Chiral arene ruthenium complexes. Part 3. [Ruthenium(η6-arene)(η4-1,5-cyclooctadiene)] complexes with N or O donor functions in the arene side chain

Journal of Organometallic Chemistry 641 (2002) 90–101

www.elsevier.com/locate/jorganchem

Chiral arene ruthenium complexes Part 3.^ꢀ

[Ruthenium(h⁶-arene)(h⁴-1,5-cyclooctadiene)] complexes with N or

O donor functions in the arene side chain

Gregor Bodes, Frank W. Heinemann, Guido Marconi, Stefan Neumann,

Ulrich Zenneck *

Institut fu¨r Anorganische Chemie, Uni6ersita¨t Erlangen-Nu¨rnberg, Egerlandstraße 1, D-91058 Erlangen, Germany

Received 11 June 2001; accepted 14 August 2001

Abstract

Arene ruthenium(0) complexes with carbonyl side chain functionalities like [Ru(h⁶-C₆H₅COR)(h⁴-COD)] or [Ru(h⁶-o-

C₆H₄{R¹}COR)(h⁴-COD)] (COD=1,5-cyclooctadiene; R=H, CH₃; R¹=H, CH₃, OCH₃) are easily accessible by replacing the

naphthalene ligand of [Ru(h⁶-naphthalene)(h⁴-COD)] (1) through an arene exchange reaction. These carbonyl species are

susceptible to standard organic reactions of the carbonyl function, thus allowing the introduction of dangling side chains bearing

highly polar functions like hydroxyl or amino groups. Aldol reaction of [Ru(o-C₆H₄{CH₃}COCH₃)(COD)] (3) with (−)-men-

thylchloroformate in the presence of LDA (LDA=lithium diisopropylamide) leads to a diastereomeric mixture of [Ru(menthyl-

{3-oxo-3-h⁶-o-tolyl}propionate)(COD)] (10). However, treatment of 3 with LDA and o-tolylaldehyde or benzaldehyde affords the

unexpected products [Ru(1-h⁶-o-tolyl-3-o-tolylpropan-1-one)(COD)] (11) and [Ru(1-h⁶-o-tolyl-1-phenylpropan-1-one)(COD)]

(12). A diastereoselective addition (88% de) of deprotonated menthylacetate to [Ru(o-tolylaldehyde)(COD)] (4) results in the

formation of [Ru(menthyl 3-h⁶-o-tolyl-3-hydroxypropionate)(COD)] (13). Racemic planar-chiral aldehyde complexes 2 and 4 react

with amines giving the imination products in good yield. In case of reaction between 2 and (R)-N-amino-2-(methoxymethyl)-

pyrrolidine (RAMP), diastereomeric [Ru(N-[[h⁶-(2-methylphenyl]methylene]-(R)-2-(methoxymethyl)-1-pyrrolidinamine)(COD)]

(17) is formed. The diastereomers (R,R)-17 and (S,R)-17 have been separated by fractional crystallisation. Asymmetric arene

ruthenium complexes with a deﬁned planar-chiral conﬁguration are thus accessible. Reduction of [Ru(3-h⁶-phenyl-(R)-methylbu-

tyrate)(COD)] (7) with LiAlH₄yields the chiral g-alcohol [Ru(3-h⁶-phenyl-(R)-1-butanol)(COD)] (18). A Wittig oleﬁnation

converts the aldehyde complex 4 into a mixture of E- and Z-isomeric [Ru(1-h⁶-o-tolyl-2-phenylethylene)(COD)] 21a and 21b,

Keywords: Aldol reaction; Arene complexes; Chirality; Lithiation; Ruthenium; Wittig oleﬁnation

1. Introduction

groups, which are transferred into chiral alcohols or

amines [6]. Enantiomerically pure 1,2-diamines or b-

amino-alcohols are the co-ligands of choice.

Chiral Ru(h⁶-arene) complexes are accessible by dif-

ferent routes. This includes the redox states 0 [2] and

+2 [3–5] of the metal. An effective application of

Ru^II(arene) complexes with chiral co-ligands has been

found recently. They are excellent enantioselective hy-

drogen-transfer catalysts for organic carbonyl and imin

To the best of our knowledge, activity and selectivity

of the arene ruthenium catalysts are mainly studied as a

function of the co-ligands, rather than the Ru(h⁶-arene)

fragment itself. This led us to the approach to study

new synthetic strategies for the preparation of com-

plexes in which the chirality depends on the arene

ligand. We are mainly interested in three aspects: intro-

duction of a functionalised arene ligand; further modiﬁ-

cations of the side chain to introduce N or O donor

groups and chiral information; and ﬁnally the isolation

of optically pure complexes.

^ꢀPart 2: see Ref. [1].

* Corresponding author. Tel.: +49-9131-852-7464; fax: +49-

9131-852-7376.

E-mail address: zenneck@chemie.uni-erlangen.de (U. Zenneck).

PII: S0022-328X(01)01312-2

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

91

An easy access to Ru⁰(h⁶-arene) compounds is the

naphthalene displacement reaction in [Ru⁰(naphthal-

ene)(COD)] by treatment with the arene of choice [7].

This pathway is limited to volatile arenes with only

moderately reactive functional groups such as car-

bonyls, esters or halogen atoms. Several attempts by

our group to introduce arenes with proton active

groups like ꢀOH or ꢀNRH in this way failed until now.

In this paper we report about the preparation of

[Ru⁰(arene)(COD)] complexes with carbonyl side chain

functions by arene displacement reaction and the con-

version of the carbonyl groups by standard organic

reactions into alcohols, imines, or alkenes. This in-

cludes the targeted introduction of a deﬁned stereogenic

centre by using arenes with chiral side chains and

reactions between achiral or racemic [Ru(h⁶-carbony-

larene)(COD)] species with chiral agents.

Scheme 1.

2. Results and discussion

2.1. Naphthalene–arene exchange reaction

Following our earlier work [1,8], we reacted [Ru(n-

aphthalene)(COD)] (1) with eight different mono- or

disubstituted arenes, which bear aldehyde, ketone, es-

ter, or amide functions as part of the side chain. The

reactions proceed well and result in the formation of

the desired [Ru(h⁶-carbonylarene)(COD)] complexes 2–

9 under mild reaction conditions in moderate to good

yields (Scheme 1).

The smaller yields are observed for the aromatic

amides and 3-bromoacetophenone. We believe that

losses are caused in these cases by the more difﬁcult

removal of the obligatory excess of the incoming arenes

due to their high boiling points as free ligands. In the

case of o- or m-unsymmetrically disubstituted arenes,

the planar-chiral complexes 2–5 are formed as race-

mates. Compounds 7 and 9 are examples for the

targeted introduction of a deﬁned stereogenic centre

within the complexes. As assumed, the stereogenic cen-

tre of optically active [Ru(h⁶-(R)-3-phenyl-methylbu-

tyrate)(COD)] (7) remains unaffected by the

coordination reaction. Its molecular structure, includ-

ing the absolute conﬁguration of the benzyl carbon

atom was evaluated by an X-ray crystal structure deter-

mination (Fig. 1).

Fig. 1. Absolute molecular structure of 7 in the solid state. Hydrogen

atoms are omitted for clarity. Selected bond lengths [pm]: Ru1ꢀC11

226.4(3), Ru1ꢀC12 220.4(3), Ru1ꢀC13 226.6(3), Ru1ꢀC14 224.8(4),

Ru1ꢀC15 220.8(3), Ru1ꢀC16 229.7(2); Ru1ꢀC41 214.5(3), Ru1ꢀC44

215.7(3), Ru1ꢀC45 213.4(3), Ru1ꢀC48 214.9(3).

bond forming processes for the preparation of complex

organic molecules. As for the arene chromium tricar-

bonyl complexes [9], [Ru(h⁶-carbonylarene)(COD)] sys-

tems are thus prone to the aldol type reaction. This

includes electrophilic as well as nucleophilic reactivities

when an enolizable moiety is present in the side chain

of the arene ligand. In both cases, there is the possibil-

ity to get access to various functionalised arene ruthe-

nium complexes. Examples for both reaction types will

be given.

As for the free carbonylarene, it is possible to depro-

tonate the methyl group of [Ru(h⁶-o-methylacetophe-

none)(h⁴-COD)] (3) with LDA at low temperatures,

and trap the generated enolate ion with (−)-(R)-men-

thylchloroformate as an electrophile. A diastereoiso-

meric mixture of [Ru(menthyl-{3-oxo-3-h⁶-o-tolyl}-

propionate)(COD)] (10) is obtained in 80% yield

(Scheme 2).

Owing to the acidity of the a-hydrogen atoms, com-

plex 7 is a useful starting material for derivatization

reactions at the neighbouring position to the stereo-

genic centre of the arene side chain (vide infra).

2.2. Aldol reaction of [Ru(p⁶-carbonylarene)(p⁴-COD)]

complexes

If compound 3 is reacted with LDA and o-tolylalde-

hyde or benzaldehyde, respectively, then the isolated

products did not consist of the expected b-hydroxyke-

Enolate chemistry plays an important role in the CꢀC

92

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

Scheme 2.

benzylbromide was added as the electrophile. After the

standard workup procedure, [Ru(h⁶-((R)-(3-phenyl))-2-

benzylbutyric acid methylester)(h⁴-COD)] (14) was iso-

lated in 75% yield as a mixture of diastereomers. The

stereogenic centre in the vicinity of the reaction site

ensures a diastereoselectivity of 80% de (Scheme 5).

On the basis of the reactivity of Ru(arenealdehyde)

complexes, a diastereoselective additon of nucleophiles

to the carbonyl group seems to be possible and this

tones or a-b-unsaturated compounds. The ketones

[Ru(1-h⁶-o-tolyl-3-o-tolyl-propane-1-one)(h⁴-COD)] (11)

and [Ru(h⁶-1-o-tolyl-3-phenylpropane-1-one)(h⁴-COD)]

(12) are formed instead. The yields, however, are quite

good: 53% for 11 and 71% for 12 (Scheme 3).

The molecular structure of 11 was determined by a

single-crystal X-ray structure analysis (Fig. 2).

This crystal structure determination proves that all

carbon atoms of both reaction components of the

ruthenium complex 3 and the o-tolylaldehyde are

present in product 11, but the expected hydroxyl group

of C103 is missing. The bonding distance between the

carbon atoms C102 and C103 is typically in the range

of a carbon–carbon single bond. As all hydrogen

atoms of 11 have been located, this rules out a CꢀC

double bond. The NMR spectra of 11 and 12 are

consistent with the ﬁndings of the crystal structure

determination of 11.

Scheme 3.

The formation of complexes 11 and 12 can be related

to an interaction of the ruthenium atom with one of the

intermediate products of the reaction sequence, but the

mechanism is unclear. In contrast to the rather unreac-

tive carbonyl group of [Ru(h⁶-o-methylacetophe-

none)(h⁴-COD)] (3) that one of [Ru(h⁶-o-tolyl-

aldehyde)(h⁴-COD)] (4) is well suited as an acceptor

function towards all sort of nucleophiles, especially

enolate ions, and the resulting b-hydroxycarbonyl com-

pounds are stable enough for isolation. When 4 is

reacted with the optically active enolate ion of (R)-men-

thylacetate, a diastereoisomeric mixture of [Ru(3-h⁶-o-

tolyl-3-hydroxy menthylpropionate)(h⁴-COD)] (13) is

isolated as a yellow oil in 80% yield (Scheme 4).

In this combination of an enantiopurepure enolate

ion with a racemic aldehyde, a diastereoselective out-

come of the aldol reaction was veriﬁed. According to

the NMR spectra, the diastereoselectivity is 88% de.

This ﬁts the result obtained by the addition of phenyl-

lithium to 4 [1], thus the same conformational prefer-

ences of the carbonyl group of starting material 4 apply

to this type of reaction. With a cyclic transition state of

the aldol reaction and a co-group, which is oriented

opposite to the methyl group, the attack of the enolate

is in favour to proceed from the distal side.

Fig. 2. Molecular structure of 11 in the solid state (one of the two

independent molecules, one enantiomer). Hydrogen atoms are omit-

ted for clarity. Selected bond lengths [pm]: Ru1ꢀC111 226.2(4),

Ru1ꢀC112 223.3(6), Ru1ꢀC113 225.9(6), Ru1ꢀC114 221.6(5),

Ru1ꢀC115 222.9(5), Ru1ꢀC116 227.1(5); Ru1ꢀC131 214.1(6),

Ru1ꢀC138 214.6(6), Ru1ꢀC134 215.8(5), Ru1ꢀC135 214.4(5)

C102ꢀC103 147.2(6).

The optically pure complex 7 was tested as the

starting material for an asymmetric aldol reaction. The

deprotonation of the diastereotopic methylene protons

was obtained again with LDA at low temperatures and

Scheme 4.

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

93

[Ru(h⁶- 2 - (o - methoxyphenyl) - (S) - ethylphenylimine)-

(h⁴-COD)] (15), [Ru(h⁶-2-(2-methylphenyl)1,3 - (N,N -

dimethyl)diazaoctatetrahydroindane)(h⁴-COD)]

(16),

and [Ru(N - [[h⁶- (2 - methylphenyl]methylene] - (R) - 2 -

(methoxymethyl) - 1 - pyrrolidinamine)(COD)] (17) are

formed straightforward. Owing to the racemic character

of 2 and 4, no diastereomeric excess was found in the

reaction products. Attempts to separate the

diastereomers have been successful for the hydrazone

system 17 (Scheme 6).

Scheme 5.

The separation of the diastereomers 17a/17b can be

achieved by fractional crystallisation from n-hexane.

The success of the separation progress can be monitored

by NMR. As 17a formed crystals of good quality, the

crystal structure has been solved including the absolute

conﬁguration of the stereogenic centres. As the R-

conﬁguration of the heterocycle was reproduced cor-

rectly, it was possible to assign the R-conﬁguration to

the Ru atom of 17a. Consequently, the ruthenium atom

in 17b has got a S-conﬁguration (Fig. 3).

2.3. Reduction of ruthenium-coordinated arylesters and

amides with LiAlH₄

Until now we have not been able to coordinate arenes

containing free hydroxy or primary amino functions in

the arene side chain directly to the ruthenium atom. As

such groups are of interest as dangling bonds with

respect to the ruthenium atom, we tried the reduction of

the ester group of enantiopure 7 with LiAlH₄.

Scheme 6.

As expected, the reduction is chemospeciﬁc and does

not touch the stereogenic centre of the side chain. It thus

transforms the enantiomerically pure arylester complex

7 into the optically active arylalcohol complex [Ru(h⁶-

(R)-3-phenylbutan-1-ol)(h⁴-COD)] (18). This reaction

seems to be a general one, which allows generating

chiral [Ru(arene)(COD)] complexes which carry hy-

droxy functions at the side chain of the arene, thus the

analogous reduction of 13 with LiAlH₄affords a corre-

sponding diastereomeric mixture of complexes 19 with a

1,3-dihydroxyl substitution pattern in the side chain of

the ruthenium-coordinated arene ligand (Scheme 7).

In contrast to esters, amides are less reactive towards

reduction with LiAlH₄. Nevertheless, the reduction of

ruthenium-coordinated arylamides is possible with

LiAlH₄. This is shown in the reduction of [Run(h⁶-

N,N,-diethyl-2-phenylacetamide)(h⁴-COD)] (8) which

Fig. 3. Absolute molecular structure of 17a in the solid state. Hydro-

gen atoms are omitted for clarity. Selected bond lengths [pm]:

Ru1ꢀC11 227.5(6), Ru1ꢀC12 226.5(6), Ru1ꢀC13 219.1(7), Ru1ꢀC14

224.8(7), Ru1ꢀC15 230.1(7), Ru1ꢀC16 222.8(5); Ru1ꢀC41 210.3(7),

Ru1ꢀC44 212.9(6), Ru1ꢀC45 212.1(9), Ru1ꢀC48 213.4(6), C11ꢀC18

146.7(8), N1ꢀC18 127.1(7), N1ꢀN2 135.9(6).

could lead to pathways towards planar-chiral systems in

enantiomerically pure form. A simple approach to such

planar-chiral compounds utilises the separation of a

suited mixture of diastereomers. If [Ru(h⁶-o-methoxy-

benzaldehyde)(h⁴-COD)] (2) and [Ru(h⁶-o-tolylalde-

hyde)(h⁴-COD)] (4) are reacted with chiral amines such

as (S)-phenylethylamine, (R,R)-N,N-dimethyl-1,2-di-

aminocyclohexane or (R)-N-amino-2-(methoxymethyl)-

pyrrolidine (RAMP) the diastereomeric complexes

forms

[Ru(h⁶-diethyl-2-phenylethylamine)(h⁴-COD)]

(20) in 60% yield.

2.4. The Wittig oleﬁnation of carbonylarene ruthenium

complexes

The Wittig reaction of alkylidenephosphoranes with

aldehydes and ketones is a valuable and general method

for regiospeciﬁc alkene formation. This includes car-

94

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

bonylarene chromium tricarbonyl complexes [10]. To

complete our screening on the reactivity of p-coordi-

nated carbonylarenes, we decided to apply this coupling

reaction to one of our complexes. Thus, the aldehyde

complex 4 was treated with in situ prepared benzyliden-

phosphorane (benzyltriphenylphosphoniumbromide–n-

butyllithium) and the coupling results in a 55:45

mixture (¹H-NMR) of the E- and Z-isomeric p-coordi-

nated stilbenes 21a and 21b. The mixture was obtained

in 48% yield as an orange solid. In lithium salt-free

reaction conditions [11,12] (sodium bis(trimethylsi-

lyl)amide as base) the E:Z ratio (33:66; 21a:21b) is

affected in as expected. The separation of the isomers

21a and 21b was accomplished by fractional crystallisa-

tion from n-hexane (Scheme 8).

pounds with even complex substitution patterns are

accessible in a few steps. Especially, the successful

separation of diastereomers, which contain a planar-

chiral arene ligand open the gate to planar-chiral

arene–ruthenim complexes in enantiomerically pure

form.

4. Experimental

All reactions were carried out under a dry oxygen

free nitrogen atmosphere. Solvents were puriﬁed by

conventional methods, distilled and stored under nitro-

gen. NMR spectra were recorded close to room temper-

ature (r.t.) in JEOL FT-NMR-EX 270, FT-JNM-GX

270, FT-JNM-LA-400 spectrometers, using dimethyl-

polysiloxane and solvent signals as internal standards.

Mass spectra were recorded in a varian MAT 212

spectrometer. Microanalyses were performed at the an-

alytical department of the institute, using Carlo Erba

Elemental Analyser Mod. 1106. Column chromatogra-

phy (15×1 cm) was accomplished with neutral de-

gassed alumina (Merck, activity III). The complexes

[Ru(naphthalene)(COD)] (1) [7] and [Ru(o-tolylalde-

hyde)(COD)] [1] (4) were prepared as reported in the

literature.

3. Conclusions

Standard organic synthetic procedures can be applied

easily and in great diversity to the synthesis of new side

chain functionalised arene ruthenium cyclooctadiene

compounds. Especially the utilisation of carbonyl

groups as functionalities for the further derivatization

of arene ligands already complexed to the ruthenium

atom provides a wide variety of possible reaction path-

ways. With aldol type reactions arene ruthenium com-

4.1. Synthesis of [Ru(arene)(COD)] 2, 3, 5–9. General

procedure

Starting complex 1, the desired arene ligand and

MeCN are dissolved in THF and the mixture is stirred

at r.t. for 2 days. Solvent, the excess of the arene and

naphthalene are removed in vacuo. The resulting dark

solid is dissolved and ﬁltered through Al₂O₃(activity

III) with light petroleum ether or light petroleum

ether–toluene (2:1). Removal of the solvent under re-

duced pressure yields the product complexes, which can

be recrystallised from light petroleum ether, or a mix-

ture of light petroleum ether–toluene.

4.1.1. [Ru(p⁶-o-methoxybenzaldehyde)(p⁴-COD)] (2)

[Ru(naphthalene)(COD)] (1) (1.73 g, 5.15 mmol), 2

ml MeCN, 11 g o-methoxybenzaldehyd and 100 ml

THF; yield 1.378 g (3.98 mmol, 77%) [Ru(o-methoxy-

benzaldehyd)(COD)] (2) as a red solid.

¹H-NMR (C₆D₆, 270 MHz): l 10.54 (s, 1H, aldehyd);

Scheme 7.

3

4

5.37 [dd, 1H, arene, J_HꢀH=5.4 Hz, J_HꢀH=1.35 Hz];

3

4

4.94 [dt, 1H, arene, J_HꢀH=5.4 Hz, J_HꢀH=1.35 Hz];

3

4.79 [t, 1H, arene, J_HꢀH=5.4 Hz]; 4.06 [d, 1H, arene,

³J_HꢀH=5.4 Hz); 3.43–3.30 (m, 4H, COD_olef); 2.79 (s,

3H, OCH₃); 2.25–2.19 (m, 8H, COD_aliph). ¹³C-NMR

(C₆D₆, 100.4 MHz): l 186.8 (carbonyl); 92.7 (arene);

83.3 (arene); 79.8 (arene); 79.8 (arene); 79.1 (arene);

70.0 (arene); 65.4 (COD_olef); 64.7 (COD_olef); 55.3

(OCH₃); 34.5 (COD_aliph); 33.7 (COD_aliph). FDMS (2

Scheme 8.

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

95

kV); m/z: 345 [M⁺] (100%). Anal. Found: C, 55.45; H,

6.04. Calc. for C₁₆H₂₀O₂Ru: C, 55.61; H, 5.86%.

¹H-NMR (C₆D₆, 269.9 MHz): l 5.45 (t, 1H, arene);

4.65 (d, 2H, arene); 4.48 (t, 2H, arene H); (all J_HꢀH

3

arene=6 Hz); 3.45 (s, 4H, COD_olef); 3.42 (s, 3H,

OCH₃); 2.95–2.78 (m, 2H, CH₂); 2.50–2.25 (m, 9H,

COD_aliph; CH_benzyl); 1.37 (d, 3H, CH₃). ¹³C-NMR

(C₆D₆, 67.9 MHz): l 112.5 (arene); 89.0 (arene); 84.9

(arene); 84.6 (arene); 84.1 (arene); 83.7 (arene); 61.4

(COD_olef); 61.3 (COD_olef); 51.1 (OCH₃); 43.0 (CH₂);

34.4 (CH); 34.3 (COD_aliph); 34.1 (COD_aliph); 21.2 (CH₃).

FDMS (2 kV); m/z: 387 [M⁺] (100%). Anal. Found: C,

59.47; H, 7.14. Calc. for C₁₉H₂₆O₂Ru: C, 58.90; H,

6.81%. Optical rotation: [h]²_D⁵= −26.7°.

4.1.2. [Ru(p⁶-o-methylacetophenone)(p⁴-COD)] (3)

[Ru(naphthalene)(COD)] (1) (1.09 g, 3.23 mmol), 1.0

ml MeCN, 10 ml o-methylacetophenone and 80 ml

THF; yield 986 mg (89%) [Ru(o-methylacetophe-

none)(COD)] (3) as an orange solid.

¹H-NMR (C₆D₆, 269.9 MHz): l 4.95 (1, 1H, arene);

4.77 (d, 1H, arene); 4.51 (t, 1H, arene); 4.40 (d, 1H,

3

arene); (all J_HꢀHarene=6 Hz); 3.45–3.35 (m, 2H,

COD_olef); 3.30–3.20 (m, 2H, COD_olef); 2.40–2.10 (m,

8H, COD_aliph); 2.25 (s, 3H, CH₃); 2.12 (s, 3H, CH₃).

¹³C-NMR (100.4 MHz, C₆D₆): l 189.9 (carbonyl);

101.6 (arene); 93.0 (arene); 91.4 (arene); 88.7 (arene);

87.8 (arene); 82.4 (arene); 65.6 (COD_olef); 63.9

(COD_olef); 34.5 (COD_aliph); 33.4 (COD_aliph); 28.5 (CH₃);

19.6 (CH₃). EIMS (70 eV); m/z: 343 [M⁺] (100%),

C₁₇H₂₂ORu.

4.1.6. [Ru(p⁶-N,N,-diethyl-2-phenyl

acetamide)(p⁴-COD)] (8)

[Ru(naphthalene)(COD)] (1) (394 mg, 1.16 mmol),

5.0 ml N,N,-diethyl-2-phenyl acetamide, 1.5 ml MeCN,

50 ml THF; yield 200 mg (0.50 mmol, 43%) [Ru(h⁶-

N,N,-diethyl-2-phenyl acetamide)(h⁴-COD)] (8) as a

pale-brown solid.

¹H-NMR (C₆D₆, 270 MHz): l 5.05 (d, 2H, arene-H_o,

4.1.3. [Ru(p⁶-m-bromoacetophenone)(p⁴-COD)] (5)

[Ru(naphthalene)(COD)] (1) (502 mg, 1.48 mmol),

1.3 ml MeCN, 11.0 ml m-bromoacetophenone and 40

ml THF; yield 214 mg (0.52 mmol, 36%) [Ru(3-bro-

moacetophenone)(1,5-COD)] (5) as a red solid.

3

³J_HꢀH=5.4 Hz); 4.98 (t, 1H, arene-H_p, J_HꢀH=5.4 Hz);

4.77 (t, 2H, arene-H_m, ³J_HꢀH=5.4 Hz); 3.39 (s, 4H,

3

COD_olef); 3.14 (q, 2H, NCH₂, J_HꢀH=7.2 Hz); 3.05 (s,

2H, PhCH₂); 2.72 (q, 2H, NCH₂³J_HꢀH=7.2 Hz); 2.42–

3

2.20 (m, 8H, COD_aliph); 0.92 (t, 3H, CH₃, J_HꢀH=7.2

¹H-NMR (C₆D₆, 270 MHz): l 5.83 (s, 1H, arene);

Hz); 0.66 (t, 3H, CH₃, ³J_HꢀH=7.2 Hz). ¹³C-NMR

(C₆D₆, 67.7 MHz): l 168.8 (CO); 99.9 (arene); 88.1

(arene); 87.9 (arene); 85.9 (arene); 62.0 (COD_olef); 42.5

(CH₂); 40.8 (CH₂); 38.3 (CH₂); 34.7 (COD_aliph); 14.9

(CH₃); 13.7 (CH₃). FDMS (2 kV); m/z: 400 [M⁺]

(100%). Anal. Found: C, 60.17; H, 7.16; N, 3.39. Calc.

for C₂₀H₂₉NORu: C, 60.00; H, 7.29; N, 3.49%.

3

5.74 (d, 1H, arene, J_HꢀH=5.8 Hz); 5.06 (d, 1H, arene,

³J_HꢀH=6.0 Hz); 4.51 (t, 1H, arene, ³J_HꢀH=6.0 Hz);

3.61–3.50 (m, 2H, COD_olef); 3.37–3.27 (m, 2H,

COD_olef); 2.18 (s, 8H, COD_aliph); 2.05 (s, 3H, CH₃).

¹³C-NMR (C₆D₆, 100.4 MHz): l 194.8 (carbonyl); 92.3

(arene); 91.7 (arene); 90.6 (arene); 88.5 (arene); 86.9

(arene); 83.7 (arene); 70.8 (COD_olef); 67.5 (COD_olef);

33.9 (COD_aliph); 33.5 (COD_aliph); 25.5 (CH₃). FDMS (2

kV); m/z: 407 [M⁺] (100%), C₁₆H₁₉OBrRu.

4.1.7. [Ru(p⁶-N-((S)-2-phenylethyl)isobutyric acid

amide)(p⁴-COD)] (9)

[Ru(naphthalene)(COD)] (1) (395 mg, 1.17 mmol),

2.6 g N-((S)-2-phenylethyl)isobutyric acid amide, 1.5

ml MeCN, 100 ml THF; yield 110 mg (0.27 mmol,

4.1.4. [Ru(2-p⁶-phenylethylacetate)(p⁴-COD)] (6)

[Ru(naphthalene)(COD)] (1) (313 mg, 0.93 mmol),

5.0 ml 2-phenylethylacetate, 1.0 ml MeCN, 50 ml THF;

yield 210 mg (0.56 mmol, 60%) [Ru(2-h⁶-phenylethylac-

etate)(h⁴-COD)] (6) as a brown solid.

23%)

[Ru(h⁶-N-((S)-2-phenylethyl)isobutyric

acid

amide)(h⁴-COD)] (9) as a yellow solid.

¹H-NMR (C₆D₆, 270 MHz): l 5.90 (d (br), 1H, NH,

³J_HꢀH=7.5 Hz); 5.35 (t, 1H, arene, ³J_HꢀH=5.4 Hz);

4.96 (qi; 1H, PhCH, ³J_HꢀH=7.2 Hz); 4.79 (d, 1H,

¹H-NMR (C₆D₆, 270 MHz): l 4.93–4.80 (d+t, 3H,

3

arene); 4.71 (t, 2H, arene); (all J_HꢀHarene=6 Hz);

3

3.88 (q, 2H, OCH₂); 3.33 (s, 4H, COD_olef); 2.93 (s, 2H,

PhCH₂); 2.33 (s, 8H, COD_aliph); 0.94 (s, 3H, CH₃).

¹³C-NMR (C₆D₆, 67.6 MHz): l 170.1 (carbonyl); 96.6

(arene); 87.4 (arene); 87.0 (arene); 85.6 (arene); 61.7

(COD_olef); 60.6 (OCH₂); 39.2 (PhCH₂); 34.1 (COD_aliph);

14.1(CH₃). FDMS (2 kV); m/z: 374 [M⁺] (100%),

C₁₈H₂₄O₂Ru.

arene, J_HꢀH=5.4 Hz); 4.64 (t, 1H, arene, J_HꢀH=5.4

3

Hz); 4.54 (d, 1H, arene, J_HꢀH=5.4 Hz); 4.24 (t, 1H,

arene, ³J_HꢀH=5.4 Hz); 3.40 (s, 4H, COD_olef); 2.25–2.20

3

(m, 8H, COD_aliph); 2.15 (ht, 1H, (CH₃)₂CH, J_HꢀH=6.9

3

Hz); 1.33 (d, 3H, CH₃CH, J_HꢀH=6.6 Hz); 1.14 (d, 6H,

CH_3-isopropyl,

³J_HꢀH=6.9 Hz). ¹³C-NMR (C₆D₆, 100.4

MHz): l 175.1 (CO); 108.7 (arene); 87.5 (arene); 86.7

(arene); 86.3 (arene); 84.1 (arene); 83.6 (arene); 60.9

(COD_olef); 60.7 (COD_olef); 46.1 (PhCH); 35.9

((CH₃)₂CH); 34.4 (COD_aliph); 34.0 (COD_aliph); 20.3

(CH₃); 19.9 (CH₃); 19.8 (CH₃). FDMS (2 kV); m/z: 401

[M⁺] (100%). Anal. Found: C, 59.68; H, 6.84; N, 4.29.

Calc. for C₂₀H₂₉NORu: C, 60.00; H, 7.29; N, 3.49%.

4.1.5. [Ru(p⁶-(R)-3-phenylmethylbutyrate)(p⁴-COD)] (7)

[Ru(naphthalene)(COD)] (1) (556 mg, 1.65 mmol),

5.0 ml (R)-3-phenylmethylbutyrate, 1.0 ml MeCN and

50 ml THF; yield 434 mg (70%) [Ru((R)-3-phenyl-

methylbutyrate)(COD)] (7) as a brown solid.

96

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

4.2.2. [Ru(1-p⁶-o-tolyl-3-o-tolylpropane-1-one)-

(p⁴-COD)] (11)

4.2. Synthesis of [Ru(arene)(COD)] complexes 10–14

by aldol reaction. General procedure

[Ru(h⁶-o-methylacetophenone)(COD)] (3) (524 mg,

1.53 mmol), 0.15 ml (2.20 mmol) diisopropylamine,

0.88 ml (2.20 mmol) n-BuLi (2.5 M in hexane), 0.24 ml

(2.00 mmol) o-tolylaldehyd, 50 ml THF; yield 362 mg

(0.81 mmol, 53%) [Ru(3-h⁶-o-tolyl-1-o-tolyl-propane-1-

one)(h⁴-COD)] (11) as a red solid. ¹H-NMR (C₆D₆, 400

MHz): l 7.19–7.02 (m, 4H, tolyl); 5.41 (t, 1H, arene);

4.63 (d, 1H, arene); 4.43 (t, 1H, arene); 4.33 (d, 1H,

A

THF solution of [Ru(h⁶-o-methylacetophe-

none)(h⁴-COD)] (3) is cooled to −80 °C and added to

a freshly prepared solution of lithiumdiisopropylamid

in THF at −80 °C. After 30 min of stirring, the cold

THF solution of the carbonyl compound is added

dropwise. The mixture is allowed to reach r.t. within 3

h and 2 ml of degassed water is added. The solution is

again stirred for 30 min and the solvent is removed in

vacuo. The residue is redissolved in light petroleum

ether–toluene (2:1) and ﬁltered through Al₂O₃(activity

III). Elution with toluene and removal of the solvent

under reduced pressure yields the desired complexes.

3

arene); (all J_HꢀHarene=6 Hz); 3.38–3.34 (m, 2H,

COD_olef); 3.24–3.21 (m, 2H, COD_olef); 3.15–2.95 (m,

3H, alkyl); 2.77–2.70 (m, 1H, alkyl), 2.19 (m, 11H,

COD_aliph, +CH₃); 2.09 (s, 3H, CH₃). ¹³C-NMR (C₆D₆,

100.4 MHz): l 200.4 (CO); 140.2 (tolyl); 136.0 (tolyl);

130.5 (tolyl); 129.2 (tolyl); 126.5 (tolyl); 126.4 (tolyl);

101.7 (arene); 93.1 (arene); 91.4 (arene); 88.7 (arene);

87.2 (arene); 82.4 (arene); 65.7 (COD_olef); 64.0

(COD_olef); 41.0 (CH₂); 34.2 (COD_aliph); 33.8 (COD_aliph);

28.2 (CH₂); 19.6 (CH₃); 19.2 (CH₃). FDMS (2 kV);

m/z: 448 [M⁺] (100%). Anal. Found: C, 67.07; H, 7.08.

Calc. for C₂₅H₃₀ORu: C, 67.10; H, 6.80%.

4.2.1. [Ru(menthyl-{3-oxo-3-p⁶-o-tolyl}propionate)-

(COD)] (10)

[Ru(h⁶-o-methylacetophenone)(COD)] (3) (226 mg,

0.66 mmol), 0.19 ml (1.32 mmol) diisopropylamine,

0.53 ml (1.32 mmol) n-butyllithium (2.5 M in hexane),

0.29 ml (1.32 mmol) (−)-(R)-menthyl-chloroformate,

40 ml THF; yield 263 mg (0.50 mmol, 75%) [Ru(3-oxo-

3-h⁶-o-tolylmenthylpropionate)(h⁴-COD)] (10) as a yel-

low oil.

4.2.3. [Ru(p⁶-1-o-tolyl-3-phenylpropane-1-one)-

(p⁴-COD)] (12)

[Ru(h⁶-o-methylacetophenone)(COD)] (3) (254 mg,

0.74 mmol), 0.21 ml (1.48 mmol) diisopropylamine,

0.60 ml (1.48 mmol) n-BuLi (2.5 M in hexane), 0.16 ml

(1.48 mmol) benzaldehyde, 40 ml THF; yield 227 mg

(71%) [(h⁴-COD)(h⁶-1-o-tolyl-3-phenylpropane-1-one)-

Ru] (12) as a red solid.

¹H-NMR (C₆D₆, 270 MHz):

l 5.34 (m, 4H,

3

CH_{2-b-ketoester}); 5.25 (t, 1H, arene, J_HꢀH=5.4 Hz); 5.24

(t, 1H, arene, ³J_HꢀH=5.4 Hz); 4.86 (d, 1H, arene,

³J_HꢀH=5.5 Hz); 4.83 (d, 1H, arene, J_HꢀH=5.5 Hz);

3

¹H-NMR (C₆D₆, 270 MHz): l 7.20–6.95 (m, 5H,

phenyl); 5.45 (t, 1H, arene); 4.75 (d, 1H, arene); 4.42 (t,

1H, arene); 4.29 (d, 1H, arene); 3.40–3.31 (m, 2H,

COD_olef); 3.22–3.12 (m, 2H, COD_olef); 3.10–2.90 (m,

3H, alkyl); 2.83–2.69 (m, 1H, alkyl); 2.15 (s, 8H,

COD_aliph); 2.05 (s, 3H, CH₃). ¹³C-NMR (C₆D₆, 100.4

MHz): l 200.1 (CO); 142.2 (phenyl); 130.8 (phenyl);

128.8 (phenyl); 128.6 (phenyl); 128.3 (phenyl); 126.5

(phenyl); 101.3 (arene); 93.4 (arene); 91.5 (arene); 88.5

(arene); 87.3 (arene); 82.4 (arene); 65.7 (COD_olef); 63.9

(COD_olef); 42.4 (CH₂); 34.3(COD_aliph); 33.7 (COD_aliph);

30.8 (CH₂); 19.6 (CH₃). FDMS (2 kV); m/z: 433 [M]⁺,

C₂₄H₂₈ORu.

4.62–4.49 (m, 4H, arene+1H CH_menthyl); 4.27 (d, 1H,

3

arene; J_HꢀH=5.5 Hz); 4.25 (d, 1H, arene, J_HꢀH=5.5

Hz); 3.48–3.40 (m, 4H, COD_olef); 3.29–3.20 (m, 4H,

COD_olef); 2.33–2.20 (m, 16H, COD_aliph); 2.02–1.93 (m,

2H, menthyl); 1.91 (s, 6H, o-CH₃); 1.37–1.25 (m, 6H,

menthyl); 1.08–0.82 (m, 8H, menthyl); 0.77 (d, 3H,

3

CH_3-isopropyl, J_HꢀH=7.1 Hz); 0.75 (d, 3H, CH_3-isopropyl

,

³J_HꢀH=6.7 Hz); 0.72 (d, 3H, CH_3-isopropyl, J_HꢀH=6.7

Hz); 0.71 (d, 3H, CH_3-isopropyl, J_HꢀH=7.1 Hz); 0.64 (d,

3H, CH₃, J_HꢀH=6.3 Hz); 0.63 (d, 3H, CH₃, J_HꢀH

3

=

6.2 Hz); 0.60–0.42 (m, 2H, menthyl). ¹³C-NMR (C₆D₆,

100.4 MHz): l 153.0 (CO), 152.9 (CO); 152.6 (CO);

152.6 (CO); 106.9 (CH_{2-b-ketoester}); 100.1 (arene); 100.0

(arene); 99.5 (arene); 99.4 (arene); 86.6 (arene); 86.5

(arene); 86.3 (arene); 86.2 (arene); 86.0 (arene); 85.9

(arene); 85.8 (arene); 85.8 (arene); 79.0 (menthyl); 78.9

(menthyl); 64.7 (COD); 64.6 (COD); 63.1 COD); 63.1

(COD); 47.3 (menthyl); 40.8 (menthyl); 34.1 (COD);

34.1 (COD); 33.9 (COD); 31.3 (menthyl); 27.2 (men-

thyl); 26.5 (menthyl); 26.5 (menthyl); 23.6 (menthyl);

23.5 (menthyl); 21.9 (menthyl, 20.8 (menthyl), 20.7

(menthyl); 17.4 (menthyl); 16.5 (CH₃-arene). FDMS (2

kV); m/z: 526 [M⁺] (100%). Anal. Found: C, 63.96; H,

8.79. Calc. for C₂₈H₃₁O₃Ru: C, 63.89; H, 7.65%.

4.2.4. [Ru(3-p⁶-o-tolyl-3-hydroxy

menthylpropionate)(p⁴-COD)] (13)

A mixture of 0.21 ml diisopropylamine (1.46 mmol),

20 ml THF, 0.56 ml n-BuLi (2.5 M in hexane) (1.40

mmol) is stirred at −20 °C for 20 min. All reaction

components are then cooled to −80 °C, 0.18 ml (−)-

(R)-menthylacetate (0.85 mmol) in 5 ml THF are

added, followed by a solution of 240 mg (0.73 mmol)

[Ru(o-tolylaldehyd)(COD)] (4) in 10 ml THF 10 min

later. The reaction mixture is stirred at −80 °C for

another hour. It is allowed to reach r.t., hydrolysed

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

97

with degassed H₂O and the solvents are removed in

vacuo. Chromatography on Al₂O₃(activity III) with

toluene as eluent resulted in 312 mg (0.59 mmol, 81%)

[Ru(3-h⁶-o-tolyl-3-hydroxypropionic-acidmenthyl es-

ter)(h⁴-COD)] (13) as a yellow oil.

(COD_aliph); 16.9 (CH₃). FDMS (2 kV); m/z: 477 [M⁺]

(100%). Anal. Found: C, 66.01; H, 7.32. Calc. for

C₂₆H₃₂O₂Ru: C, 65.38; H, 6.75%.

4.3. [Ru(p⁶-2-(o-methoxyphenyl)-(S)-ethylphenylimine)-

(p⁴-COD)] (15)

¹H-NMR (major diastereomer, C₆D₆, 270 MHz): l

5.53 (m, 2H, arene); 5.23–5.10 (m, 2H, hydroxyl), 5.05

(d, 2H, arene); 4.86 (dt, 2H, menthyl); 4.45–4.30 (m,

4H, arene); 3.43–3.35 (m, 4H, COD_olef); 3.20–3.10 (m,

4H, COD_olef); 2.92–2.75 (m, 4H, CH₂); 2.57 (ddd, 2H,

CH₂); 2.35–2.15 (16 H, COD_aliph); 2.10–1.95 (m, 4H,

menthyl); 1.62 (s, 6H, o-CH₃); 1.45–1.30 (m, 4H, men-

thyl); 1.20–1.15 (m, 2H, menthyl); 1.0–0.70 (6H, men-

thyl); 0.85 (t, 12H, CH_3-isopropyl); 0.75 (d, 3H,

CH_3-menthyl); 0.62 (d, 3H, CH_3-menthyl). ¹³C-NMR (major

diastereomer, C₆D₆, 67.7 MHz): l 170.5 (CO); 108.8

(arene); 108.8 (arene); 97.9 (arene); 97.8 (arene); 88.9

(arene); 88.6 (arene); 86.0 (arene); 85.8 (arene); 85.6

(arene); 83.9 (arene); 83.6 (arene); 74.3 (CHOH); 65.5

(menthyl-C1); 62.6 (COD); 60.6 (COD); 47.3 (alkyl);

47.3 (alkyl); 43.0 (alkyl); 42.9 (alkyl); 41.3 (alkyl); 34.5

(COD); 34.4 (alkyl); 34.2 (COD); 31.4 (alkyl); 27.2

(alkyl); 26.5 (alkyl); 23.7 (alkyl); 22.1 (CH₃); 20.9

(CH₃); 16.6 (CH₃); 16.1 (CH₃). FDMS (2 kV); m/z: 526

[M⁺] (100%), C₂₈H₄₂O₃Ru.

A solution of 500 mg (1.44 mmol) [(h⁴-COD)(h⁶-o-

methoxybenzaldehyde)Ru] (2), 291 mg (2.45 mmol) (S)-

phenylethylamine and 10 mg p-toluenesulfonicacid in

100 ml THF is stirred over molecular sieves for 5 days

at r.t. The solution is ﬁltered and the solvents are

removed under reduced pressure. The oily residue is

dissolved in n-hexane and chromatography on Al₂O₃

(deactivated with 5% NEt₃) with cyclohexane–toluene

(1:2) as eluent resulted in 259 mg (0.57 mmol, 40%)

[Ru(h⁶- 2 - (o - methoxyphenyl) - (S) - ethylphenylimine)-

(h⁴-COD)] (15) as a yellow oil.

¹H-NMR (C₆D₆, 270 MHz): l 8.57 (s, 1H, imine);

8.47 (s, 1H, imine); 7.37 (d, 4H, phenyl, ³J_HꢀH=7.6

Hz); 7.20–7.00 (m, 6H, phenyl); 6.36 (d, 1H, arene,

3

³J_HꢀH=5.2 Hz); 6.22 (d, 1H, arene, J_HꢀH=6.0 Hz);

3

5.09 (t, 1H, arene, J_HꢀH=5.7 Hz); 5.01 (t, 1H, arene,

3

³J_HꢀH=5.4 Hz); 4.67 (d, 1H, arene, J_HꢀH=5.7 Hz);

4.55–4.48 (m, 2H, arene); 4.30–4.20 (3H, arene, Ben-

zyl); 3.75–3.22 (m, 8H, COD_olef); 3.11 (s, 3H, OCH₃);

3.08 (s, 3H, OCH₃); 2.45–2.05 (m, 24H, COD_aliph); 1.46

(t, 6H, 2 CH₃). ¹³C-NMR (C₆D₆, 100.4 MHz): l 155.7

(imine); 155.4 (imine); 146.8 (phenyl); 146.5 (phenyl);

139.0 (phenyl); 138.9 (phenyl); 129.2 (phenyl); 128.9

(phenyl); 128.8 (phenyl); 128.5 (phenyl); 127.7 (phenyl);

127.6 (phenyl); 127.6 (phenyl); 127.5 (phenyl); 92.6

(arene); 92.6 (arene); 83.7 (arene); 82.9 (arene); 82.8

(arene); 81.9 (arene); 79.9 (arene); 79.4 (arene); 71.5

(arene); 71.4 (arene); 71.0 (arene); 70.7 (arene); 64.4

(COD_olef); 64.4 (COD_olef); 63.7 (COD_olef); 63.6

(COD_olef); 56.4 (OCH₃); 56.3 (OCH₃); 36.3 (Benzyl);

35.8 (COD_aliph); 33.9 (COD_aliph); 33.7 (PhCH); 27.3

(CH₃); 25.5 (CH₃). FDMS (2 kV); m/z: 448 [M⁺]

(100%). Anal. Found: C, 62.83; H, 7.13; N, 2.74. Calc.

for C₂₄H₂₉NORu: C, 64.29; H, 6.52; N, 3.12%.

4.2.5. [Ru(p⁶-((R)-(3-phenyl))-2-benzylbutyric acid

methylester)(p⁴-COD)] (14)

A mixture of 0.12 ml diisopropylamine (0.80 mmol),

30 ml THF, 0.40 ml n-BuLi (1.6 M in hexane, 0.63

mmol) is stirred for 20 min at −20 °C. All reaction

components are then cooled to −80 °C, 207 mg

[Ru((R)-3-h⁶-phenylmethylbutyrate)(COD)] (7) (0.53

mmol) in 5 ml THF are added, followed by a solution

of 0.065 ml (0.53 mmol) benzylbromide 10 min later.

The reaction mixture is stirred for another hour at

−80 °C, is allowed to reach r.t. and is hydrolysed with

degassed H₂O. The solvents are removed in vacuo.

Chromatography on Al₂O₃(activity III) with toluene as

eluent resulted in 183 mg (0.38 mmol, 73%) [Ru(h⁶-

((R)-(3-phenyl))-2-benzylbutyric acid methylester)(h⁴-

COD)] (14) as a yellow oil.

¹H-NMR (major diastereomer, C₆D₆, 270 MHz): l

3

7.07–6.95 (m, 5H, phenyl); 5.33 (t, 1H, arene, J_HꢀH

=

4.4. [Ru(p⁶-2-(2-methylphenyl)1,3-(N,N-dimethyl)-

diazaoctadehydroindane)(p⁴-COD)] (16)

3

5.4 Hz); 5.19 (d, 1H, arene, J_HꢀH=5.4 Hz); 5.13 (t,

3

1H, arene, J_HꢀH=5.4 Hz); 3.99 (d, 1H, arene, J_HꢀH

=

3

5.4 Hz); 3.48 (t, 1H, arene, J_HꢀH=5.4 Hz); 3.56–3.44

(m, 2H, COD_olef); 3.38–3.26 (m, 2H, COD_olef); 3.05 (s,

3H, OCH₃); 2.92–2.62 (m, 4H, alkyl); 2.42–2.16 (m,

8H, COD_aliph); 1.43 (d, 3H, CH₃, ³J_HꢀH=5.4 Hz).

¹³C-NMR (major diastereomer, C₆D₆, 67.7 MHz): l

173.8 (CO); 140.2 (phenyl); 129.4 (phenyl); 128.7

(phenyl); 126.7 (phenyl); 110.9 (arene); 89.4 (arene);

88.8 (arene); 87.6 (arene); 82.6 (arene); 79.7 (arene);

62.1 (COD_olef); 61.3 (COD_olef); 56.2 (alkyl); 50.9

(OCH₃); 40.4 (alkyl); 35.2 (alkyl); 34.8 (COD_aliph); 33.9

A solution of 490 mg (1.48 mmol) [Ru(h⁶-o-methyl-

benzaldehyde)(h⁴-COD)] (4), 213 mg (1.50 mmol)

(R,R)-N,N-dimethyl-1,2-diaminocyclohexane and 5 mg

p-toluenesulfonicacid in 60 ml THF is stirred over

molecular sieves for 5 days at r.t. The solution is

ﬁltered and the solvents are removed under reduced

pressure. The oily residue is dissolved in n-hexane and

chromatography through Al₂O₃(deactivated with 5%

NEt₃) with cyclohexan–toluene (1:2) as eluent resulted

in 354 mg (0.78 mmol, 53%) [Ru(h⁶-2-(2-methyl-

98

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

phenyl)1,3 - (N,N - dimethyl)diazaoctadehydroindane)-

(h⁴-COD)] (16) as a yellow oil.

87.4 (aren); 87.3 (aren); 81.8 (aren); 81.5 (aren); 77.0

(NCH₂R); 76.7 (NCH₂R); 66.2 (COD); 65.9 (COD);

65.5 (NCHR₂); 65.2 (NCHR₂); 65.2 (COD); 60.8

(OCH₃); 60.7 (OCH₃); 51.0 (OCH₂R); 50.5 (OCH₂R);

36.7 (COD); 36.5 (COD); 36.0 (COD); 35.8 (COD);

32.3 (NCHR); 29.0 (CH₂); 28.9 (CH₂); 24.2 (CH₂); 24.1

(CH₂); 19.4 (CH₃); 19.3 (CH₃). FDMS (2 kV); m/z: 441

[M⁺] (100%). Anal. Found: C, 60.32; H, 7.82; N, 5.99.

Calc. for C₂₂H₃₂N₂ORu: C, 59.84; H, 7.31; N, 6.34%.

¹H-NMR (C₆D₆, 270 MHz): l 5.62–5.55 (m, 2H,

3

arene); 5.29 (t, 1H, arene, J_HꢀH=6.0 Hz); 4.27–4.71

(m, 2H, arene); 4.64 (d, 1H, arene, ³J_HꢀH=5.4 Hz);

3

4.41 (s, 1H, benzyl-H); 4.16 (t, 1H, arene, J_HꢀH=5.4

3

Hz); 4.03 (d, 1H, arene, J_HꢀH=5.4 Hz); 3.72 (s, 1H,

CH_benzyl); 3.58–3.50 (m, 2H, COD_olef); 3.45–3.37 (m,

2H, COD_olef); 3.30–3.17 (m, 4H, COD_olef); 2.78–2.69

(m, 1H, CH_cyclohex); 2.67 (s, 3H, CH₃N); 2.40–2.10 (m,

16H, COD_aliph); 2.30 (s, 3H, CH₃N); 2.28 (s, 3H,

CH₃N); 2.09–2.03 (m, 1H, CH_cyclohex); 1.93 (s, 3H,

CH₃N); 1.92 (s, 3H, o-CH₃); 1.88–1.63 (m, 6H, CH_2-cy-

clohex); 1.57 (s; 3H, o-CH₃); 1.24–0.96 (m, 10H, CH_2-

cyclohex). ¹³C-NMR (C₆D₆, 100.4 MHz): l 104.2

(arene); 103.8 (arene); 101.3 (arene); 94.6 (arene); 90.5

(arene); 90.4 (arene); 88.1 (arene); 87.4 (arene); 87.1

(arene); 86.1 (arene); 85.8 (arene); 85.6 (arene); 84.4

(benzyl); 82.3 (benzyl); 69.8 (cyclohexyl); 69.0 (cyclo-

hexyl); 68.1 (cyclohexyl); 67.2 (cyclohexyl); 63.4 (COD);

62.3 (COD); 61.1 (COD); 60.9 (COD); 40.0 (NꢀCH₃);

37.7 (NꢀCH₃); 36.5 (NꢀCH₃); 36.1 (NꢀCH3); 35.2

(COD); 34.2 (COD); 34.0 (COD); 33.2 (COD); 29.9

(cyclohexyl); 29.6 (cyclohexyl); 29.3 (cyclohexyl); 27.8

(cyclohexyl); 25.3 (cyclohexyl); 24.9 (cyclohexyl); 24.7

(cyclohexyl); 24.5 (cyclohexyl); 17.5 (o-CH₃); 16.3 (o-

CH₃). FDMS (2 kV); m/z: 453 [M⁺] (100%),

C₂₄H₃₆N₂Ru.

4.4.2. Separation of diastereomers (R,S)-17a, (S,R)-17b

The mixture of diastereomers 17 (200 mg) are dis-

solved in 3 ml n-hexane. After the threefold fractional

crystallisation at −20 °C 60 mg of 17a (R,R) are

obtained as orange blocks and 40 mg of 17b (S,R) as

1

yellow needles. According to H-NMR, both are spec-

troscopically pure (\99%) diastereomers.

1

4.4.2.1. 17a (R,R). H-NMR (C₆D₆, 270 MHz): l 6.91

(s, 1H, CH_hydrazone); 5.64 (d, 1H, arene, ³J_HꢀH=5.4 Hz);

3

5.30 (t, 1H, arene, J_HꢀH=5.7 Hz); 4.95 (t, 1H, arene,

3

³J_HꢀH=5.4 Hz); 4.37 (d, 1H, arene, J_HꢀH=5.4 Hz);

3.63–3.48 (m, 2H, pyrrolidinyl); 3.41–3.22 (m, 4H,

COD_oleﬁn, +1H pyrrolidinyl); 3.10 (s, 3H, OCH₃);

3.00–2.82 (m, 1H, pyrrolidinyl); 2.59–2.48 (m, 1H,

pyrrolidinyl); 2.40–2.21 (m, 8H, COD_aliph); 2.01 (s, 3H,

CH₃); 1.68–1.52 (m, 3H, pyrrolidinyl); 1.45–1.31 (m,

1H, pyrrolidinyl). ¹³C-NMR (C₆D₆, 67.7 MHz) l 129.0

(NꢁCꢀH); 102.3 (arene); 102.2 (arene); 91.1 (arene);

86.4 (arene); 85.8 (arene); 81.5 (arene); 77.0 (NCH₂R);

66.2 (COD_olef); 65.9 (NCHR₂); 65.5 (COD_olef); 60.8

(OCH₃); 50.5 (OCH₂R); 36.5 (COD_aliph); 35.8

(COD_aliph); 29.0 (CH₂); 24.2 (CH₂); 19.4 (CH₃). Optical

4.4.1. [Ru(N-[[p⁶-(2-methylphenyl]methylene]-(R)-

2-(methoxymethyl)-1-pyrrolidinamine)-(COD)] (17)

A solution of 800 mg (2.43 mmol) [Ru(h⁶-o-methyl-

benzaldehyde)(h⁴-COD)] (4), 0.32 m (2.43 mmol) (R)-

N-amino-2-(methoxymethyl)-pyrrolidine and 10 mg

p-toluenesulfonicacid in 80 ml THF is stirred over

molecular sieves for 5 days at r.t. The solution is

ﬁltered and the solvents are removed under reduced

pressure. The oily residue is dissolved in n-hexane and

chromatography on Al₂O₃(activity III) with toluene as

eluent resulted in 1 g (2.26 mmol, 93%) of 17 as a

orange solid.

rotation angles (r.t., toluene): [h]₅₈₉= −342°; [h]₅₇₈

−366°; [h]₆₃₃= −257°.

=

1

4.4.2.2. 17b (S,R). H-NMR (C₆D₆, 270 MHz): l 6.92

(s, 1H, CH_hydrazone); 5.69 (d, 1H, arene, ³J_HꢀH=5.4 Hz);

3

5.27 (t, 1H, arene, J_HꢀH=5.7 Hz); 4.89 (t, 1H, arene,

3

³J_HꢀH=5.4 Hz); 4.42 (d, 1H, arene, J_HꢀH=5.4 Hz);

3.63–3.48 (m, 2H, pyrrolidinyl); 3.41–3.22 (m, 4H,

COD_olef, +1H, pyrrolidinyl); 3.05 (s, 3H, OCH₃);

3.00–2.82 (m, 1H, pyrrolidinyl); 2.59–2.48 (m, 1H,

pyrrolidinyl); 2.40–2.21 (m, 8H, COD_aliph); 1.96 (s, 3H,

CH₃); 1.68–1.52 (m, 3H, pyrrolidinyl); 1.45–1.31 (m,

1H, pyrrolidinyl). ¹³C-NMR (C₆D₆, 67.7 MHz): l 127.9

(NꢁCꢀH); 100.4 (arene); 99.9 (arene); 90.1 (arene); 86.0

(arene); 85.4 (arene); 80.0 (arene); 75.1 (NCH₂R); 64.3

(COD); 63.5 (NCHR₂); 63.3 (COD); 58.8 (OCH₃); 49.1

(OCH₂R); 34.7 (COD); 33.9 (COD); 27.0 (CH₂); 22.3

(CH₂); 17.4 (CH₃). Optical rotation angles (r.t., tolu-

ene): [h]₅₈₉= +310°; [h]₅₇₈= +342°; [h]₆₃₃= +236°.

¹H-NMR (C₆D₆, 270 MHz):

CH_hydrazon); 5.69 (d, 1H, arene, ³J_HꢀH=5.4 Hz); 5.64 (d,

l 6.91 (s, 2H,

3

1H, arene, J_HꢀH=5.4 Hz); 5.30 (t, 1H, arene, J_HꢀH

=

3

5.7 Hz); 5.27 (t, 1H, arene, J_HꢀH=5.7 Hz); 4.95 (t, 1H,

arene, J_HꢀH=5.4 Hz); 4.89 (t, 1H, arene, J_HꢀH=5.4

Hz); 4.42 (d, 1H, arene, J_HꢀH=5.4 Hz); 4.37 (d, 1H,

3

arene, ³J_HꢀH=5.4 Hz); 3.63–3.48 (m, 4H, pyrrolidinyl);

3.41–3.22 (m, 8H, COD_olef, +2H, pyrrolidinyl); 3.10

(s, 3H, OCH₃); 3.05 (s, 3H, OCH₃); 3.00–2.82 (m, 2H,

pyrrolidinyl); 2.59–2.48 (m, 2H, pyrrolidinyl); 2.40–

2.21 (m, 16H, COD_aliph); 2.01 (s, 3H, CH₃); 1.96 (s, 3H,

CH₃); 1.68–1.52 (m, 6H, pyrrolidinyl); 1.45–1.31 (m,

2H, pyrrolidinyl). ¹³C-NMR (C₆D₆, 67.7 MHz): l 129.0

(NꢁCꢀH); 102.3 (aren); 102.2 (aren); 100.4 (aren); 99.9

(aren); 92.1 (aren); 92.1 (aren); 87.8 (aren); 87.5 (aren);

4.5. [Ru(p⁶-(R)-3-phenylbutan-1-ol)(p⁴-COD)] (18)

To a suspension of 65 mg LiAlH₄(1.70 mmol) in 50

ml Et₂O a solution of 1.1 g (2.84 mmol) of Ru(methyl-

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

99

(R)-3-phenylbutyrate)(COD) (7) in 10 ml of Et₂O is

added dropwise. The yellow solution is stirred for 5 h

and then hydrolysed with an excess of Na₂SO₄·12H₂O.

After ﬁltration and removal of the solvents, 1.01 g

(80%) [Ru((R)-3-h⁶-phenyl-1-butanol)(h⁴-COD)] (18) is

isolated as a yellow oil.

phenylethylamine)(h⁴-COD)] (20) as a yellow oil.

¹H-NMR (C₆D₆, 270 MHz): l 4.99 (t, 1H, arene,

³J_HꢀH=6.0 Hz); 4.75–4.68 (m, 4H, arene); 3.44 (s, 4H,

COD_olef); 2.69–2.22 (m, 8H, COD_aliph+8H, CH₂); 0.91

(t, 6H, CH₃). ¹³C-NMR (C₆D₆, 67.7 MHz): l 106.6

(aren); 89.4 (aren); 88.0 (aren); 86.4 (aren); 62.7

(COD_olef); 56.3 (CH_2-benzyl); 48.6 (CH₂); 35.7 (COD_aliph);

33.3 (CH₂); 31.7 (CH₂); 13.9 (CH₃). FDMS (2 kV);

m/z: 386 [M⁺] (100%), C₂₀H₃₁NRu.

¹H-NMR (C₆D₆, 270 MHz): l 5.34 (t, 1H, arene);

4.80–4.72 (m, 2H, arene); 3.51–3.35 (m, 6 H, COD_olef

,

CH₂); 2.43–2.17 (m, 8H, COD_aliph, +1H, OH, +1H,

H_benzyl); 1.70 (sept, 1H, CH₂); 1.50 (sept, 1H, CH₂);

1.22 (d, 3H, CH₃). ¹³C-NMR (C₆D₆, 100.4 Mhz): l

114.3 (arene); 89.4 (arene); 85.6 (arene); 84.7 (arene);

84.0 (arene); 82.8 (arene); 61.4 (COD_olef); 61.1

(COD_olef); 60.6 (CH₂O); 41.5 (CH₂); 34.6 (COD_aliph);

34.1 (COD_aliph); 33.9 (CH_benzyl); 21.3 (CH₃). FDMS (2

kV); m/z: 359 [M]⁺, C₁₈H₂₆Oru. Optical rotation an-

gles (r.t., toluene): [h]₅₈₉= −64°; [h]₅₇₈= −16°;

[h]₆₃₃= −24°.

4.8. [Ru(1-p⁶-o-methylphenyl-2-phenyl-ethene)-

(p⁴-1,5-COD)] (21a, 21b)

A solution of 0.32 ml (0.8 mmol) n-butyllithium (2.5

M in hexane) is added dropwise to a stirred suspension

of 346 mg (0.8 mmol) benzyltriphenylphosphoniumbro-

mide in THF at −20 °C. After 5 min a THF solution

of 165 mg (0.5 mmol) [Ru(h⁶-o-tolylaldehyde)(h⁴-1,5-

COD)] (4) is added to the dark-red reaction mixture.

The cooling bath is removed and the mixture is warmed

to r.t. over a period of 2 h. The solution is evaporated

to dryness, redissolved in 20 ml of toluene and 10 ml of

water is added. After 20 min of stirring, the toluene

phase is collected with a syringe, dried over MgSO₄and

ﬁltered through Al₂O₃. The alumina is extracted by

light petroleum ether–toluene 10:1. The combined or-

ganic phases afford 190 mg of a mixture of 21a and

21b. The mixture is dissolved in n-hexane and within a

few days at −30 °C orange crystals are obtained.

Chromatography on Al₂O₃(activity III, eluent light

petroleum ether–toluene 10:1) gave 96 mg [Ru(E-1-h⁶-

o-methylphenyl-2-phenyl-ethene)(h⁴-COD)] (21).

4.6. [Ru(1-p⁶-o-tolyl-propane-1,3-diol)(p⁴-COD)] (19)

To a suspension of 13 mg (0.332 mmol) LiAlH₄in 50

ml Et₂O a solution of 236 mg (0.44 mmol) [Ru(3-h⁶-o-

tolyl-3-hydroxymenthylpropionate)(h⁴-COD)] (13) in 5

ml Et₂O is added. The yellow solution is stirred for 3 h.

The mixture is hydrolyzed with degassed water and

after stirring for 30 min the solvents are evaporated

under reduced pressure. Redissolution with light

petroleum ether–toluene (2:1) and chromatography on

SiO₂(deactivated with 5% H₂O) with THF–toluene

(1:1) as eluent afforded 127 mg (76%) of pure yellow

[Ru(1-h⁶-o-tolyl-propane-1,3-diol)(h⁴-COD)] (19). ¹H-

NMR (C₆D₆, 270 MHz): l 5.73 (t, 1H, arene); 5.18 (d,

1H, arene); 4.68 (dd, 1H, OH); 4.51 (d, 1H, arene); 4.29

(1H, arene); 3.88–3.75 (m, 1H, alkyl); 3.73–3.65 (m,

1H, alkyl); 3.44–3.20 (m, 2H, COD_olef); 3.17–3.09 (m,

2H, COD_olef); 2.81 (broad, 1H, OH); 2.35–2.12 (m, 8H,

COD_aliph); 1.85–1.79 (m, 1H, alkyl); 1.75–1.60 (m, 1H,

alkyl); 1.48 (s, 3H, CH₃). ¹³C-NMR (C₆D₆, 67.7 MHz):

l 109. 8 (arene); 96.5 (arene); 89.4 (arene); 86.5 (arene);

85.1 (arene); 84.0 (arene); 67.5 (CꢀOH); 62.2 (COD_olef);

60.8 (CꢀOH); 60.4 (COD_aliph); 39.8 (CH₂); 15.8 (CH₃).

FDMS (2 kV); m/z: 375 [M⁺] (100%). Anal. Found: C,

57.72; H, 6.75. Calc. for C₁₈H₂₆O₂Ru: C, 57.60; H,

7.00%.

1

4.8.1.1. E-isomer 21a. H-NMR (C₆D₆, 399.65 MHz): l

7.32 (m, 2H, H_phenyl); 7.08 (m, 3H, H_phenyl); 7.00 (d, 1H,

H_olef.

,

³J_HꢀH=16 Hz); 6.71 (d, 1H, H_olef.

,

³J_HꢀH=16

3

Hz); 5.14 (t, 1H_arene, J_HꢀH=5.6 Hz); 5.05 (t, 1H_arene

,

³J_HꢀH=5.6 Hz); 4.86 (d, 1H_arene, J_HꢀH=5.6); 4.40 (d,

3

1H_arene, J_HꢀH=5.6 Hz); 3.35 (m, 4H, COD_olef); 2.32

(m, 8H, COD_aliph.); 1.90 (s, 3H, CH₃). ¹³C-NMR (C₆D₆,

100.40 MHz): l 137.9 (phenyl); 130.1 (phenyl); 129.0

(phenyl); 126.7 (phenyl_.); 124.9 (phenyl); 101.4 (arene);

98.6 (arene); 89.8 (arene); 85.9 (arene); 85.7 (arene);

80.1 (arene); 64.6 (COD_olef); 64.0 (COD_olef); 34.6

(COD_aliph); 34.0 (COD_aliph); 17.4 (CH₃). EIMS (70 eV);

m/z: 404 [M]⁺(100%).

4.7. [Ru(p⁶-N,N-diethyl-2-phenylethylamine)(p⁴-COD)]

(20)

1

4.8.1.2. Z-isomer 21b. H-NMR (C₆D₆, 399.65 MHz): l

3

To a suspension of 7 mg (0.15 mmol) LiAlH₄in 35

ml THF a solution of 100 mg (0.24 mmol) [Ru(h⁶-

N,N,-diethyl-2-phenyl acetamide)(h⁴-COD)] 8 in 5 ml

THF is added. The yellow solution is reﬂuxed for 2 h

and then stirred over night. Hydrolysis and ﬁltration

through Al₂O₃(activity III) with toluene–THF (1:1) as

eluent resulted in 62 mg (67%) [Ru(h⁶-N,N-diethyl-2-

7.00 (m, 5H_phenyl); 6.46 (d, 1H, H_olef., J_HꢀH=12 Hz);

6.27 (d, 1H, H_olef.

,

³J_HꢀH=12 Hz); 4.92 (t, 1H_arene

3

³J_HꢀH=5.2 Hz); 4.81 (t, 1H_arene, J_HꢀH=5.2 Hz); 4.68

(d, 1H_arene, ³J_HꢀH=5.2 Hz); 4.44 (d, 1H_arene, ³J_HꢀH=5.2

Hz); 3.35 (m, 4H, COD_olef); 2.32 (m, 8H, COD_aliph.);

1.82 (s, 3H, CH₃). ¹³C-NMR (C₆D₆, 100.40 MHz): l

137.9 (phenyl); 130.1 (phenyl); 129.0 (phenyl); 126.7

100

G. Bodes et al. / Journal of Organometallic Chemistry 641 (2002) 90–101

Table 1

Crystal data and structure reﬁnement parameters for 7, 11, 17a

7

11

17a

Empirical formula

Formula weight

Temperature (K)

Colour, shape

Crystal system

Space group

C₁₉H₂₆O₂Ru

387.47

200(2)

Yellow, block

Orthorhombic

P2₁2₁2₁

C

447.56

200(2)

Red, plate

Monoclinic

P2₁/c

₂₅H₃₀ORu

C₂₂H₃₂N₂ORu

441.57

298(2)

Orange, block

Orthorhombic

P2₁2₁2₁

Unit cell dimensions

,

a (A)

6.520(1)

12.513(2)

20.385(3)

90.0

1663.1(4)

4

1.547

0.948

Empirical [15]

800

28.651(2)

10.364(1)

14.039(2)

90.0

103.34(1)

90.0

4056.2(8)

8

1.466

7.472(3)

8.345(2)

32.965(11)

90.0

2056(1)

4

1.427

0.775

None

,

b (A)

,

c (A)

h (°)

i (°)

k (°)

V (A )

3

,

Z

z_calc(g cm⁻¹

)

Absorption coefﬁcient, (mm⁻¹

Absorption correction

F(000)

)

0.785

Empirical [15]

1856

920

Crystal size (mm)

0.80×0.50×0.36

5358

4417

0.50×0.45×0.20

11600

8844

668

–

0.0404

0.0931

0.800

1.402; −0.984

0.38×0.20×0.10

Reﬂections measured

Independent reﬂections

No. reﬁned parameters

Absolute structure parameters

R₁[F_o]4|(F)]

3726

235

−0.03(6)

0.0455

0.0810

277

0.02(4)

0.0426

0.0775

1.023

wR₂

Goodness-of-ﬁt at F²

0.817

0.409; −0.620

−3

,

Largest difference peak and hole (e A

)

0.707; −0.595

5. Supplementary material

(phenyl); 124.9 (phenyl); 101.1 (arene); 99.9 (arene);

88.1 (arene); 86.7 (arene); 85.5 (arene); 84.4 (arene);

63.7 (COD_olef); 34.4 (COD_aliph.); 34.2 (C_CODaliph.); 17.3

(s, CH₃). EIMS (70 eV); m/z: 404 [M]⁺(100%).

Crystallographic data for structural analysis have

been deposited with the Cambridge Crystallographic

Data Centre, CCDC nos. 163135, 163136 and 163137

for compounds 7, 11, 17a, respectively. Copies of this

information may be obtained free of charge from The

Director, CCDC, 12 Union Road, Cambridge, CB2

1EZ, UK (Fax: +44-1223-336033; e-mail: deposit@

ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).

4.9. Crystal structures determination

Suitable crystals of 7, 11 and 17a were taken directly

out of the mother liquor. Data were collected in a

Siemens P4 diffractometer for 7, 11 and in a Nicolet

R3m/V for 17a, using Mo–K_aradiation (u=0.71073

,

A) and a graphite monochromator. The crystal struc-

Acknowledgements

tures were solved by direct methods and reﬁned on F²

using full-matrix least-squares procedures (SHELXTL

5.03 [13] or SHELXTL NT 5.10 [14]). Non-hydrogen

atoms were reﬁned anisotropically. For 7 and 11 hydro-

gen atom positions were taken from a difference

Fourier synthesis and reﬁned with a ﬁxed common

isotropic displacement parameter. For 17a hydrogen

atoms were geometrically positioned with an isotropic

displacement parameter tied to those of their carrier

atoms by a factor of 1.2 or 1.5. Other experimental

details are given in Table 1 [15].

We thank the Deutsche Forschungsgemeinschaft and

the Fonds der Chemischen Industrie for ﬁnancial sup-

port and Drs G. Vitulli and P. Pertici, Pisa for many

helpful discussions.

References

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(1997) 1321.

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[4] (a) H. Brunner, Angew. Chem. 111 (1999) 1248;

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1565;

[9] E.P. Kundig, R. Liu, A. Ripa, Helv. Chim. Acta 75 (1992) 2657.

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[13] SHELXTL 5.03, Siemens Analytical X-ray Instrument, Madison,

WI, USA, 1995.

(b) B. Therrien, T.R. Ward, Angew. Chem. Int. Ed. Engl. 38

(1999) 405.

[14] SHELXTL NT 5.10, Bruker AXS, Madison, WI, USA, 1998.

[15] Absorption correction with XABS2: S. Parkin, B. Moezzi, H.

[6] K.J. Haack, S. Hashiguchi, A. Fujii, T. Ikariya, R. Noyori,

Angew. Chem. 109 (1997) 297.

Hope, J. Appl. Crystallogr. 28 (1995) 53 (T_min=0.0575, T_max

0.1527, T_min=0.472, T_max=0.995).

=

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Chiral arene ruthenium complexes. Part 3. [Ruthenium(η6-arene)(η4-1,5-cyclooctadiene)] complexes with N or O donor functions in the arene side chain

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