6-1-Bromo-4-fluorobenzene)(COD)Ru] (10): Reaction mixture: 2
(1729 mg, 5.12 mmol), 1-bromo-4-fluorobenzene (10 g, 57 mmol)
in 60 mL of THF and 1.5 mL of acetonitrile. Yield 512 mg
(1.33 mmol, 26%) of 10. MS (EI, 70 eV): m/z ϭ 384 [Mϩ]. 1H NMR
(269.6 MHz, C6D6): δ ϭ 5.02 (m, 2 H, aromat. H); 4.87 (m, 2 H,
aromat. H); 3.55 (m, 4 H, olefin. COD); 2.30 (m, 8 H, aliphat.
COD) ppm. 13C{1H} NMR (67.7 MHz, C6D6): δ ϭ 126.0, 88.7
(aromat. C), 86.0 (d, CF), 75.9, 75.7 (aromat. C); 67.8 (C olefin.
COD); 34.0 (C aliphat. COD) ppm. 13C{1H} NMR (67.8 MHz,
C6D6): δ ϭ 88.7 (aromat. C), 86.0 (d, CF), 75.9, 75.6 (aromat. C); [(COD)(di-tert-butyl-η6-phenylphosphane)Ru] (17): Reaction mix-
67.9 (C olefin. COD); 34.0 (C aliphat. COD) ppm. C14H16BrFRu ture: 13 (170 mg, 0.46 mmol) in 25 mL of Et2O, n-butyllithium
(384.2): calcd. C 43.76, H 4.19; found C 43.29, H 4.01.
(0.24 mL, 0.6 mmol), and di-tert-butylchlorophosphane (0.11 mL,
288
Eur. J. Inorg. Chem. 2003, 281Ϫ292

Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes
FULL PAPER
0.6 mmol). Yield 156 mg (0.36 mmol, 78%) of 16. MS (EI, 70 eV):
1.70 (s, 3 H, CH3); 1.07 (s, 9 H, CH3 tBu) ppm. 13C{1H} NMR
m/z ϭ 432 [Mϩ]. 1H NMR (269.6 MHz, C6D6): δ ϭ 5.55 (t, (67.7 MHz, C6D6): δ ϭ 208 (CO); 104.5, 97.7, 86.0, 85.4, 84.4, 81.9
3
3J{HpHm} ϭ 6 Hz, 1 H, Hp); 4.85 (dd, 3J{HoHm} ϭ 6, J{HoP} ϭ
(aromat. C); 64.6, 63.9 (C olefin. COD); 45.2 (Cquart tBu); 34.6,
5 Hz, 2 H, Ho); 4.40 (t, 2 H, Hm); 3.55 (s, 4 H, H olefin. COD); 33.6 (C aliphat. COD); 27.5 (CH3 tBu); 17.4 (CH3 tolyl) ppm.
3
2.10Ϫ2.40 (m, 8 H, H aliphat. COD); 1.25 (d, J{HP} ϭ 13.4 Hz, C20H28ORu (385.5): calcd. C 62.31, H 7.32; found C 62.93, H 7.48.
18 H, H-tBu) ppm. 13C{1H} NMR (67.7 MHz, C6D6): δ ϭ 100.2
[(COD)(4-tert-butylphenyl η6-phenyl ketone)Ru] (22): Reaction mix-
(d, J{CP} ϭ 13.8 Hz, C-ipso); 91.8 (d, J{CP} ϭ 21.3 Hz, C2/6);
87.7 (s, C4); 85.1 (d, 3J{CP} ϭ 3.9 Hz), C3/5; 62.8 (C olefin. COD);
34.0 (C aliphat. COD); 32.8 (d, J{CP} ϭ 22.8 Hz, C-tBu); 31.2 (d,
J{CP} ϭ 13.6 Hz, C-tBu) ppm. 31P NMR (109.6 MHz, C6D6): δ ϭ
33.7 (s) ppm. C22H35PRu (431.6): calcd. C 61.26, H 8.17; found C
61.01, H 8.37.
1
2
ture: 13 (264 mg, 0.72 mmol) in 20 mL of THF, n-butyllithium
(0.34 mL, 0.86 mmol), and 4-tert-butylbenzoyl chloride (0.17 mL,
0.86 mmol). Yield 202 mg (0.45 mmol, 67%) of 22. MS (EI, 70 eV):
m/z ϭ 448 [Mϩ]. 1H NMR (269.6 MHz, C6D6): δ ϭ 8.22 (d, J{H6/
9H7/8} ϭ 8.0 Hz, 2 H, H6/9); 7.33 (d, J{H6/9H7/8} ϭ 8.0 Hz, 2 H,
H7/8); 5.48 (d, J{HoHm} ϭ 6.2 Hz, 2 H, Ho); 5.38 (t, J{HpHm} ϭ
5.7 Hz, 1 H, Hp); 4.53 (t, 2 H, Hm); 3.55 (m, 4 H, H olefin. COD);
2.25 (m, 8 H, H aliphat. COD), 1.28 (s, 9 H, H tBu) ppm. 13C{1H}
NMR (67.70 MHz, C6D6): δ ϭ 194.8 (CO); 155.0, 136.7, 129.7;
125.4, 93.3, 88.3, 87.5, 84.6 (aromat. C); 64.9 (C olefin. COD); 34.9
(Cquart tBu); 33.8 (C aliphat. COD); 31.1 (C-tBu) ppm.
[(COD)(diphenyl-η6-2-tolylphosphane)Ru] (18): Reaction mixture:
14 (250 mg, 0.65 mmol) in 20 mL of THF, n-butyllithium (0.32 mL,
0.8 mmol), and chlorodiphenylphosphane (0.15 mL, 0.8 mmol).
Yield 230 mg (0.474 mmol, 73%) of 18. MS (EI, 70 eV): m/z ϭ 486
[Mϩ]. 1H NMR (269.6 MHz, C6D6): δ ϭ 7.7 (dt, 3J{HH} ϭ 12,
3J{HP} ϭ 5 Hz, 2 H, aromat. H); 7.45 (dt, 3J{HH} ϭ 12,
3J{HP} ϭ 13.7 Hz, 2 H, aromat. H); 7.17Ϫ7.0 (m, 6 H, aromat.
(؊)-[(COD)(camphanoyl η6-phenyl ketone)Ru] (23): Reaction mix-
ture: 13 (300 mg, 0.8 mmol) in 15 mL of THF, n-butyllithium
(0.3 mL, 0.75 mmol), and (1S)-(Ϫ)-camphanoyl chloride (177 mg,
0.8 mmol). Yield 160 mg (0.34 mmol, 43%) of 23. MS (FDϩ):
m/z ϭ 468 [Mϩ]. 1H NMR (269.6 MHz, C6D6): δ ϭ 6.0 (d, 3J{HH} ϭ
3
3
H). 5.47 (t, J{HpHm} ϭ J{HpHmЈ} ϭ 6 Hz, 1 H, Hp/m); 4.73 (dd,
3J{HoHm} ϭ 6, J{HoP} ϭ 5 Hz, 1 H, Ho); 4.65 (d, J{HmЈHp} ϭ
6 Hz, 1 H, HmЈ); 4.05 (t, 3J{HmHp} ϭ 3J{HmHo} ϭ 6 Hz, 1 H,
Hm/p); 3.43 (s, 4 H, H olefin. COD); 2.25Ϫ2.40 (m, 8 H, H aliphat.
COD); 1.63 (s, 3 H, CH3) ppm. 13C{1H} NMR (100.4 MHz, C6D6):
δ ϭ 137.5, 136.3 (d, 1J{CP} ϭ 13.2 Hz, aromat. C); 135.3 (d,
2J{CP} ϭ 20.7 Hz, aromat. C2/6); 133.6 (d, 2J{CP} ϭ 19.8 Hz,
aromat. C2Ј/6Ј); 128.83 (d, 3J{CP} ϭ 6.6 Hz, aromat. C3/5); 128.6
(d, 3J{CP} ϭ 6.6 Hz, aromat. C3Ј/5Ј); 128.81, 128.5 (aromat. C4),
99.7 (d, 1J{CP} ϭ 24.8 Hz, C1-ipso); 96.1 (d, 2J{CP} ϭ 18.2 Hz,
3
3
3
6 Hz, 1 H, Ho); 5.5 (m, 2 H, Ho/p); 4.55 (t, J{H H} ϭ 6 Hz, 1 H,
Hm); 3.58 (m, 4 H, H olefin. COD); 2.24 (m, 8 H, H aliphat. COD);
0.97, 0.88 (s, 3 H, CH3) ppm. 13C{1H} NMR (100.4 MHz, C6D6):
δ ϭ 194.3 (CO); 177.7, 129.3, 128.5, 125.6, 96.6 (aromat. ipso-C);
91.0, 90.9, 90.4, 87.5, 86.1 (aromat. C); 66.3, 65.5 (C olefin. COD);
34.2, 33.8 (C aliphat. COD); 16.9, 9.7 (CH3) ppm. C24H30O3Ru
(467.6): calcd. C 61.65, H 6.46; found C 59.44, H 6.66. [α]D
Ϫ312, [α]578 ϭ Ϫ152, [α]633 ϭ Ϫ92 (25 °C, toluene).
ϭ
2
aromat.C); 90.9 (d, J{CP} ϭ 3.3 Hz, aromat. C); 90.1, 85.9, 84.1
(aromat. C); 64.1, 62.2 (C olefin. COD); 34.2 (C aliphat. COD);
17.4 (d, 3J{CP} ϭ 19.7 Hz, CH3) ppm. 31P NMR (109.6 MHz,
C6D6): δ ϭ Ϫ17.6 (s) ppm.
[(COD){1-phenyl-2-(η6-2-tolyl)ethanol}Ru] (24a, b): Reaction mix-
ture: 14 (500 mg, 1.3 mmol) in 100 mL of THF, n-butyllithium
(0.6 mL, 1.5 mmol), and (R)-(ϩ)-styrene epoxide (0.18 mL,
1.5 mmol). Yield 169 mg (0.4 mmol, 31%) of 24a and 24b as a 1:1
mixture of diastereomers. MS (EI, 70 eV): m/z ϭ 422 [Mϩ]. 1H
NMR (269.6 MHz, C6D6): δ ϭ 7.16 (d, J ϭ 14.8 Hz, 2 H, aromat.
H); 7.14 (d, J ϭ 14.8 Hz, 2 H, aromat. H); 7.03Ϫ6.87 (m, 6 H,
aromat. H); 5.12 (t, 3J{HpHm} ϭ 3J{HpHmЈ} ϭ 8 Hz, 1 H, Hp); 5.00
(t, 3J{Hp2Hm2} ϭ 3J{Hp2HmЈ2} ϭ 8 Hz, 1 H, Hp2); 4.55 (d, J ϭ 8 Hz,
1 H, aromat. H); 4.5Ϫ4.38 (m, 2 H, aromat. H); 4.27 (d, 1 H,
aromat. H); 4.10 (d, 3J{HH} ϭ 3 Hz, 1 H, OH); 4.02 (m, 2 H, arom
[(COD)(η6-2-methylacetophenone)Ru] (19): MS (EI, 70 eV): m/z ϭ
343 [Mϩ]. 1H NMR (269.9 MHz, C6D6): δ ϭ 4.95 (t, 1 H, aromat.
H); 4.77 (d, 1 H, aromat. H); 4.51 (t, 1 H, aromat. H); 4.40 (d, all
3Jarom ϭ 6 Hz, 1 H, aromat. H); 3.45Ϫ3.35 (m, 2 H, H olefin.
COD); 3.30Ϫ3.20 (m, 2 H, H olefin. COD); 2.40Ϫ2.10 (m, 8 H, H
aliphat. COD); 2.25 (s, 3 H, CH3); 2.12 (s, 3 H, CH3) ppm. 13C{1H}
NMR (100.4 MHz, C6D6): δ ϭ 189.9 (CO); 101.6; 93.0, 91.4; 88.7,
87.8, 82.4 (aromat. C); 65.6; 63.9 (C olefin. COD); 34.5, 33.4 (C
aliphat. COD); 28.5, 19.6 (C-CH3) ppm. C17H22ORu, M ϭ 343.4.
3
H); 3.62 (d, J{HH} ϭ 3 Hz, 1 H, OH); 3.25Ϫ3.05, 3.00Ϫ2.90 [m,
4 H, H olefin. COD, COD(2)]; 2.45Ϫ1.85 [m, 20 H, H aliphat. COD,
COD(2), H aliphat. CH2 and CH2(2)]; 1.35 (s, 3 H, CH3); 1.34 [s, 3
H, CH3(2)] ppm. 13C{1H} NMR (67.7 MHz, C6D6): δ ϭ 144.8,
129.2, 128.6, 127.8, 127.4, 126.2, 126, 101.3, 101.1, 100.5, 97.4, 91.2,
90.4, 88.0, 87.5, 86.3, 86.1, 86.0, 84.5 (aromat.C); 73.2, 72.5 (C-alco-
hol); 62.9, 62.3, 61.3, 61.1 (C olefin. COD); 41.8, 41.0 (C aliphat.
CH2); 34.6; 34.5, 33.7, 33.6 (C aliphat. COD); 17.0,16.5 (CH3) ppm.
[(COD)(tert-butyl η6-phenyl ketone)Ru] (20): Reaction mixture: 13
(240 mg, 0.65 mmol) in 20 mL of THF, n-butyllithium (0.31 mL,
0.78 mmol), and pivalyl chloride (0.1 mL, 0.78 mmol). Yield
252 mg (0.68 mmol, 94%) of 20. MS (EI, 70 eV): m/z ϭ 372 [Mϩ].
1H NMR (399.65 MHz, C6D6): δ ϭ 5.17 (t, J{HpHm} ϭ 5.4 Hz, 1
H, Hp); 5.16 (d, J{HoHm} ϭ 6.3 Hz, 2 H, Ho); 4.16 (t, 2 H, Hm);
3.21 (m, 4 H, H olefin. COD); 1.92 (s, 8 H, H aliphat. COD), 1.06
(s, 9 H, H tBu) ppm. 13C{1H} NMR (100.40 MHz, C6D6): 203.6
(CO); 91.7, 87.8, 87.3, 84.4 (aromat.C); 65.2 (C olefin. COD); 44.1
(Cquart tBu); 34.1 (C aliphat. COD); 29.1 (C tBu) ppm. C19H26ORu
(371.5): calcd. C 61.43, H 7.05; found C 61.96, H 7.42.
[(COD)(dimethyl-η6-phenylmethanol)Ru] (25): Reaction mixture: 13
(220 mg, 0.59 mmol) in 20 mL of THF, n-butyllithium (0.35 mL,
0.88 mmol), and acetone (0.06 mL, 0.88 mmol). Yield 132 mg
(0.38 mmol, 65%) of 25. MS (EI, 70 eV): m/z ϭ 346 [Mϩ]. 1H NMR
(399.65 MHz, C6D6): δ ϭ 5.29 (t, J{HpHm} ϭ 5.4 Hz, 1 H, Hp);
4.60 (d, J{HoHm} ϭ 5.7 Hz, 2 H, Ho); 4.14 (t, 2 H, Hm); 3.17 (m,
4 H, H olefin. COD); 1.94 (m, 8 H, H aliphat. COD), 1.23 (s, 6 H,
CH3) ppm. 13C{1H} NMR (100.40 MHz, C6D6): δ ϭ 115.2, 86.1,
85.7, 84.8 (aromat. C); 70.8 (C alcohol.); 60.2 (C olefin. COD);
34.1 (C aliphat. COD); 31.3 (CH3) ppm.
[(COD)(tert-butyl η6-2-tolyl ketone)Ru] (21): Reaction mixture: 14
(207 mg, 0.54 mmol) in 20 mL of THF, n-butyllithium (0.25 mL,
0.6 mmol), and pivalyl chloride (0.075 mL, 0.6 mmol). Yield
191 mg (0.49 mmol, 91%) of 21. MS (EI, 70 eV): m/z ϭ 386 [Mϩ].
1H NMR (269.6 MHz, C6D6): δ ϭ 5.15 (t, 1 H, aromat. H); 4.65
(d, 1 H, aromat. H); 4.55 (t, 1 H, aromat. H); 4.40 (d, all J ϭ 6 Hz,
1 H, aromat. H); 3.65Ϫ3.50 (m, 2 H, H olefin. COD); 3.48Ϫ3.38
[(COD)(η6-phenylcyclohexanol)Ru] (26): Reaction mixture: 13
(m, 2 H, H olefin. COD); 2.40Ϫ2.10 (m, 8 H, H aliphat. COD); (350 mg, 0.91 mmol) in 20 mL of THF, n-butyllithium (0.44 mL,
Eur. J. Inorg. Chem. 2003, 281Ϫ292 289

G. Bodes, F. W. Heinemann, G. Jobi, J. Klodwig, S. Neumann, U. Zenneck
FULL PAPER
1.1 mmol), and cyclohexanone (0.11 mL, 1.1 mmol). Yield 242 mg [(COD)(3-hydroxypropyl η6-2-tolyl ketone)Ru] (31): Reaction mix-
(0.63 mmol, 69%) of 26. MS (EI, 70 eV): m/z ϭ 386 [Mϩ]. 1H NMR ture: 14 (180 mg, 0.47 mmol) in 20 mL of THF, n-butyllithium
(399.65 MHz, C6D6): δ ϭ 5.32 (t, J{HpHm} ϭ 5.5 Hz, 1 H, Hp); (0.3 mL, 0.48 mmol), and γ-butyrolactone (0.036 mL, 0.47 mmol).
4.63 (d,, J{HoHm} ϭ 6.0 Hz 2 H, Ho); 4.14 (t, 2 H, Hm); 3.18 (m,
4 H, H olefin. COD); 1.95 (m, 8 H, H aliphat. COD), 1.68 (m, 4
H, H aliphat. cyclohexane), 1.28 (m, 6H, H aliphat. cyclohexane)
Yield 80 mg (0.21 mmol, 44%) of 31. MS (FDϩ): m/z ϭ 388 [Mϩ].
3
1H NMR (399.65 MHz, C6D6): δ ϭ 5.36 (t, J{HH}ϭ 8 Hz, 1 H,
aromat. H); 4.82 (d,3J{HH} ϭ 8 Hz, 1 H, aromat. H); 4.43 (t,
3
ppm. 13C{1H} NMR (100.40 MHz, C6D6): δ ϭ 116.2, 86.2, 85.8, 3J{HH} ϭ 8 Hz, 1 H, aromat. H); 4.31 (t, J{HH} ϭ 8 Hz, 1 H,
85.1 (aromat.C); 70.1 (C alcohol.); 60.1 (C olefin. COD); 39.2 (C
aliphat. cyclohexane); 34.3 (C aliphat. COD); 26.1 (C aliphat.
cyclohexane); 22.8 (C aliphat. cyclohexane) ppm.
aromat. H); 3.42 (m, 2 H, CH2OH); 3.37 (m, 2 H, H olefin. COD.);
3.20 (m, 2 H, H olefin.COD); 2.72 (m, 1 H, CH2CO); 2.63 (m, 1
H, CH2CO); 2.19 (m, 8 H, H aliphat. COD); 2.02 (s, 3 H, CH3);
1.86 (quint, 2 H, CH2) ppm. 13C{1H} NMR (100.40 MHz, C6D6):
δ ϭ 202.3 (CO); 101.3, 93.2, 91.6, 88.6, 87.6, 82.3 (aromat. C); 65.7,
64.0 (C olefin. COD); 62.17 (CH2OH); 37.1 (CH2 CO); 34.4, 33.6
(C aliphat. COD); 27.8 (CH2); 19.6 (CH3) ppm.
[(COD)(3-hydroxypropyl η6-phenyl ketone)Ru] (27): Reaction mix-
ture: 13 (380 mg, 1.03 mmol) in 30 mL of THF, n-butyllithium
(0.44 mL, 1.1 mmol), and γ-butyrolactone (88.7 mg, 1.03 mmol).
Yield 80 mg (0.21 mmol, 21%) of 27 and 150 mg (0.23 mmol, 45%)
of 28. MS (FDϩ): m/z ϭ 374 [Mϩ]. 1H NMR (399.65 MHz, C6D6):
[(COD){(6-methoxy-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-5-
yl)(η6-phenyl)methanol}Ru] (32a, 32b): Reaction mixture: 13
(455 mg, 1.24 mmol) in 15 mL of THF, n-butyllithium (0.75 mL,
1.2 mmol), and 1,2-O-isopropylidene-3-O-methyl-α--xylopentodi-
aldofuranose-(1,4) (250 mg, 1.24 mmol). Yield 290 mg (0.59 mmol,
48%) of 32a, 32b. MS (FDϩ): m/z ϭ 490 [Mϩ]. 1H NMR
3
3
δ ϭ 5.31 (d, J{HH}ϭ 6 Hz, 2 H, Ho); 5.24 (t, J{HH} ϭ 6 Hz; 1
H, Hp); 4.52 (t, 3J{HH} ϭ 6 Hz, 1 H, Hm); 3.45 (m, 2 H, CH2OH);
3.40 (m, 4 H, H olefin. COD); 2.59 (t, 2 H, CH2CO); 2.10 (m, 8
H, H aliphat. COD); 1.88 (quint, 2 H, CH2CH2CH2) ppm.
13C{1H} NMR (100.40 MHz, C6D6): δ ϭ 199.0 (CO); 91.3, 88.8,
86.8, 82.9 (aromat. C.); 64.4 (C olefin. COD); 62.1 (COH); 34.5
(CCO); 33.9 (C aliphat. COD); 27.7 (CH2) ppm.
3
(399.65 MHz, C6D6): δ ϭ 5.91 (d, J{HH} ϭ 4 Hz, 1 H, aromat.
3
3
H); 5.84 (d, J{HH} ϭ 4 Hz, 1 H, aromat. H); 5.51 (d, J{HH}ϭ
3
Data for 1,1-Bis[(COD)(η6-phenyl)Ru]-1,4-butanediol (28): MS
(FDϩ): m/z ϭ 662 [Mϩ]. 1H NMR (399.65 MHz, C6D6): δ ϭ 5.52
5 Hz, 2 H, aromat. H); 5.36 (t, J{HH} ϭ 5 Hz, 1 H, aromat. H);
5.19 (t, 3J{HH} ϭ 5 Hz, 1 H, aromat. H); 4.87 (t, 3J{HH} ϭ 5 Hz,
3
3
1 H, aromat. H); 4.84 (t, J{HH}ϭ 5 Hz, 1 H, aromat. H); 4.79 (t,
(t, J ϭ 6 Hz, 2 H, aromat. H); 5.21 (d, 2 H, aromat. H); 5.03 (d,
3J{HH} ϭ 5 Hz, 1 H, aromat. H); 4.70 (d, J{HH} ϭ 5 Hz, 2 H,
3
3
2 H, aromat. H); 4.39 (tt, all J ϭ 6 Hz, 4 H, aromat. H); 3.4 (m,
aromat. H); 4.54 (d, 3J{HH} ϭ 5 Hz, 1 H, aromat. H); 4.47 (td,
3J{HH} ϭ 4 Hz, 2 H, aromat. H); 4.43 (t, 3J{HH}ϭ 5 Hz, 1 H,
aromat. H); 4.34 (d, 3J{HH} ϭ 4 Hz, 1 H, aromat. H); 4.26 (d,
4 H, H2/4; 8 H, H olefin. COD); 2.20 (m, 16 H, H aliphat. COD);
1.79 (m, 2 H, H3) ppm. 13C{1H} NMR (100.40 MHz, C6D6): δ ϭ
114.5, 86.5, 85.8, 85.7, 84.8 (aromat. C); 75.2 (C1); 63.2 (C4); 61.3,
61.1 (C olefin. COD.); 40.5 (C2); 34.3, 34.2 (C aliphat. COD); 27.6
(C3) ppm.
3J{HH} ϭ 4 Hz, 1 H, aromat. H); 4.10 (t, J{HH} ϭ 5 Hz, 1 H,
3
aromat. H); 4.05 (d, 3J{HH} ϭ 3 Hz, 2 H, aromat. H); 3.46 (d,
3J{HH} ϭ 3 Hz, 2 H, aromat. H); 3.58Ϫ3.33 (m, 4 H, H olefin.
COD.); 3.20 (s, 3 H, H OMe); 3.01 (s, 1 H, OH); 2.83 (s, 3 H, H
OMe); 2.81 (d, J{HH} ϭ 7 Hz, 1 H, HOH); 2.38Ϫ2.05 (m, 8 H,
H aliphat. COD); 1.40 (d, 3 H , H isoprop. endo); 1.11 (d, 3 H, H
isoprop. exo) ppm. 13C{1H} NMR (100.40 MHz, C6D6): δ ϭ 112.0,
111.8 (aromat. C); 110.0, 106.0 (isoprop. C); 106.0 (d, C-OH); 88.7,
87.7, 87.6, 87.4, 87.0, 86.6, 86.5 (aromat. C); 85.4,84.9, 84.8
(Cfuranose); 84.5 (aromat. C); 84.2 (Cfuranose); 83.9, 83.7 (aromat. C);
82.4, 82.0, 71.2, 69.5 (Cfuranose); 61.4, 60.6 (C olefin. COD.); 58.2,
57.0 (COMe); 34.8, 34.3 (C aliphat. COD.); 27.4, 27.3, 26.7. 26.6
(CH3 isoprop.) ppm.
[(COD)(η6-4-fluorophenyl 3-hydroxypropyl ketone)Ru] (29): Reac-
tion mixture: 10 (353 mg, 0.92 mmol) in 45 mL of THF, n-butylli-
thium (0.58 mL, 0.92 mmol), and γ-butyrolactone (79 mg,
0.92 mmol). Yield 140 mg (0.36 mmol, 40%) of 29 and 50 mg
(0.07 mmol, 16%) of 30. MS (FDϩ): m/z ϭ 392 [Mϩ]. 1H NMR
(269.71 MHz, C6D6): δ ϭ 5.39 (dd, 2 H, aromat. H); 5.02 (dd, 2
H, aromat. H); 3.54 (m, 4 H, H olefin. COD.); 3.54 (t, 2 H,
CH2OH); 2.58 (t, 2 H, CH2CO); 2.25 (m, 8 H, H aliphat. COD);
1.86 (m, 2 H, CH2CH2CH2) ppm. 13C{1H} NMR (67.8 MHz,
C6D6): δ ϭ 197.9 (CO); 139.8, 135.8, 92.1 (aromat. C.); 82.8 (d,
CF); 77.3, 77.0 (aromat. C) 66.8 (C olefin. COD); 61.8 (COH); 34.8
(CCO); 33.8 (C aliphat. COD); 27.3 (CH2) ppm.
Data for [1,1-bis{[COD(η6-4-fluoropheny)Ru}-1,4-butanediol] (30):
[(COD)(menthyl η6-1,4-xylene-2-carboxylate)Ru] (33a and 33b): Re-
MS (FDϩ): m/z ϭ 697 [Mϩ], 488 [M Ϫ Ru(COD)]ϩ. 1H NMR action mixture: 8 (380 mg, 0.96 mmol) in 10 mL of THF, n-butylli-
(269.71 MHz, C6D6): δ ϭ 5.02 (m, 2 H, aromat.H); 4.95 (m; 2 H, thium (0.5 mL, 1.25 mmol), and (Ϫ)-menthyl chloroformate
aromat. H); 4.90 (m; 2 H, aromat. H); 4.74 (m, 2 H, aromat. H); (0.3 mL, 1.3 mmol). Yield 200 mg (0.4 mmol, 42%) of 33a and 33b.
3.66 (m, 8 H, H olefin. COD.); 3.23 (q, 2 H, H3); 2.32 (m, 16 H, MS (FDϩ): m/z: 497 [Mϩ]. 1H NMR (269.6 MHz, C6D6): δ ϭ 5.52
H aliphat. COD.); 2.11 (t, 2 H, H3); 1.68 (m, 2 H, H2) ppm. (s, 1 H, aromat. H); 5.13 (m, 1 H, ester H); 4.88 (dt, 1 H, aromat.
13C{1H} NMR (67.8 MHz, C6D6): δ ϭ 143.6, 139.6, 116.0 (aromat.
H); 4.75 (dt, 1 H, aromat. H); 4.32 (t, 1 H, aromat. H); 4.04 (t, 1
C), 80.8, 79.8 (d, C-F), 74.7, 74.4, 73.1 (aromat. C); 72.7 (C1); 63.9, H, aromat. H); 3.48 (m, 2 H, H olefin. COD); 3.14 (m, 2 H, H
63.7 (C olefin. COD.); 62.8 (C4); 40.1 (C2); 34.2, 33.6 (C aliphat.
COD); 26.6 (C3) ppm.
olefin. COD); 2.2Ϫ2.4 (m, 8 H, H aliphat. COD); 0.7Ϫ1.7 (19 H,
menthyl) ppm.
290
Eur. J. Inorg. Chem. 2003, 281Ϫ292

Introduction of Functional Side Chains into (Arene)ruthenium(0) Complexes
FULL PAPER
[(COD)(o-hydroxyphenyl η6-2-tolyl ketone)Ru] (34): Reaction mix-
ture: 14 (300 mg, 0.79 mmol) in 30 mL of THF, n-butyllithium COD); 1.68 (s, 3 H, CH3) ppm. 13C{1H} NMR (100.40 MHz,
(0.32 mL, 0.79 mmol), and o-acetylsalicoyl chloride (156 mg, C6D6): δ ϭ 193.8 (CO); 142. 3, 141.4, 138.1, 136.7, 136.6, 135.7,
H, H3); 3.59 (m, 4 H, H olefin. COD); 2.25 (m, 8 H, H aliphat.
0.79 mmol). Yield 200 mg (0.47 mmol, 60%) of 34. MS (FDϩ): 130.9, 130.7, 129.5, 129.4, 129.1, 128.7, 128.7, 125.9 (phenyl. C,
1
m/z ϭ 422 [Mϩ]. H NMR (399.65 MHz, [D8]THF): δ ϭ 12.62 (s, olefin. C); 102.2, 101.9, 99.4, 88.8, 86.2, 83.4 (aromat. C); 70.2, 68.4
1 H, phenol. H.); 8.50 (d, 3J{H5H6} ϭ 8 Hz, 1 H, H5); 7.08 (t,
3J{H5/8H6/7} ϭ 8 Hz, 1 H, H6/7); 7.01 (d, 3J{H7H8}ϭ 8 Hz, 1 H,
(C olefin. COD.); 34.5, 33.8 (C aliphat. COD); 18.4 (CH3) ppm.
H8); 6.56 (t, J{H5/8H6/7}ϭ 8 Hz, 1 H, H6/7); 5.24 (t, J{H2H1/3}ϭ
5.5 Hz), 1 H, H2; 4.78 (d, 3J{H4H3}ϭ 5.5 Hz, 1 H, H4); 4.60 (d,
3J{H1H2}ϭ 5.5 Hz, 1 H, H1); 4.31 (t, 3J{H3H2/4}ϭ 5.5 Hz, 1 H,
H3); 3.48 (m, 4 H, H olefin. COD); 2.38 (m, 8 H, H aliphat. COD);
1.63 (s, 3 H, CH3) ppm. 13C{1H} NMR (100.40 MHz, [D8]THF):
δ ϭ 201.8 (CO); 163.7 (C-OH); 136.8, 134.0, 120.6, 118.8, 118.4
(aromat. C); 99.4 (ipso-C); 96.0 (π-tolyl-C); 89.4, 88.6, 85.0, 83.6
(arom-C), 65.3 (C olefin. COD); 64.3;34.1 (C aliphat. COD); 33.5;
17.2 (CH3) ppm.
3
3
Crystal Structure Determinations: Suitable crystals of 10, 11, 28,
and 30 were taken directly from the mother liquor. Data were col-
lected with a Siemens P4 diffractometer for 10, 11, and 28 and with
a Nonius KappaCCD for 30, with use of Mo-Kα radiation (λ ϭ
˚
0.71073 A) and a graphite monochromator. The crystal structures
were solved by direct methods and refined by use of the SHELXTL
5.03[18] programs for 10 and 28, and SHELXTL NT 5.10[19] for 11
and 30. Non-hydrogen atoms were refined anisotropically. Hydro-
gen atoms are either geometrically positioned (10 and 28) or their
positions were derived from a difference Fourier map and refined
with a fixed common isotropic displacement parameter (11 and 30).
Other experimental details are given in Tables 2 and 3. Crystallo-
graphic data for the structures reported in this paper have been
deposited with the Cambridge Crystallographic Data Center as
supplementary publication nos. CCDC-186921 (10), -186922 (11), -
186923 (28), and -186924 (30). Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road, Cam-
bridge CB21EZ, UK [Fax: (internat.) ϩ 44-1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk or www: http://www.ccdc.ca.ac.uk].
Table 2. Crystallographic data for 10 and 11
[(COD)(η6-1-{2-fluoro-4-tolyl} o-hydroxyphenyl ketone)Ru] (35):
Reaction mixture: 5 (550 mg, 1.7 mmol) in 30 mL of THF, n-butyl-
lithium (0.68 mL, 1.7 mmol), and o-acetylsalicoyl chloride (300 mg,
1.5 mmol). Yield 300 mg (0.68 mmol, 40%) of 35. MS (FDϩ):
10
11
Empirical formula
Formula mass
Color, shape
Size [mm]
C14H16BrFRu
384.25
yellow, plate
0.90ϫ0.52ϫ0.10 0.70ϫ0.35ϫ0.20
monoclinic
P21/c
13.003(1)
8.316(1)
12.586(1)
110.04(1)
1278.6(2)
4
1.996
4.337
294(2)
ψ-scan
0.017/0.059
752
C14H16BrIRu
492.15
yellow, needle
1
m/z ϭ 440 [Mϩ]. H NMR (300.13 MHz, C6D6):δ ϭ 12.46 (s, 1 H,
phenol. H); 8.81 (m, 1 H, aromat. H); 7.06 (m, 2 H, aromat. H);
3
Crystal system
Space group
monoclinic
P21/n
6.66 (m, 1 H, aromat. H); 4.50 (dd, J{HH} ϭ 6, J{HF} ϭ 3 Hz,
1 H, aromat. H); 4.41 (dd, 3J{HH} ϭ 6, J{HF} ϭ 3 Hz, 1 H,
˚
a [A]
14.702(2)
6.369(2)
16.062(3)
113.14(1)
1383.0(5)
4
2.364
6.230
200(2)
ψ-scan
0.049/0.120
928
3
aromat. H); 4.27 (d, J{HF} ϭ 4 Hz, 1 H, aromat. H); 3.54 (m, 4
˚
b [A]
H, H, olefin. COD); 2.18 (m, 8 H, H aliphat. COD); 1.72 (s, 3 H,
˚
c [A]
CH3) ppm. 13C{1H} NMR (75.47 MHz, C6D6): δ ϭ 197.2 (CO);
β [°]
163.4 (C-OH); 137.4, 134.2 (aromat. C); 127.3 (1J{CF}
ϭ
3
˚
Volume [A ]
Z
Ϫ271 Hz, π-aromat. C); 120.8, 118.8,118.6 (aromat. C); 99.4
(3J{CF} ϭ 6 Hz, π-aromat. C); 89.2 (d, 2J{CF} ϭ 17 Hz, π-aromat.
C), 79.7 (3J{CF} ϭ 2 Hz, π-aromat. C); 85.0 (π-aromat. C); 75.2
ρcalcd. [g·cmϪ1
]
µ [mmϪ1
T [K]
]
2
(d, π-aromat. C, J{CF} ϭ 22 Hz); 67.6 (C olefin. COD); 33.5 (C
Absorption correction
Tmin/Tmax
F(000)
aliphat. COD); 18.3 (CH3) ppm.
Reflections measured
Independent reflections
Observed reflections
[Fo Ն 4σ(F)]
No. refined parameters
Goodness-of-fit on F2
R1 [Fo Ն 4σ(F)]
3606
2795
2063
4362
3335
2630
202
154
1.077
0.0585
0.1766
3.007/Ϫ3.076
1.029
0.0550
0.1470
wR2 (all data)
Max/min resid. density [e·AϪ3] 1.034/Ϫ1.487
˚
[(η6-1-{2-chloro-4-tolyl}-2,3-diphenylprop-2-en-1-one)(COD)Ru]
(36): Reaction mixture: 6 (275 mg, 0.82 mmol) in 20 mL of THF, n-
butyllithium (0.36 mL, 0.9 mmol), and α-phenylcinnamoyl chloride
(218 mg, 0.9 mmol). Yield 180 mg (0.33 mmol, 41%) of 36. MS
(FDϩ): m/z ϭ 542 [Mϩ]. 1H NMR (399.65 MHz, C6D6): δ ϭ 7.93
Acknowledgments
3
(s, 1 H, olefin. H); 7.1 (m, 10 H, phenyl. H); 5.25 (d, J{H2H3} ϭ
We thank the Deutsche Forschungsgemeinschaft (SFB, 583) and
3
5.5 Hz, 1 H, H2); 5.03 (s, 1 H, H1); 4.10 (d, J{H2H3}ϭ 5.5 Hz, 1 the Fonds der Chemischen Industrie for financial support.
Eur. J. Inorg. Chem. 2003, 281Ϫ292
291

G. Bodes, F. W. Heinemann, G. Jobi, J. Klodwig, S. Neumann, U. Zenneck
FULL PAPER
ishi Petrochemical Co., Ltd.), Eur. Pat. Appl. EP 537,625
(Chem. Abstr. 1993, 119, 94953p); J. Ookago, S. Ichikawa, T.
Yoneyama, N. Sumya (Mitsubishi Petrochemical Co.), Jpn. Ko-
kai Tokyo Koho JP 05,186,377 (93,186,377) (Chem. Abstr.
Table 3. Crystallographic data for 28 and 30
28
30
1993, 119, 250721u); J. Ookago, N. Sumya, S. Ichikawa (Mitsu-
[a]
Empirical formula
Formula mass
Color, shape
Size [mm]
C32H42O2Ru2 C39H48F2O2Ru2
660.80
788.91[a]
Yellow, block Yellow, block
bishi Petrochemical Co.), Jpn. Kokai Tokyo Koho JP
05,310,631 (93,310,631) (Chem. Abstr. 1994, 120, 269654s).
P. Pertici, V. Ballantini, P. Salvadori, M. A. Bennett, Organo-
metallics 1995, 14, 2565.
[6]
[7]
0.75ϫ0.38ϫ0.30 0.28ϫ0.24ϫ0.15
Crystal system
Space group
triclinic
P1
monoclinic
C2/c
J. Takehara, S. Hashiguchi, A. Fujii, S. Inoue, T. Ikariya, R.
Noyori, Chem. Commun. 1996, 233.
A. Fujii, S. Hasahiguchi, N. Uematsu, T. Ikariya, R. Noyori,
J. Am. Chem. Soc. 1996, 118, 2521.
N. Uematsu, A. Fujii, S. Hashiguchi, T. Ikariya, R. Noyori, J.
Am. Chem. Soc. 1996, 118, 4916.
E. L. Muetterties, J. R. Bleeke, A. C. Sievert, J. Organomet.
Chem. 1979, 178, 197; P.M. Maitlis, Chem. Soc. Rev. 1981,
10, 1.
P. Pertici, G. Vitulli, S. Bertozzi, R. Lazzaroni, Inorg. Chim.
Acta 1988, 149, 235.
P. Pertici, G. Vitulli, R. Lazzaroni, P. Salvadori, P. L. Barili, J.
Chem. Soc., Dalton Trans. 1982, 1019; G. Vitulli, P. Pertici, P.
Salvadori, J. Chem. Soc., Dalton Trans. 1984, 2255; P. Pertici,
E. Pitzalis, F. Marchetti, C. Rosini, P. Salvadori, M. A. Ben-
nett, J.Organomet. Chem. 1994, 466, 221.
¯
˚
[8]
a [A]
8.725(4)
14.455(5)
23.190(9)
107.14(2)
90.76(4)
106.38(4)
2667(2)
4
36.1071(6)
8.9293(2)
21.7669(4)
90.0
112.294(1)
90.0
6493.3(2)
8
1.614
˚
b [A]
˚
[9]
c [A]
α [°]
β [°]
γ [°]
[10]
3
˚
Volume [A ]
Z
[11]
[12]
ρcalcd. [g·cmϪ1
]
1.646
µ [mmϪ1
T [K]
]
1.161
200(2)
0.977
100(2)
Absorption correction
Tmin/Tmax
F(000)
Reflections measured
Independent reflections
Observed reflections
[Fo Ն 4σ(F)]
ψ-scan
0.501/0.712
1352
multi-scan
0.701/0.769
3232
[13]
13619
33917
F. Heinemann, J. Klodwig, F. Knoch, M. Wündisch, U. Zen-
neck, Chem. Ber./Recueil 1997, 130, 123.
11365
8342
9246
6534
[14]
[15]
H. Schmidt, M. L. Ziegler, Chem. Ber. 1976, 109, 132.
Some examples: M. D. Rausch, D. J. Ciappenelli, J. Organomet.
Chem. 1967, 10, 127; C. Elschenbroich, J. Organomet. Chem.
1968, 14, 157; M. F. Semmelhack, J. Bisaha, M. Czarny, J. Am.
Chem. Soc. 1979, 101, 168; M. Uemura, K. Isobe, Y. Hayashi,
Chem. Lett. 1985, 91; F. Rose-Munch, E. Rose, Curr. Org.
Chem. 1999, 3, 445.
No. refined parameters
Goodness-of-fit at F2
R1 [Fo Ն 4σ(F)]
wR2 (all data)
663
544
1.011
0.0346
0.0728
0.604/Ϫ0.590
1.093
0.0636
0.1723
Max/min resid. density [e·AϪ3] 2.608/Ϫ1.175
˚
[16]
[17]
G. Marconi, H. Baier, F. W. Heinemann, P. Pinto, H. Pritzkow,
U. Zenneck, in preparation.
[a]
Includes one molecule of solvent (toluene).
Some examples: R. J. Card, W. S. Trahanovsky, J. Org. Chem.
1980, 45, 2560; M. F. Semmelhack, G. R. Clark, J. L. Garcia,
J. J. Harrison, Y.Thebtaranonth, W. Wulff, A. Yamashita, Tet-
rahedron 1981, 37, 3957; C. Bohm, K. Muniz, C. Ganter, New
J. Chem. 1998, 1371; S. Pache, C. Botuha, R. Franz, J. Einhorn,
E. P. Kündig, Helv. Chim. Acta 2000, 83, 2436.
SHELXTL 5.03, Siemens Analytical X-ray Instrument, Madi-
son, WI, U.S.A., 1995.
[1]
G. Bodes, F. W. Heinemann, G. Marconi, S. Neumann, U. Zen-
neck, J. Organomet. Chem. 2002, 641, 90.
P. Pertici, G. Vitulli, C. Bigelli, R. Lazzaroni, J. Organomet.
Chem. 1984, 275, 113.
[2]
[3]
[4]
[5]
[18]
[19]
M.A. Bennett, H. Neumann, M. Thomas, X. Wang, G. Vitulli,
P. Pertici, P. Salvadori, Organometallics 1991, 10, 3237.
P. Pertici, G. Uccello Barretta, F. Burzagli, P. Salvadori, M. A.
Bennett, J. Organomet. Chem. 1991, 413, 303.
SHELXTL NT 5.10, Bruker AXS, Madison, WI, U.S.A., 1998.
Received June 6, 2002
Y. Ohgomori, S. Ichikawa, T. Yoneyama, N. Sumitani (Mitsub-
[I02300]
292
Eur. J. Inorg. Chem. 2003, 281Ϫ292