Synthesis, molecular structure, substitution and C-C coupling reactions of ruthenium complexes containing (g5-C9H7) Ru(PPh3) as a molecular unit

Inorganica Chimica Acta 358 (2005) 1510–1520

www.elsevier.com/locate/ica

Synthesis, molecular structure, substitution and C–C

coupling reactions of ruthenium complexes containing

(g⁵-C₉H₇)Ru(PPh₃) as a molecular unit

*

Helmut Werner , Gerhard Munch, Matthias Laubender

¨

Institut fu¨r Anorganische Chemie, Universita¨t Wu¨rzburg, Am Hubland, D-97074 Wu¨rzburg, Germany

Received 20 July 2004; accepted 7 September 2004

Dedicated to Professor F. Gordon A. Stone in recognition of his inspiring work in organometallic chemistry

Abstract

The 2-methallyl complex [(g⁵-C₉H₇)Ru(g³-2-MeC₃H₄)(PPh₃)] (3), prepared from [(g⁵-C₉H₇)Ru(PPh₃)₂Cl] (2) and

2-MeC₃H₄MgCl, reacts with HX (X = Cl, CF₃CO₂) in the presence of ethene to give the chiral-at-metal compounds [(g⁵-

C₉H₇)Ru(C₂H₄)(PPh₃)X] (4, 5) in nearly quantitative yields. Treatment of

2

with AgPF₆and ethene aﬀords [(g⁵-

C₉H₇)Ru(C₂H₄)(PPh₃)₂]PF₆(6), which reacts with acetone to give the substitution product [(g⁵-C₉H₇)Ru(OCMe₂)(PPh₃)₂]PF₆

(7). The molecular structure of 7 has been determined crystallographically. Whereas treatment of 4 with CH(CO₂Et)N₂yields

the oleﬁn complex [(g⁵-C₉H₇)Ru{g²-(Z)-C₂H₂(CO₂Et)₂}(PPh₃)Cl] (8), the reactions of 4 and 5 with Ph₂CN₂, PhCHN₂

and (Me₃Si)CHN₂lead to the formation of the carbeneruthenium(II) derivatives [(g⁵-C₉H₇)Ru(@CRR⁰)(PPh₃)Cl] (9–11) and

[(g⁵-C₉H₇)Ru(@CRR⁰)(PPh₃)(j¹-O₂CCF₃)] (12–14), respectively. Treatment of 9 (R = R⁰= Ph), 10 (R = H, R⁰= Ph) and 11

(R = H, R⁰= SiMe₃) with MeLi produces the hydrido(oleﬁn) complexes [(g⁵–C₉H₇)RuH(g²-CH₂@CPh₂)(PPh₃)] (15), [(g⁵-

C₉H₇)RuH(g²-CH₂@CHPh)(PPh₃)] (18a,b) and [(g⁵-C₉H₇)RuH(g²-CH₂@CHSiMe₃)(PPh₃)] (19) via C–C coupling and b-hydride

shift. The analogous reactions of 11 with PhLi gives the g³-benzyl compound [(g⁵-C₉H₇)Ru{g³-(Me₃Si)CHC₆H₅}(PPh₃)] (20).

The g³-allyl complex [(g⁵-C₉H₇)Ru(g³-1-PhC₃H₄)(PPh₃)] (17) was prepared from 10 and CH₂@CHMgBr by nucleophilic attack.

Keywords: Ruthenium; Ethene complexes; Carbene complexes; Allyl complexes; C–C coupling reactions

1. Introduction

[RuCl₂(@CHPh)(PCy₃)₂], being honoured in 1998 as

‘‘the compound of the year’’, is accessible in two steps

from [RuCl₂(PPh₃)₃] and phenyldiazomethane as the

carbene source [3]. Prior to the early 1990s, this ‘‘dia-

zoalkane route’’, mainly introduced by Herrmann [4]

and Roper [5], had only rarely been applied, most nota-

bly for the preparation of metal carbenes with d⁶and d⁸

metal centers.

Carbeneruthenium(I) complexes of the general com-

position [RuCl₂(@CHR)(L)₂] with L = tertiary phos-

phines, which were ﬁrst prepared by Grubbs and his

group [1], belong to the most frequently used organome-

tallic compounds both in organic synthesis and homoge-

neous catalysis [2]. The best known representative

In the context of our studies on the chemistry of

cyclopentadienyl and pentamethylcyclopentadienyl

ruthenium complexes with vinylidene and allenylidene

ligands [6], we recently described a synthetic protocol

that is also applicable to the corresponding carbene

*

Corresponding author. Tel.: +49 931 888 5270; fax: +49 931 888

4623.

E-mail address: helmut.werner@mail.uni-wuerzburg.de (H.

Werner).

doi:10.1016/j.ica.2004.09.005

H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

1511

derivatives [(g⁵-C₅H₅)Ru(@CRR⁰)(PPh₃)X] and [(g⁵-

C₅Me₅)Ru(@CRR⁰)(PPh₃)X] (X = Cl, CF₃CO₂) [7].

Although these compounds are highly reactive toward

C-nucleophiles such as methyllithium, phenyllithium

and vinyl Grignard reagents, in contrast to the

Grubbs-type ruthenium carbenes they are inactive in

oleﬁn metathesis.

By considering these results and taking into account

that g⁵-indenyl transition-metal complexes are some-

times more reactive toward nucleophiles than their

g⁵-cyclopentadienyl counterparts [8–10], we set out to

prepare ruthenium compounds of the general composi-

tion [(g⁵-C₉H₇)Ru(@CRR⁰)(PPh₃)X]. In this paper, we

describe the synthesis of corresponding derivatives with

X = Cl and CF₃CO₂and report on the reactivity of these

complexes toward organolithium and Grignard rea-

gents. The preparation of some halfsandwich-type

ethene ruthenium(II) compounds will also be described.

The 2-methallyl complex 3 reacts with HCl and

CF₃CO₂H in toluene at ꢀ40 ꢁC under an ethene atmos-

phere to give orange, air-sensitive solids of the general

composition [(g⁵-C₉H₇)Ru(C₂H₄)(PPh₃)X] (4, 5). Both

compounds (in particular 5) are rather labile but can

be stored at ꢀ60 ꢁC under argon for days. Typical spect-

roscopic features are the two multiplets at 3.04 and 2.42

ppm (for 4) and 3.00 and 2.91 ppm (for 5) due to the

1

ethene protons in the H NMR spectra, and the singlet

at 53.3 ppm (for 4) and 56.0 ppm (for 5) due to the olef-

inic carbon atoms in the ¹³C NMR spectra. The signals

for the quarterary carbon atoms C¹and C⁵of the C₉H₇

unit (for assignment, see Fig. 1) appear at ca. 107–109

ppm, indicating that the indenyl ligand, similarly as in

2 and the precursor 3, is mainly coordinated in a g⁵

fashion. For indenyl complexes, in which a g³bonding

mode predominates, the corresponding resonances are

usually observed at somewhat lower ﬁelds [14].

The preparation of the cationic ethene complex 6 has

been achieved by treatment of the neutral compound 2

with AgPF₆in the presence of C₂H₄(see Scheme 1).

The yellow microcrystalline solid could be isolated in

95% yield. We note that the synthesis of the correspond-

ing perchlorate [(g⁵-C₉H₇)Ru(C₂H₄)(PPh₃)₂]ClO₄has

already been described, though in this case the yield

was only moderate [15].

Since the ethene-to-metal bond in 6 is rather weak,

the oleﬁnic ligand is easily displaced by acetone. Stirring

a solution of 6 in acetone at 50 ꢁC for 10 min gave the

substitution product 7 as a yellow air-stable solid in al-

most quantitative yield. Conductivity measurements in

nitromethane conﬁrm for both 6 and 7 the existence of

1:1 electrolytes. The IR spectrum of 7 shows a strong

2. Results and discussion

Following previous work by Lehmkuhl et al. [11] on

the chemistry of [(g⁵-C₅H₅)Ru(g³-2-MeC₃H₄)(PPh₃)]

(1), the analogous g⁵-indenyl complex 3 was prepared

by treatment of the starting material 2 with the Grignard

reagent 2-MeC₃H₄MgCl (Scheme 1). Compound 3 is a

yellow, only moderately air-sensitive solid, which in con-

trast to 1 is inert toward water and methanol. This is an

advantage for the work-up procedure since excess of the

1

Grignard reagent can be easily removed. The H NMR

spectrum of 3 displays the expected two signals for the

allylic-CH₂protons in syn and anti position of which

that for H_antiat 0.38 ppm is split into a doublet due to

¹H–³¹P coupling. While for the related carbonyl com-

pounds [(g⁵-C₅R₅)Ru(g³-2-MeC₃H₄)(CO)] (R = H,

Me) a mixture of exo/endo conformational isomers

was observed in solution [12,13], the H and ¹³C NMR

1

spectra of 3 indicate that in this case only the exo isomer

exists.

2-MeC₃H₄MgCl

HX

Ru

Ph₃P

C₂H₄

X

3

4: X = Cl

5: X = O₂CCF₃

Ru

Ph₃P

Cl

PF₆

2

CH₃

AgPF₆

acetone

- C₂H₄

Ru

Ph₃P

C₂H₄

Ph₃P

O

Ph₃P

Fig. 1. Molecular structure of the cation of compound 7. Hydrogen

atoms are omitted for clarity; only the ipso-carbon atoms of the phenyl

rings are shown.

6

7

Scheme 1.

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H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

band at 1720 cm^ꢀ1, which is assigned to the m(C@O)

stretching mode of the O@CMe₂molecule. The ¹³C

NMR spectrum of 7 displays a singlet at 206.0 ppm

for the carbonyl carbon atom and another singlet at

30.4 ppm for the methyl carbon atoms of coordinated

acetone. These data are in good agreement with those

reported by Esteruelas et al. [16] and Valerga and his

group [17] for the cationic complexes [(g⁵-C₅H₅)Ru-

(O@CMe₂)(CO)(PiPr₃)]⁺and [(g⁵-C₅Me₅)Ru(O@CMe₂)-

(CO)(PMeiPr₂)]⁺, respectively.

CH(CO₂Et)N₂

Ru

Cl

Ru

Cl

CO₂Et

Ph₃P

4

8

Scheme 2.

ane to the Ru@C bond followed by elimination of N₂, to

yield the product.

The molecular structure of 7 was established by

X-ray crystallography. As shown in Fig. 1, the cation

possesses the expected three-legged piano-stool conﬁgu-

In contrast to CH(CO₂Et)N₂other diazoalkanes such

as Ph₂CN₂, PhCHN₂and (Me₃Si)CHN₂react with both

4 and 5 in toluene or toluene/hexane at room tempera-

ture to give the halfsandwich-type ruthenium carbenes

9–14 in 66–85% yield (Scheme 3). An alternative proce-

dure for the preparation of 14 consists in treatment of

the g³-allyl complex 3 with an equimolar amount of

CF₃CO₂H to generate as an intermediate the chelate

˚

ration with a Ru–O distance of 2.167(5) A (Table 1).

This distance diﬀers only slightly from the bond lengths

found in other ruthenium(II) compounds with a Ru–O

link [6a,18]. The slip-fold parameter D [19], which results

from the diﬀerence between the distances Ru–C(1), Ru–

˚

C(5) and Ru–C(2), Ru–C(4) is 0.160(7) A and thus sim-

ilar to that in [(g⁵-C₉H₇)Ru(@C@CMe₂)(PPh₃)₂]⁺

compound

[(g⁵-C₉H₇)Ru(j²-O₂CCF₃)(PPh₃)]

[¹⁹F

NMR (376.5 MHz, C₆D₆): d ꢀ75.0 (br s); ³¹P NMR

(162.0 MHz, C₆D₆): d 56.3 (br s)], which reacts with

(Me₃Si)CHN₂by partial opening of the four-membered

chelate ring to give 14. The carbene complexes 9–14 are

green moderately air-stable solids which can be stored

under argon for weeks without decomposition. Regard-

ing the spectroscopic data of 9–14, the most characteris-

tic feature is the low-ﬁeld signal due to the carbene

carbon atom at d 302.6–358.6 ppm in the ¹³C NMR

5

˚

(0.197(7) A) [20] and [(g -C₉H₇)Rh(C₂H₄)₂] (0.161 A)

[21]. The parameter, together with the hinge angle HA

(6.9(7)ꢁ) and the fold angle FA (8.4(7)ꢁ) [19,22], indi-

cates that in 7 a considerable slippage of the indenyl

moiety from a g⁵to a g³bond mode had occurred.

The reaction of complex 4 with ethyl diazoacetate

also leads to the displacement of the ethene ligand but

aﬀords instead of the anticipated ruthenium carbene

[(g⁵-C₉H₇)Ru(@CHCO₂Et)(PPh₃)Cl] the diethyl male-

ate complex 8 in excellent yield (Scheme 2 ). Diagnostic

of the chiral-at-metal compound 8 is the observation of

two ¹H NMR resonances due to the oleﬁnic CH protons

(which remain unchanged between 273 and 343 K) and

of two sets of signals due to the ¹³C carbon nuclei of the

CHCO₂Et units. The chemical shifts of these signals are

in good agreement with those for some cyclopentadie-

nylruthenium(II) complexes with diethyl maleate as lig-

and [7b,23]. With regard to the mechanism of the

reaction of 4 with ethyl diazoacetate we assume that in

the initial step the expected carbene derivative [(g⁵-

C₉H₇)Ru(@CHCO₂Et)(PPh₃)Cl] is generated, which

rapidly reacts with a second molecule of CH(CO₂Et)N₂,

possibly through a [3 + 2] cycloaddition of the diazoalk-

spectra, which is split into a doublet due to C–³¹P cou-

1

pling. The signals for the bridging carbon atoms ¹³C and

C⁵of the C₉H₇unit (for assignment, see Fig. 1) appear

at d 117.8–131.5 ppm indicating that the bonding mode

of the indenyl ligand is best described as lying between

1

g⁵and g³[19,24]. The H NMR spectra of 10, 11 and

13, 14 display a resonance for the carbene CH proton

with a chemical shift at around d 17.2 ppm (10, 13)

and d 20.6 ppm (11, 14), which is the same region as that

observed for [(g⁵-C₅H₅)Ru(@CHR)(PPh₃)X] (R = Ph,

SiMe₃; X = Cl, CF₃CO₂) [7b] and for the Grubbs-type

catalyst [RuCl₂(@CHPh)(PCy₃)₂] [3].

RR’CN₂

Table 1

R

Ru

˚

Selected bond distances (A) and bond angles (ꢁ ) with estimated S.D.

for the cation of compound 7

Ph₃P

C

Ph₃P

X

R’

˚

Bond distances (A)

4, 5

9 - 14

Ru–C(1)

Ru–C(2)

Ru–C(3)

Ru–C(4)

2.337(6)

2.186(7)

2.157(7)

2.173(6)

Ru–C(5)

Ru–P(1)

Ru–P(2)

Ru–O

2.342(6)

2.424(2)

2.302(2)

2.167(5)

X = Cl

R

R’

X = CF₃CO₂

R

R’

9

10

11

Ph

H

12

13

14

Ph

H

Ph

SiMe₃

Ph

SiMe₃

Bond angles (ꢁ)

Ru–O–C(10)

P(1)–Ru–P(2)

142.1(6)

103.39(6)

P(1)–Ru–O

P(2)–Ru–O

84.4(2)

87.2(1)

Scheme 3.

H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

1513

Taking the results obtained with the cyclopentadienyl

complexes [(g⁵-C₅H₅)Ru(@CRR⁰)(PPh₃)X] into consid-

eration [7b], we also became interested in ascertaining

the behavior of the indenylruthenium counterparts to-

ward organolithium compounds and Grignard reagents.

Treatment of a solution of 9 in toluene with a solution

of methyllithium in diethyl ether at room temperature,

followed by addition of acetone, gave a yellow-brown

reaction mixture from which after evaporation of the

solvent and extraction with pentane a yellow solid ana-

lyzing as [(g⁵-C₉H₇)RuH(CH₂@CPh₂)(PPh₃)] (15) could

CH₂CHMgBr

Ph

Ru

Cl

C

Ph₃P

Ph

17

H

10

MeLi

Ph

Ru

+

Ph

Ph₃P

1

H

be isolated in 80% yield. The H NMR spectrum of 15

18a

18b

displays (in C₆D₆) a high-ﬁeld resonance at d ꢀ12.56

ppm due to the metal-bonded hydride as well as two

well-separated signals at d 3.18 and 1.75 ppm due to

the oleﬁnic protons. These data, together with those

from the ¹³C NMR spectrum, leave no doubt that the

proposed structure of 15 shown in Scheme 4 is correct.

With regard to the course of formation of 15, it seems

conceivable that the initial product of the reaction is

the carbene(methyl)ruthenium(II) compound [(g⁵-

C₉H₇)RuCH₃(@CPh₂)(PPh₃)], which by migratory

insertion gives the 16-electron alkylmetal intermediate

[(g⁵-C₉H₇)Ru(CPh₂CH₃)(PPh₃)] and then, by b-hydride

shift, the (hydrido)oleﬁn complex 15.

The reaction of 10 with the vinyl Grignard reagent

CH₂@CHMgBr in toluene/THF also leads to the dis-

placement of the chloro ligand and aﬀords the g³-allyl

compound 17 (Scheme 5). It is a yellow microcrystalline,

slightly air-sensitive solid that was isolated in 76% yield.

The ¹H NMR spectrum of 17 displays the signal for the

terminal CHPh proton of the allylic ligand at d 2.55 ppm

as a doublet-of-doublets with a small J(PH) and a larger

J(HH) coupling constant. The corresponding resonance

for the CHPh carbon atom appears in the ¹³C NMR

spectrum at d 54.0 ppm as a doublet. By comparison

of these data with those of [Rh(g³-1-PhC₃H₄)(PiPr₃)₂]

[25], we assume that the phenyl group of the CHPh moi-

ety is in syn and the proton in anti position. We note

that compound 16, even after stirring for 15 h in

C₆D₆, does not rearrange to the syn isomer, which is

supposed to be thermodynamically more stable [26].

The indenyl complexes 10 and 11, containing a sec-

ondary metal-bonded carbene, behave analogously to

9 toward methyllithium and aﬀord in toluene/diethyl

ether the hydrido(oleﬁn) derivatives 18 and 19 in good

yields (Schemes 5 and 6). Owing to the NMR spectro-

Scheme 5.

MeLi

SiMe₃

Ru

SiMe₃

C

Ph₃P

Cl

11

H

19

PhLi

Ru

Ph₃P

Me₃Si

20

Scheme 6.

scopic data, in the case of the hydrido(styrene) com-

pound a mixture of two isomers 18a and 18b is

obtained in which the phenyl substituent at the C@C

double bond is either pointing away (exo) or toward

(endo) the indenyl ligand. Diagnostic for the exo isomer

is a multiplet for the @CHPh proton at d 3.53 ppm and

both a doublet at d 3.05 ppm and a doublet-of-doublets

at d 1.10 ppm for the magnetically and stereochemically

1

diﬀerent @CH₂protons in the H NMR spectrum. For

the endo isomer, the corresponding resonances appear

at d 2.81 (triplet), 1.81 (doublet-of-doublets) and 0.86

(triplet) ppm. For the hydrido(vinylsilane) complex 19,

the ¹H NMR spectrum displays two singlets for the

@CH₂protons at d 1.80 and 1.24 ppm and also a singlet

for the @CHSiMe₃proton up-ﬁeld at d 0.43 ppm. The

hydride signal for 18a, 18b and 19 is observed at around

d ꢀ12.0 to ꢀ13.0 ppm.

In contrast to the cyclopentadienyl compound [(g⁵-

C₅H₅)Ru(@CPh₂)(PPh₃)Cl], which upon treatment with

PhLi aﬀords

a

mixture of products with [(g⁵-

Ph

MeLi

PhLi

Ph

C₅H₅)Ru(g³-Ph₂CC₆H₅)(PPh₃)] as the dominating spe-

cies [7b], the reaction of 11 with phenyllithium proceeds

cleanly and gives, after recrystallization of the crude

product from pentane, the g³-benzyl complex 20 as a

Ru

Cl

Ph

Ph₃P

C

Ph₃P

H

Ph

16

Ph

15

9

Scheme 4.

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H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

light yellow solid in 85% yield (see Scheme 2). The most

characteristic feature in the ¹³C NMR spectrum of 19

are the three signals for the metal-bonded benzylic car-

bon atoms at d 95.5, 65.9 and 32.4 ppm, of which two

are split into doublets due to ¹³C–³¹P coupling. The

observed chemical shifts are similar to those of related

g³-benzyl compounds such as [(g⁵-C₅H₅)Mo{g³-

(Ph₃Sn)CHC₆H₅}(CO)₂] [27] and [(g⁵-C₅H₅)Ru(g³-

PhCHC₆H₅)(PPh₃)] [7b], respectively. The ¹H NMR

spectrum of 20 shows the resonances for the benzylic

protons at d 2.98 ppm (CH of the ring) and ꢀ0.81

ppm (CHSiMe₃). The relative large ³J(PH) coupling

constants of both signals (11.4 and 13.6 Hz) support

the assumption that not only the CH-ring proton but

also the CHSiMe₃proton is in an anti position with re-

spect to the substituent at the central allylic carbon

atom.

In summarizing, the present work has shown that not

only cyclopentadienyl- but also indenylruthenium(II)

complexes with CPh₂, CHPh and CHSiMe₃as carbene

ligands can be prepared in high yields using the ‘‘dia-

zoalkane route’’. Although they seem to be, despite

the relatively weak indenyl-to-metal linkage, poor cata-

lysts for oleﬁn metathesis, they are potentially useful

starting materials for making C–C bonds with the car-

bene ligand as one building block and organolithium

or Grignard compounds as coupling reagents. Whether

the hydrido(oleﬁn) complexes 15, 18 and 19, similarly

to analogous cationic rhodium derivatives [28], can be

employed as catalysts for the oligomerization or polym-

erization of alkenes is the topic of ongoing research in

our group.

stirred for 45 min at 80 ꢁC. After the reaction mixture

was cooled to r.t., 20 ml of degassed water was added

and the suspension was stirred for 10 min. The aqueous

phase was separated and the organic phase was brought

to dryness in vacuo. The remaining yellow solid was

washed three times with 20-ml portions of methanol

and dried; yield 561 mg (86%), m.p. (decomposition)

114 ꢁC. Anal. Calc. for C₃₁H₂₉PRu: C, 69.78; H, 5.48;

Ru, 18.94. Found: C, 69.49; H, 5.60; Ru, 19.46%. MS

(70 eV): m/z 534 (M⁺), 479 (M⁺ꢀ MeC₃H₄), 272

1

(M⁺ꢀ PPh₃). H NMR (C₆D₆, 200 MHz): d 7.38–6.89

(br m, 19H, C₆H₅and C₆H₄part of C₉H₇), 5.13 [t,

3

1H, J(HH) = 2.6 Hz, H²of C₃H₃part of C₉H₇], 4.21

3

[d, 2H, J(HH) = 2.6 Hz, H¹and H³of C₃H₃part of

C₉H₇], 2.62 (s, 2H, H_synof MeC₃H₄), 2.08 (s, 3H, CH₃

of MeC₃H₄), 0.38 [d, 2H, ³J(PH) = 16.1 Hz, H_antiof

MeC₃H₄]. ¹³C NMR (C₆D₆, 50.3 MHz): d 136.9 [d,

¹J(PC) = 37.0

Hz,

ipso-C

of

C₆H₅],

134.9

[d, ²J(PC) = 10.2 Hz, ortho-C of C₆H₅], 128.9 [d,

⁴J(PC) = 1.8 Hz, para-C of C₆H₅], 127.6 [d,

³J(PC) = 9.2 Hz, meta-C of C₆H₅], 123.6, 123.3 (both

s, C^6,9and C^7,8of C₉H₇), 100.7 (s, C^1,5of C₉H₇), 84.0

(s, C³of C₉H₇), 82.3 [d, ²J(PC) = 1.8 Hz, CCH₃of

2

MeC₃H₄], 77.1 [d, J(PC) = 4.6 Hz, C^2,4of C₉H₇], 35.4

2

[d, J(PC) = 4.6 Hz, CH₂of MeC₃H₄], 28.6 (s, CCH₃

of MeC₃H₄); for assignment of indenyl carbon atoms,

see Fig. 1. ³¹P NMR (C₆D₆, 81.0 MHz): d 67.0 (s).

3.2. Preparation of [(g⁵-C₉H₇)Ru(C₂H₄)(PPh₃)Cl]

(4)

A slow stream of ethene was passed through a solu-

tion of 100 mg (0.19 mmol) of 3 in 10 ml of toluene at

ꢀ40 ꢁC. After 2 min, 1.6 ml of a 0.30 M solution of

HCl (0.48 mmol) in toluene was added. The solution

was slowly warmed to r.t. and stirred for 5 min. The sol-

vent was evaporated in vacuo, the remaining orange so-

lid was washed twice with 2-ml portions of pentane and

dried; yield 100 mg (97%), m.p. (decomposition) 60 ꢁC.

Anal. Calc. for C₂₉H₂₆ClPRu: C, 64.26; H, 4.84. Found:

C, 64.01; H, 4.71.%. ¹H NMR (C₆D₆, 400 MHz): d 8.34–

6.55 (br m, 19H, C₆H₅and C₆H₄part of C₉H₇), 5.65 (s,

1H, H¹or H³of C₃H₃part of C₉H₇), 4.93 [t, 1H,

³J(HH) = 2.6 Hz, H²of C₃H₃part of C₉H₇], 4.05 (s,

1H, H¹or H³of C₃H₃part of C₉H₇), 3.04, 2.42 (both

m, 2H each, C₂H₄). ¹³C NMR (C₆D₆, 100.6 MHz): d

3. Experimental

All experiments were carried out under an atmos-

phere of argon by Schlenk techniques. The starting

material 2 was prepared as described in the literature

[15]. IR spectra were recorded on a Perkin–Elmer 1420

Infrared spectrometer and NMR spectra at room tem-

perature (r.t.) on Bruker AC 200 and AMX 400 instru-

ments. Abbreviations used: s, singlet; d, doublet; t,

triplet; q, quartet; sept, septet; m, multiplet; br, broad-

ened signal. Mass spectra were measured on a Finnigan

90 MAT instrument. Conductivity measurements were

carried out with a Schott Konduktometer CG 851.

Melting points were determined by Diﬀerential Thermal

Analysis (DTA).

1

137.9 [d, J(PC) = 40.6 Hz, ipso-C of C₆H₅], 130.0 [d,

⁴J(PC) = 1.9 Hz, para-C of C₆H₅], 128.2 [d,

²J(PC) = 12.4 Hz, ortho-C of C₆H₅], 127.8 [d,

³J(PC) = 10.0 Hz, meta-C of C₆H₅], 126.4, 124.9,

121.3, 119.6 (all s, C^6–9of C₉H₇), 109.3 [d,

²J(PC) = 5.1 Hz, C¹or C⁵of C₉H₇], 107.2 [d,

²J(PC) = 6.1 Hz, C¹or C⁵of C₉H₇], 92.3 (s, C³of

C₉H₇), 79.8, 65.8 (both s, C^2,4of C₉H₇), 53.3 (s,C₂H₄);

for assignment of indenyl carbon atoms, see Fig. 1.

³¹P NMR (C₆D₆, 162.0 MHz): d 63.2 (s).

3.1. Preparation of [(g⁵-C₉H₇)Ru(g³-2-MeC₃H₄)

(PPh₃)] (3)

A suspension of 1.00 g (1.22 mmol) of 2 Æ 1/2CH₂Cl₂

in 20 ml of toluene was treated with 5.0 ml of a 0.60 M

solution of 2-MeC₃H₄MgCl (3.00 mmol) in THF and

H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

1515

3.3. Preparation of [(g⁵-C₉H₇)Ru(C₂H₄)(PPh₃)-

3.5. Preparation of [(g⁵-C₉H₇)Ru{O@

C(CH₃)₂}- (PPh₃)₂]PF₆(7)

(j¹-O₂CCF₃)] (5)

A slow stream of ethene was passed through a solu-

tion of 99 mg (0.19 mmol) of 3 in 10 ml of toluene at

ꢀ40 ꢁC. After 2 min, 15 ll (0.19 mmol) of triﬂuoroace-

tic acid was added. The solution was slowly warmed to

r.t. and stirred for 5 min. The solvent was evaporated

in vacuo, the remaining yellow solid was washed twice

with 5-ml portions of pentane and dried; yield 112 mg

(95%), m.p. (decomposition) 121 ꢁC. IR (C₆H₆):

A solution of 100 mg (0.11 mmol) of 6 in 5 ml of ace-

tone was stirred for 10 min at 50 ꢁC. After the solution

was cooled to r.t., the solvent was evaporated in vacuo

and the remaining yellow solid washed three times with

3-ml portions of diethyl ether; yield 98 mg (94%), m.p.

(decomposition) 140 ꢁC. Anal. Calc. for C₄₈H₄₃F₆O-

P₃Ru: C, 61.08; H, 4.59. Found: C, 60.85; H, 4.41%.

Conductivity: K (CH₃NO₂) 75 cm²Æ X^ꢀ1Æ mol^ꢀ1. IR

1

m(C@O) 1691 cm^ꢀ1

.

¹H NMR (C₆D₆, 200 MHz): d

(KBr): m(C@O) 1720 cm^ꢀ1. H NMR (acetone-d₆, 400

7.54–6.77 (br m, 19H, C₆H₅and C₆H₄part of C₉H₇),

5.65 (br s, 1H, H²of C₃H₃part of C₉H₇), 4.26, 4.03

(both br s, 1H each, H¹and H³of C₃H₃part of

C₉H₇), 3.00, 2.91 (both m, 2H each, C₂H₄). ¹³C

NMR (C₆D₆, 50.3 MHz): d 163.2 [q, ²J(FC) = 36.1

Hz, CCF₃], 136.7 [d, ¹J(PC) = 40.7 Hz, ipso-C of

C₆H₅], 133.6 [d, ³J(PC) = 9.2 Hz, meta-C of C₆H₅],

130.3 [d, ⁴J(PC) = 1.9 Hz, para-C of C₆H₅], 129.3,

127.7, 127.0, 122.3 (all s, C^6–9of C₉H₇), 128.4 [d,

²J(PC) = 10.2 Hz, ortho-C of C₆H₅], 115.4 [q,

¹J(FC) = 293.1 Hz, CF₃], 109.0 [d, ²J(PC) = 2.8 Hz,

C¹or C⁵of C₉H₇], 107.0 [d, ²J(PC) = 3.7 Hz, C¹or

C⁵of C₉H₇], 89.2 (s, C³of C₉H₇), 72.2, 64.9 (both s,

C^2,4of C₉H₇), 56.0 (s, C₂H₄); for assignment of indenyl

carbon atoms see Fig. 1. ¹⁹F NMR (C₆D₆, 188.3

MHz): d ꢀ74.5 (s). ³¹P NMR (C₆D₆, 81.0 MHz): d

60.2 (s).

MHz): d 7.68–6.80 (br m, 34H, C₆H₅and C₆H₄part

of C₉H₇), 5.70 (m, 2H, H¹and H³of C₃H₃part of

C₉H₇), 4.73 (m, 1H, H²of C₃H₃part of C₉H₇), 2.43

(s, 6H, CH₃). ¹³C NMR (acetone-d₆, 100.6 MHz): d

206.0 (s, CH₃CO), 135.3 (br s, ipso-C of C₆H₅), 134.3,

129.3 (both br s, ortho- and meta-C of C₆H₅), 132.5 (s,

para-C of C₆H₅), 130.7, 125.6 (both s, C^6,9and C^7,8of

C₉H₇), 106.7 (s, C¹and C⁵of C₉H₇), 90.7 (s, C³of

C₉H₇), 81.9 (s, C^2,4of C₉H₇), 30.4 (s, CH₃); for assign-

ment of indenyl carbon atoms see Fig. 1. ³¹P NMR (ace-

tone-d₆, 162.0 MHz): d 46.3 (s, PPh₃), ꢀ144.0 [sept,

¹J(PF) = 704.7 Hz, PF₆^ꢀ].

3.6. Preparation of [(g⁵-C₉H₇)Ru{g²-(Z)

-C₂H₂- (CO₂Et)₂}(PPh₃)Cl] (8)

A solution of 100 mg (0.18 mmol) of 4 in 10 ml of tol-

uene was treated with a solution of 37 ll (0.36 mmol) of

CH(CO₂Et)N₂in 2 ml of toluene at r.t. After the reac-

tion mixture was stirred for 5 min, the solvent was evap-

orated, the remaining brown solid was washed twice

with 5-ml portions of diethyl ether and dried; yield 105

mg (85%), m.p. 32 ꢁC. Anal. Calc. for C₃₅H₃₄ClO₄PRu:

C, 61.27; H, 5.00. Found: C, 61.10; H, 4.97%. IR

3.4. Preparation of [(g⁵-C₉H₇)Ru(C₂H₄)(PPh₃)₂]PF₆

(6)

A slow stream of ethene was passed through a solu-

tion of 106 mg (0.13 mmol) of 2 Æ 1/2CH₂Cl₂in 10 ml

of dichloromethane at r.t. for 2 min. After 33 mg (0.13

mmol) of AgPF₆was added to the solution, the reaction

mixture was stirred for 5 min. The oﬀ-white precipitate

(AgCl) was ﬁltered and the ﬁltrate was evaporated in va-

cuo. The remaining yellow solid was washed three times

with 5-ml portions of pentane and dried; yield 113 mg

(95%), m.p. (decomposition) 136 ꢁC. Conductivity: K

(C₆H₆): m(C@O) 1729, 1689 cm^ꢀ^{1 1}H NMR (C₆D₆,

.

400 MHz): d 7.65–6.40 (br m, 19H, C₆H₅and C₆H₄part

of C₉H₇), 5.90 (m, 1H, H²of C₃H₃part of C₉H₇), 5.15,

4.64 (both m, 1H each, H¹and H³of C₃H₃part of

3

C₉H₇), 4.06, 4.01 [both q, 2H each, J(HH) = 4.7 Hz,

CH₂CH₃], 3.80, 3.55 (both m, 1H each, @CH), 1.00,

1

(CH₃NO₂) 89 cm²Æ X^ꢀ1Æ mol^ꢀ1. H NMR (acetone-d₆,

3

0.95 [both t, 3H each, J(HH) = 4.7 Hz, CH₂CH₃]. ¹³C

200 MHz): d 7.62–6.80 (br m, 34H, C₆H₅and C₆H₄part

of C₉H₇), 5.73 (m, 2H, H¹and H³of C₃H₃part of

C₉H₇), 5.04 (m, 1H, H²of C₃H₃part of C₉H₇), 2.45 [t,

NMR (C₆D₆, 100.6 MHz): d 173.8, 173.5 (both s,

CO₂Et), 138.7 (br s, ipso-C of C₆H₅), 135.8 [d,

²J(PC) = 10.1 Hz, ortho-C of C₆H₅], 130.0 (s, para-C

2

4 H, J(PH) = 3.1 Hz, C₂H₄]. ¹³C NMR (acetone-d₆,

3

of C₆H₅), 132.3 [d, J(PC) = 9.3 Hz, meta-C of C₆H₅],

50.3 MHz): d 135.7 [d, ¹J(PC) = 40.0 Hz, ipso-C of

C₆H₅], 134.5, 129.5 (both m, ortho- and meta-C of

C₆H₅), 131.8 (s, para-C of C₆H₅), 132.7, 124.0 (both s,

C^6,9and C^7,8of C₉H₇), 106.8 (s, C¹and C⁵of C₉H₇),

90.9 (s, C³of C₉H₇), 82.2 (s, C^2,4of C₉H₇), 50.8 (s,

C₂H₄); for assignment of indenyl carbon atoms, see

Fig. 1. ³¹P NMR (acetone-d₆, 81.0 MHz): d 45.4 (s,

130.3, 129.0, 128.4, 125.4 (all s, C^6–9of C₉H₇), 113.6,

113.0 (both s, C¹and C⁵of C₉H₇), 95.6 [d,

²J(PC) = 3.0 Hz, C³of C₉H₇], 83.8 [d, ²J(PC) = 10.0

Hz, C²or C⁴of C₉H₇], 72.2 (s, C²or C⁴of C₉H₇),

60.7, 60.3 (both s, CH₂CH₃), 54.2, 53.9 (both s,

@CH), 14.4, 14.2 (both s, CH₂CH₃); for assignment of

indenyl carbon atoms see Fig. 1. ³¹P NMR (C₆D₆,

162.0 MHz): d 47.0 (s).

1

PPh₃), 142.6 [sept, J(PF) = 707.6 Hz, PF₆^ꢀ].

1516

H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

3.7. Preparation of [(g⁵-C₉H₇)Ru(@CPh₂)(PPh₃)Cl]

(9)

³J(PC) = 2.6 Hz, para-C of PC₆H₅], 128.6 (s, para-C of

CC₆H₅), 128.5, 128.0, 124.0, 123.0 (all s, C^6–9

of C₉H₇), 128.3, 127.2 (both s, ortho- and meta-C of

3

A solution of 108 mg (0.20 mmol) of 4 in 10 ml of tol-

uene was treated with a solution of 39 mg (0.20 mmol)

of Ph₂CN₂in 2 ml of toluene at r.t. After the reaction

mixture was stirred for 5 min, the solvent was evapo-

rated. The residue was dissolved in 3 ml of dichloro-

methane and the solution was chromatographed on

Al₂O₃(neutral, activity grade V, height of column 5

cm). With CH₂Cl₂a green fraction was eluted and

brought to dryness in vacuo. The remaining green solid

was washed twice with 5-ml portions of pentane and

dried; yield 113 mg (83%), m.p. (decomposition) 116

ꢁC. Anal. Calc. for C₄₀H₃₂ClPRu: C, 70.63; H, 4.74;

Ru, 14.86. Found: C, 70.37; H, 4.56; Ru, 14.99%. MS

(FAB, 2-nitrophenyloctylether): m/z 680 (M⁺), 645

(M⁺ꢀ Cl), 565 (M⁺ꢀ C₉H₇). ¹H NMR (C₆D₆, 400

MHz): d 7.40–6.45 (br m, 29H, C₆H₅and C₆H₄part

of C₉H₇), 5.32, 5.09 (both br s, 1H each, H¹and H³of

CC₆H₅), 128.2 [d, J(PC) = 9.0 Hz, meta-C of PC₆H₅],

2

124.9 [d, J(PC) = 6.3 Hz, C¹or C⁵of C₉H₇], 119.5 [d,

²J(PC) = 2.6 Hz, C¹or C⁵of C₉H₇], 106.5 [d,

²J(PC) = 2.5 Hz, C³of C₉H₇], 81.0 [d, ²J(PC) = 15.3

2

Hz, C²or C⁴of C₉H₇], 64.4 [d, J(PC) = 7.6 Hz, C²or

C⁴of C₉H₇]; for assignment of indenyl carbon atoms

see Fig. 1. ³¹P NMR (C₆D₆, 162.0 MHz): d 55.0 (s).

3.9. Preparation of [(g⁵-C₉H₇)Ru(@CHSiMe₃)-

(PPh₃)Cl] (11)

A solution of 94 mg (0.17 mmol) of 4 in 10 ml of toluene

was treated with 100 ll of a 2.0 M solution of Me₃SiCHN₂

(0.20 mmol) in hexane and then stirred for 5 min atr.t. The

solvent was evaporated in vacuo and the residue extracted

with 10 ml of pentane. The extract was brought to dryness

in vacuo, the residue was dissolved in 5 ml of acetone and

the solution was ﬁltered. After the solvent was removed

from the ﬁltrate, an olive-green solid was obtained which

was washed with small amounts of acetone (0 ꢁC) and

dried; yield 80 mg (78%), m.p. (decomposition) 48 ꢁC.

Anal. Calc. for C₃₁H₃₂ClPRuSi: C, 61.99; H, 5.37. Found:

C, 61.68; H, 5.33%. ¹H NMR (C₆D₆, 400 MHz): d 20.74

3

C₃H₃part of C₉H₇), 4.73 [t, 1H, J(HH) = 3.0 Hz, H²

of C₃H₃part of C₉H₇]. ¹³C NMR (C₆D₆, 100.6 MHz):

d 316.5 [d, ²J(PC) = 14.6 Hz, Ru@C], 162.9 [d,

³J(PC) = 4.5 Hz, ipso-C of CC₆H₅], 135.2 [d,

¹J(PC) = 43.3 Hz, ipso-C of PC₆H₅], 134.6 [d,

²J(PC) = 10.3 Hz, ortho-C of PC₆H₅], 129.1 [d,

³J(PC) = 2.4 Hz, para-C of PC₆H₅], 127.9, 127.6,

123.1, 122.4 (all s, C^6–9of C₉H₇), 127.8 [d,

³J(PC) = 9.6 Hz, meta-C of PC₆H₅], 127.5 (s, para-C

of CC₆H₅), 127.0, 125.6 (both s, ortho- and meta-C of

CC₆H₅), 124.6 (s, C¹or C⁵of C₉H₇), 117.8 [d,

²J(PC) = 2.5 Hz, C¹or C⁵of C₉H₇], 105.0 [d,

²J(PC) = 1.9 Hz, C³of C₉H₇], 71.1 [d, ²J(PC) = 11.4

Hz, C²or C⁴of C₉H₇], 69.3 (s, C²or C⁴of C₉H₇); for

assignment of indenyl carbon atoms, see Fig. 1. ³¹P

NMR (C₆D₆, 162.0 MHz): d 52.3 (s).

3

[d, 1H, J(PH) = 21.2 Hz, @CHPh], 7.93–6.74 (br m,

19H, C₆H₅and C₆H₄part of C₉H₇), 6.48, 6.20, 3.66 (all

br s, 1H each, H^1–3of C₃H₃part of C₉H₇), 0.33 (s, 9H,

SiCH₃). ¹³C NMR (C₆D₆, 100.6 MHz): d 352.7 [d,

2

²J(PC) = 11.0 Hz, Ru@C], 134.6 [d, J(PC) = 10.2 Hz,

1

ortho-C of C₆H₅], 134.1 [d, J(PC) = 45.8 Hz, ipso-C of

2

C₆H₅], 131.5 [d, J(PC) = 2.5 Hz, C¹or C⁵of C₉H₇],

129.9 [d, ³J(PC) = 2.5 Hz, para-C of C₆H₅], 128.3, 127.2,

3

124.2, 122.9 (all s, C^6–9of C₉H₇), 128.0 [d, J(PC) = 9.0

2

Hz, meta-C of C₆H₅], 121.1 [d, J(PC) = 2.5 Hz, C¹or

2

C⁵of C₉H₇], 103.2 [d, J(PC) = 3.0 Hz, C³of C₉H₇],

3.8. Preparation of [(g⁵-C₉H₇)Ru(@CHPh)(PPh₃)Cl]

(10)

84.7 [d, ²J(PC) = 15.1 Hz, C²or C⁴of C₉H₇], 65.9 (s, C²

or C⁴of C₉H₇), ꢀ1.2 (s, SiCH₃); for assignment of indenyl

carbon atoms, see Fig. 1. ²⁹Si NMR (C₆D₆, 39.8 MHz): d

ꢀ21.4 (s). ³¹P NMR (C₆D₆, 162.0 MHz): d 52.3 (s).

This compound was prepared analogously as de-

scribed for 9, with 103 mg (0.19 mmol) of 4 and 22

mg (0.19 mmol) of PhCHN₂as starting materials. The

isolated green solid still contained some impurities

which could not be completely removed either by col-

umn chromatography or fractional crystallization; yield

98 mg. Data for 10: MS (FAB, 2-nitrophenyloctylether):

3.10. Preparation of [(g⁵-C₉H₇)Ru(@CPh₂)(PPh₃)-

(j¹-O₂CCF₃)] (12)

This compound was prepared analogously as de-

scribed for 9, with 108 mg (0.17 mmol) of 5 and 33

mg (0.17 mmol) of Ph₂CN₂as starting materials. Light

green solid; yield 109 mg (85%), m.p. (decomposition)

104 ꢁC. Anal. Calc. for C₄₂H₃₂F₃O₂PRu: C, 66.57; H,

4.26; Ru, 13.34. Found: C, 66.32; H, 4.31; Ru, 13.48%.

1

m/z 604 (M⁺), 568 (M⁺ꢀ HCl). H NMR (C₆D₆, 400

MHz): d 17.28 [d, 1H, ³J(PH) = 22.8 Hz, @CHPh],

7.80–6.68 (br m, 24H, C₆H₅and C₆H₄part of C₉H₇),

6.12, 5.61 (both br s, 1H each, H¹and H³of C₃H₃part

of C₉H₇), 4.90 [t, 1H, ³J(HH) = 3.0 Hz, H²of C₃H₃part

of C₉H₇]. ¹³C NMR (C₆D₆, 100.6 MHz): d 302.6 [d,

²J(PC) = 15.3 Hz, Ru@C], 157.6 (s, ipso-C of CC₆H₅),

1

IR (C₆H₆): m(C@O) 1688 cm^ꢀ1. H NMR (C₆D₆, 400

MHz): d 7.38–6.85 (br m, 29H, C₆H₅and C₆H₄part

of C₉H₇), 6.66, 4.53, 4.48 (all br s, 1H each, H^1–3of

C₃H₃part of C₉H₇). ¹³C NMR (C₆D₆, 100.6 MHz): d

2

134.5 [d, J(PC) = 10.2 Hz, ortho-C of PC₆H₅], 133.6

[d, ¹J(PC) = 51.3 Hz, ipso-C of PC₆H₅], 130.0 [d,

2

321.3 [d, J(PC) = 9.0 Hz, Ru@C], 162.8 (s, ipso-C of

H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

1517

CC₆H₅), 133.6 [d, ²J(PC) = 10.8 Hz, ortho-C of PC₆H₅],

tion of Me₃SiCHN₂(0.20 mmol) in hexane as starting

materials. Green solid; yield 72 mg (66%).

1

132.2 [d, J(PC) = 31.7 Hz, ipso-C of PC₆H₅], 129.8 [d,

³J(PC) = 1.9 Hz, para-C of PC₆H₅], 129.2, 127.5,

126.7, 121.6 (all s, C^6–9of C₉H₇), 128.3 (s, para-C of

3

CC₆H₅), 128.2 [d, J(PC) = 9.6 Hz, meta-C of PC₆H₅],

3.12.2. Method b

A solution of 95 mg (0.18 mmol) of 3 in 5 ml of tol-

uene was treated at ꢀ40 ꢁC with 14 ll (0.18 mmol) of tri-

ﬂuoracetic acid. The solution was slowly warmed to 0 ꢁC

and then 90 ll of a 2.0 M solution of Me₃SiCHN₂(0.18

mmol) in hexane was added. After the evolution of gas

(N₂) was ﬁnished, the solvent was evaporated in vacuo.

The residue was extracted with 10 ml of pentane, the ex-

tract was concentrated to ca. 1 ml in vacuo and the solu-

tion was stored for 12 h at ꢀ60 ꢁC. Green crystals

precipitated, which were separated from the mother liq-

uor, washed twice with small amounts of pentane (0 ꢁC)

and dried; yield 90 mg (75%), m.p. (decomposition) 96

ꢁC. Anal. Calc. for C₃₃H₃₂F₃O₂PRuSi: C, 58.48; H,

4.76; Ru, 14.91. Found: C, 58.52; H, 4.97; Ru, 15.04%.

MS (FAB, 2-nitrophenyloctylether): m/z 678 (M⁺), 592

(M⁺ꢀ CHSiMe₃), 564 (M⁺ꢀ CF₃CO₂H). ¹H NMR

127.3, 125.0 (both s, ortho- and meta-C of CC₆H₅),

2

122.2 [d, J(PC) = 1.2 Hz, C¹or C⁵of C₉H₇], 118.6 [d,

²J(PC) = 3.1 Hz, C¹or C⁵of C₉H₇], 115.7 [q,

¹J(FC) = 291.2 Hz, CF₃], 102.6 (s, C³of C₉H₇), 68.9

2

[d, J(PC) = 10.2 Hz, C²or C⁴of C₉H₇], 63.6 (s, C²or

C⁴of C₉H₇); for assignment of indenyl carbon atoms,

see Fig. 1; signal for COCF₃carbon atom not exactly lo-

cated. ¹⁹F NMR (C₆D₆, 376.5 MHz): d ꢀ74.6 (s). ³¹P

NMR (C₆D₆, 162.0 MHz): d 37.2 (s).

3.11. Preparation of [(g⁵-C₉H₇)Ru(@CHPh)(PPh₃)-

(j¹-O₂CCF₃)] (13)

This compound was prepared analogously as de-

scribed for 9, with 100 mg (0.16 mmol) of 5 and 19

mg (0.16 mmol) of PhCHN₂as starting materials. Ol-

ive-green solid; yield 76 mg (69%); m.p. (decomposition)

92 ꢁC. Anal. Calc. for C₃₆H₂₈F₃O₂PRu: C, 63.43; H,

4.14; Ru, 14.83. Found: C, 66.32; H, 4.31; Ru, 13.48%.

MS (FAB, 2-nitrophenyloctylether): m/z 682 (M⁺), 568

3

(C₆D₆, 400 MHz): d 20.45 [d, 1H, J(PH) = 17.3 Hz,

@CHPh], 7.47–6.51 (br m, 19H, C₆H₅and C₆H₄part

of C₉H₇), 6.39, 5.88, 3.66 (all br s, 1H each, H^1–3of

C₃H₃part of C₉H₇), 0.18 (s, 9H, SiCH₃). ¹³C NMR

(C₆D₆, 100.6 MHz): d 358.6 [d, ²J(PC) = 10.2 Hz,

1

3

(M⁺ꢀ CF₃CO₂H). IR (C₆H₆): (C@O) 1707 cm^ꢀ1. H

Ru@C], 162.8 [q, J(FC) = 35.2 Hz, COCF₃], 133.9 [d,

3

NMR (C₆D₆, 400 MHz): d 17.21 [d, 1H, J(PH) = 15.2

²J(PC) = 10.5 Hz, ortho-C of C₆H₅], 132.9 [d,

¹J(PC) = 45.8 Hz, ipso-C of C₆H₅], 130.2 [d,

³J(PC) = 1.9 Hz, para-C of C₆H₅], 129.3, 128.6, 123.7,

Hz, @CHPh], 7.78–6.61 (br m, 24H, C₆H₅and C₆H₄

3

part of C₉H₇), 6.40 [d, 1H, J (HH) = 7.6 Hz, H¹or

3

H³of C₃H₃part of C₉H₇], 4.96 (br s, 1H, H²of C₃H₃

part of C₉H₇), 3.71 (br s, 1H, H¹or H³of C₃H₃part

of C₉H₇). ¹³C NMR (C₆D₆, 100.6 MHz): d 304.8 [d,

123.2 (all s, C^6–9of C₉H₇), 128.3 [d, J(PC) = 10.5 Hz,

2

meta-C of C₆H₅], 126.1 [d, J(PC) = 2.5 Hz, C¹or C⁵

of C₉H₇], 121.1 [d, ²J(PC) = 3.8 Hz, C¹or C⁵of

C₉H₇], 115.4 [q, ¹J(FC) = 291.6 Hz, CF₃], 100.5 [d,

²J(PC) = 3.8 Hz, C³of C₉H₇], 80.5 [d, ²J(PC) = 12.4

Hz, C²or C⁴of C₉H₇], 66.0 (s, C²or C⁴of C₉H₇),

ꢀ1.1 (s, SiCH₃); for assignment of indenyl carbon atoms

see Fig. 1. ¹⁹F NMR (C₆D₆, 376.5 MHz): d ꢀ74.0 (s).

²⁹Si NMR (C₆D₆, 79.5 MHz): d ꢀ21.0 (s). ³¹P NMR

(C₆D₆, 162.0 MHz): d 48.2 (s).

3

²J(PC) = 12.8 Hz, Ru@;C], 163.6 [dq, J (FC) = 35.3,

⁵J(PC) = 1.9 Hz, COCF₃], 156.7 (s, ipso-C of CC₆H₅),

2

133.7 [d, J(PC) = 10.2 Hz, ortho-C of PC₆H₅], 133.3

[d, ¹J(PC) = 43.9 Hz, ipso-C of PC₆H₅], 130.2 [d,

³J(PC) = 2.6 Hz, para-C of PC₆H₅], 129.5, 127.6 (both

s, ortho- and meta-C of CC₆H₅), 129.3 (s, para-C of

CC₆H₅), 128.6, 128.1, 124.5, 122.8 (all s, C^6–9of

3

C₉H₇), 128.3 [d, J(PC) = 10.0 Hz, meta-C of PC₆H₅],

2

123.1 [d, J(PC) = 3.2 Hz, C¹or C⁵of C₉H₇], 119.8 [d,

3.13. Preparation of [(g⁵-C₉H₇)RuH(CH₂@CPh₂)-

(PPh₃)] (15)

²J(PC) = 1.3 Hz, C¹or C⁵of C₉H₇], 115.9 [q,

2

¹J(FC) = 292.4 Hz, CF₃], 103.1 [d, J(PC) = 2.1 Hz, C³

of C₉H₇], 76.9 [d, ²J(PC) = 12.7 Hz, C²or C⁴of

C₉H₇], 63.8 [d, ²J(PC) = 3.1 Hz, C²or C⁴of C₉H₇];

for assignment of indenyl carbon atoms, see Fig. 1.

¹⁹F NMR (C₆D₆, 376.5 MHz): d ꢀ74.1 (s). ³¹P NMR

(C₆D₆, 162.0 MHz): d 46.6 (s).

A solution of 105 mg (0.15 mmol) of 9 in 5 ml of toluene

was treated with 0.19 ml of a 1.60 M solution of methyl-

lithium (0.30 mmol) in diethyl ether at r.t. After the solu-

tion was stirred for 30 min, 5 ml of acetone was added, and

the solution was again stirred for 15 min. The solvent was

evaporated in vacuo and the residue was extracted four

times with 10-ml portions of pentane. The combined ex-

tracts were concentrated to ca. 5 ml and the solution

was then stored for 12 h at ꢀ60 ꢁC. Yellow crystals precip-

itated, which were separated from the mother liquor,

washed twice with small amounts of pentane (0 ꢁC) and

dried; yield 79 mg (80%); m.p. (decomposition) 58 ꢁC.

Anal. Calc. for C₄₁H₃₅PRu: C, 74.64; H, 5.35. Found:

3.12. Preparation of [(g⁵-C₉H₇)Ru(@CHSiMe₃)

(PPh₃)(j¹-O₂CCF₃)] (14)

3.12.1. Method a

The procedure was the same as that described for 11,

with 100 mg (0.16 mmol) of 5 and 100 ll of a 2.0 M solu-

1518

H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

C, 74.22; H, 5.07%. MS (FAB, 2-nitrophenyloctylether):

m/z 660 (M⁺), 544 (M⁺ꢀ C₉H₈), 479 (M⁺ꢀ H–

3.15. Preparation of exo/endo- [(g⁵-C₉H₇)RuH(CH₂@

CHPh)(PPh₃)] (18a,18b)

1

CH₂@CPh₂). H NMR (C₆D₆, 400 MHz): d 7.64–6.72

(br m, 29H, C₆H₅and C₆H₄part of C₉H₇), 5.83 [t, 1H,

³J(HH) = 2.6 Hz, H²of C₃H₃part of C₉H₇], 4.41, 3.55

(both br s, 1H each, H¹and H³of C₃H₃part of C₉H₇),

3.18 (br s, 1H, one H of @CH₂), 1.75 [dd, 1H,

This compound was prepared analogously as de-

scribed for 15, with 104 mg (0.17 mmol) of 10 and

0.22 ml of a 1.60 M solution of methyllithium (0.34

mmol) in diethyl ether. Yellow microcrystalline solid;

yield 64 mg (64%); m.p. (decomposition) 79 ꢁC. Anal.

Calc. for C₃₅H₃₁PRu: C, 72.01; H, 5.36. Found: C,

71.50; H, 5.81%. Owing to the NMR spectroscopic data

a mixture of exo/endo isomers 18a,18b in the ratio of 4:3

was obtained. Data for 18a: ¹H NMR (C₆D₆, 400

MHz): d 7.48–6.55 (br m, C₆H₅and C₆H₄part of

C₉H₇), 5.29 [dt, 1H, ²J(PH) = 1.6, ³J(HH) = 2.6 Hz,

H²of C₃H₃part of C₉H₇], 4.75, 4.56 (both br s, 1H

each, H¹and H³of C₃H₃part of C₉H₇), 3.53 (m, 1H,

@CHPh), 3.05 [d, 1H, ³J(HH) = 10.1 Hz, one H of

@CH₂], 1.10 [dd, 1H, ³J(PH) = 10.7, ³J(HH) = 10.1

3

³J(PH) = 13.2, J(HH) = 1.6 Hz, one H of @CH₂], ꢀ

12.56 [d, 1H, ²J(PH) = 36.0 Hz, RuH]. C¹³NMR

(C₆D₆, 100.6 MHz): d 153.5, 149.8 (both s, ipso-C of

CC₆H₅), 137.6 [d, J(PC) = 43.0 Hz, ipso-C of PC₆H₅],

1

2

133.8 [d, J(PC) = 10.6 Hz, ortho-C of PC₆H₅], 132.8,

128.8, 127.8, 127.2 (all s, ortho- and meta-C of CC₆H₅),

3

128.7 [d, J(PC) = 2.9 Hz, para-C of PC₆H₅], 127.5 [d,

³J(PC) = 9.6 Hz, meta-C of PC₆H₅], 125.1, 125.0 (both

s, para-C of CC₆H₅), 124.4, 123.9, 123.0, 122.4 (all s,

C^6–9of C₉H₇), 110.6, 107.5 (both s, C¹and C⁵of C₉H₇),

88.5 [d, ²J(PC) = 2.9 Hz, C³of C₉H₇], 88.3 [d,

²J(PC) = 9.6 Hz, C²or C⁴of C₉H₇], 74.0 (s, C²or C⁴of

C₉H₇), 34.4 (s, @CH₂); for assignment of indenyl carbon

atoms, see Fig. 1. ³¹P NMR (C₆D₆, 162.0 MHz): d 67.7 (s).

2

Hz, one H of @CH₂], ꢀ 12.21 [d, 1H, J(PH) = 39.1

Hz, RuH]. C¹³NMR (C₆D₆, 100.6 MHz): d 150.0 (s,

ipso-C of CC₆H₅), 136.6 [d, J(PC) = 42.9 Hz, ipso-C

1

of PC₆H₅], 133.6 [d, ²J(PC) = 10.5 Hz, ortho-C of

3.14. Preparation of [(g⁵-C₉H₇)Ru(g³-1-PhC₃H₄)-

(PPh₃)] (17)

PC₆H₅], 129.2 [d, J(PC) = 1.9 Hz, para-C of PC₆H₅],

128.1, 124.3 (both s, ortho- and meta-C of CC₆H₅),

3

127.9 [d, J(PC) = 9.5 Hz, meta-C of PC₆H₅], 126.2 (s,

A solution of 107 mg (0.18 mmol) of 10 in 5 ml of tol-

uene was treated with 0.55 ml of a 0.65 M solution of

CH₂@CHMgBr (0.36 mmol) in THF and stirred for

45 min at r.t. The reaction mixture was worked up as de-

scribed for 3. Yellow microcrystalline solid; yield 81 mg

(76%); m.p. (decomposition) 172 ꢁC. Anal. Calc. for

C₃₆H₃₁PRu: C, 72.58; H, 5.26. Found: C, 72.28; H,

5.29%. MS (FAB, 2-nitrophenyloctylether): m/z 596

(M⁺), 479 (M⁺ꢀ PhC₃H₄), 334 (M⁺ꢀ PPh₃). ¹H

NMR (C₆D₆, 400 MHz): d 7.74–6.62 (br m, 24H,

C₆H₅and C₆H₄part of C₉H₇), 4.80 [dddd, 1H,

³J(PH) = 1.5, ³J(HH) = 9.4, 9.2 and 6.9 Hz, CHCH

CH₂], 4.45, 4.40 (both br s, 1H each, H¹and H³of

para-C of CC₆H₅), 125.2, 124.3, 123.6, 123.2 (all s,

C^6–9of C₉H₇), 110.0 (s, C¹or C⁵of C₉H₇), 109.5 [d,

²J(PC) = 1.9 Hz, C¹or C⁵of C₉H₇], 87.0 [d,

²J(PC) = 2.9 Hz, C³of C₉H₇], 86.0 [d, ²J(PC) = 10.5

Hz, C²or C⁴of C₉H₇], 71.8 (s, C²or C⁴of C₉H₇),

2

48.9 (s, @CHPh), 26.9 [d, J(PC) = 4.8 Hz, @CH₂]; for

assignment of indenyl carbon atoms, see Fig. 1. ³¹P

NMR (C₆D₆, 162.0 MHz): d 71.3 (s). ꢀ Data for 18b:

¹H NMR (C₆D₆, 400 MHz): d 7.48–6.55 (br m, C₆H₅

and C₆H₄part of C₉H₇), 5.77 [d, 1H, ³J (HH) = 2.6

2

Hz, H¹or H³of C₃H₃part of C₉H₇], 5.74 [dt, 1H, J

(PH) = 1.6, ³J(HH) = 2.6 Hz, H²of C₃H₃part of

C₉H₇], 4.34 (br s, 1H, H¹or H³of C₃H₃part of

C₉H₇), 2.81 [t, 1H, ³J(HH) = 8.1 Hz, = CHPh], 1.81

[dd, 1H, ²J(PH) = 2.4, ³J(HH) = 8.1 Hz, one H of

@CH₂], 0.86 [t, 1H, ³J(HH) = 8.1 Hz, one H of

3

C₃H₃part of C₉H₇), 4.32 [t, 1H, J(HH) = 2.9 Hz, H²

of C₃H₃part of C₉H₇], 2.55 [dd, 1H, ³J(PH) = 1.2,

³J(HH) = 6.9 Hz, CH CHCH₂], 1.98 [dd, 1H,

³J(PH) = 12.6, ³J(HH) = 9.4 Hz, H_synof allyl-CH₂],

2

@CH₂], ꢀ 13.06 [d, 1H, J(PH) = 39.9 Hz, RuH]. C¹³

3

0.52 [dd, 1H, J(PH) = 15.1, J(HH) = 9.2 Hz, H_antiof

allyl-CH₂]. C¹³NMR (C₆D₆, 100.6 MHz): d 148.3 (s,

ipso-C of CC₆H₅), 136.8 [d, J(PC) = 38.2 Hz, ipso-C

NMR (C₆D₆, 100.6 MHz): d 148.9 (s, ipso-C of

CC₆H₅), 136.9 [d, J(PC) = 42.9 Hz, ipso-C of PC₆H₅],

1

2

133.7 [d, J(PC) = 10.5 Hz, ortho-C of PC₆H₅], 129.3

of PC₆H₅], 134.9 [d, ²J(PC) = 10.2 Hz, ortho-C of

PC₆H₅], 129.1 (s, para-C of PC₆H₅), 128.4, 125.4 (both

[d, ³J(PC) = 2.9 Hz, para-C of PC₆H₅], 128.2, 126.2

(both s, ortho- and meta-C of CC₆H₅), 127.8 [d,

³J(PC) = 9.5 Hz, meta-C of PC₆H₅], 126.9 (s, para-C

of CC₆H₅), 124.1, 123.8, 123.7, 121.8 (all s, C^6–9of

3

s, ortho- and meta-C of CC₆H₅), 127.7 [d, J(PC) = 8.9

Hz, meta-C of PC₆H₅], 124.5, 124.4, 123.8, 123.7 (all s,

C^6–9of C₉H₇), 122.9 (s, para-C of CC₆H₅), 101.4,

100.2 (both s, C¹and C⁵of C₉H₇), 89.2 (s, C³of

2

C₉H₇), 110.5 [d, J(PC) = 2.9 Hz, C¹or C⁵of C₉H₇],

2

109.6 [s, C¹or C⁵of C₉H₇], 87.1 [d, J(PC) = 1.9 Hz,

2

C₉H₇), 73.6, 72.8 [both d, J(PC) = 3.8 Hz, C²and C⁴

C³of C₉H₇], 79.3 [d, ²J(PC) = 10.5 Hz, C²or C⁴of

C₉H₇], 69.3 [d, ²J(PC) = 1.9 Hz, C²or C⁴of C₉H₇],

of C₉H₇], 65.9 (s, CHCHCH₂), 54.0 [d, ²J(PC) = 2.5

Hz, CHCHCH₂], 36.0 [d, ²J(PC) = 6.4 Hz, CH₂]; for

assignment of indenyl carbon atoms, see Fig. 1. ³¹P

NMR (C₆D₆, 162.0 MHz): d 64.8 (s).

2

47.2 [d, J(PC) = 1.9 Hz, = CHPh], 27.0 [s, @CH₂]; for

assignment of indenyl carbon atoms, see Fig. 1. ³¹P

NMR (C₆D₆, 162.0 MHz): d 67.9 (s).

H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

1519

1

ordinated part of CC₆H₅), 136.5 [d, J(PC) = 35.2 Hz,

3.16. Preparation of [(g⁵-C₉H₇)RuH(CH₂@CHSi-

Me₃)(PPh₃)] (19)

2

ipso-C of PC₆H₅], 135.1 [d, J(PC) = 10.5 Hz, ortho-C

of PC₆H₅], 129.2 [d, ⁴J(PC) = 1.9 Hz, para-C of

3

PC₆H₅], 127.7 [d, J(PC) = 8.6 Hz, meta-C of PC₆H₅],

This compound was prepared analogously as de-

scribed for 15, with 120 mg (0.20 mmol) of 11 and

0.25 ml of a 1.60 M solution of methyllithium (0.40

mmol) in diethyl ether. Light yellow microcrystalline so-

lid; yield 95 mg (82%); m.p. (decomposition) 68 ꢁC.

Anal. Calc. for C₃₂H₃₅PRuSi: C, 66.30; H, 6.09; Ru,

17.43. Found: C, 66.61; H, 6.28; Ru, 17.88%. MS (70

eV): m/z 580 (M⁺), 507 (M⁺ꢀ SiMe₃), 478 (M⁺ꢀ H–

102.8, 98.7 (both s, C¹and C⁵of C₉H₇), 95.5 [d,

²J(PC) = 1.9 Hz, CCHSiMe₃], 82.4 [d, ²J (PC) = 1.9

2

Hz, C²or C⁴of C₉H₇], 79.1 [d, J(PC) = 11.5 Hz, C³

of C₉H₇], 71.5 (s, C²or C⁴of C₉H₇), 65.9 (s, CH of coor-

dinated part of CC₆H₅), 32.4 [d, ²J (PC) = 2.8 Hz,

CHSiMe₃], 2.5 (s, SiCH₃); for assignment of indenyl car-

bon atoms, see Fig. 1. ²⁹Si NMR (C₆D₆, 79.5 MHz): d

0.6 (s). ³¹P NMR (C₆D₆, 162.0 MHz): d 61.8 (s).

1

CH₂@CHSiMe₃). H NMR (C₆D₆, 400 MHz): d 7.34–

6.69 (br m, 19H, C₆H₅and C₆H₄part of C₉H₇), 5.72

(br s, 1H, H²of C₃H₃part of C₉H₇), 4.88, 4.71 (both

br s, 1H each, H¹and H³of C₃H₃part of C₉H₇), 1.80,

1.24 (both s, 1H each, @CH₂), 0.43 (s, 1H, @CHSiMe₃],

3.18. Crystal structure analysis of 7

Crystals were obtained from acetone upon cooling a

saturated solution from 50 to 20 ꢁC. Crystal structure

determination of 7: C₄₈H₄₃F₆OP₃Ru, M_r= 949.85;

monoclinic, space group P2₁(no. 4), Z = 2,

2

0.24 (s, 9H, SiCH₃), ꢀ 12.86 [d, 1H, J(PH) = 37.5 Hz,

RuH]. ¹³C NMR (C₆D₆, 100.6 MHz): d 136.3 [d,

¹J(PC) = 44.8 Hz, ipso-C of C₆H₅], 133.8 [d,

²J(PC) = 10.5 Hz, ortho-C of C₆H₅], 129.1 [d,

³J(PC) = 1.9 Hz, para-C of C₆H₅], 127.7 [d,

³J(PC) = 8.6 Hz, meta-C of C₆H₅], 125.2, 125.1, 122.5,

˚

a = 10.539(7) A, b = 17.621(2) A, c = 11.520(2) A,

3

b = 96.987(9)ꢁ, V = 2124(2) A , D_calc= 1.486 g cm^ꢀ3

,

˚

k = 0.71073 A, T = 293(2) K, l(Mo Ka) = 0.540

mm^ꢀ1. Crystal size 0.20 · 0.22 · 0.46 mm³; 2H_max= 60ꢁ;

6685 reﬂections were measured, 5433 of these were inde-

pendent (R_int= 0.0315) and employed in the structure

2

122.3 (all s, C^6–9of C₉H₇), 108.3 [d, J(PC) = 3.8 Hz,

2

C¹or C⁵of C₉H₇], 104.7 [d, J(PC) = 4.8 Hz, C¹or C⁵

2

of C₉H₇], 86.6 [d, J(PC) = 2.9 Hz, C³of C₉H₇], 79.6

[d, ²J(PC) = 6.7 Hz, C²or C⁴of C₉H₇], 74.4 [d,

²J(PC) = 11.4 Hz, C²or C⁴of C₉H₇), 36.3 [d,

²J(PC) = 1.9 Hz, @CH₂], 8.7 (s, @CHSiMe₃), 1.4 (s,

SiCH₃); for assignment of indenyl carbon atoms see

Fig. 1. ²⁹Si NMR (C₆D₆, 79.5 MHz): d 24.7 [d,

³J(PSi) = 16.6 Hz]. ³¹P NMR (C₆D₆, 162.0 MHz): d

71.3 (s).

reﬁnement (534 parameters). The R values are

R₁= 0.0476 and wR ₂= 0.0763 [I > 2r(I)] and

R₁= 0.1048 and wR₂= 0.0916 (all data); reﬂex/parame-

ter ratio = 10.17; min/max residual electron density:

0.379/ꢀ0.406 e A^{ꢀ 3}. Data were collected on a Enraf-

˚

Nonius CAD 4 diﬀractometer. A semi-empirical absorp-

tion correction was applied. The structure was solved by

direct methods (^SHELXS-86) [29] and reﬁned against F²

by least-squares (SHELXL-93) [30]. All non-hydrogen

atoms were reﬁned anisotropically. The positions of all

hydrogen atoms were calculated according to ideal

3.17. Preparation of [(g⁵-C₉H₇)Ru(g³-Me₃SiCHC₆H₅)-

(PPh₃)] (20)

˚

A solution of 96 mg (0.16 mmol) of 11 in 5 ml of tol-

uene was treated with 0.18 ml of a 1.80 M solution of

phenyllithium (0.32 mmol) in cyclohexane/diethyl ether

(7:3). The reaction mixture was worked up as described

for 15. Light yellow microcrystalline solid; yield 87 mg

(85%); m.p. (decomposition) 111 ꢁC. Anal. Calc. for

C₃₇H₃₇PRuSi: C, 69.24; H, 5.81; Ru, 15.75. Found: C,

68.93; H, 5.83; Ru, 15.57%. MS (FAB, 2-nitrophenyloc-

tylether): m/z 642 (M⁺), 479 (M⁺ꢀ PhCHSiMe₃), 380

geometry (distance C–H 0.95 A) and used only in struc-

ture factor calculations.

4. Supplementary material

Crystallographic data (excluding structure factors)

for the structural analysis have been deposited with

the Cambridge Crystallographic Data Centre, CCDC

no. 243763 for compound 7. Copies of this information

may be obtained free of charge on application to 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).

1

(M⁺ꢀ PPh₃). H NMR (C₆D₆, 400 MHz): d 7.58 [d,

3

1H, J(HH) = 8.4 Hz, one H of uncoordinated part of

CC₆H₅], 7.45–6.37 (br m, 22H, PC₆H₅, C₆H₄part of

C₉H₇, and 3H of uncoordinated part of CC₆H₅), 5.37

3

[t, 1H, J (HH) = 2.6 Hz, H²of C₃H₃part of C₉H₇],

4.37, 3.94 (both br s, 1H each, H¹and H³of C₃H₃part

of C₉H₇), 2.98 [dd, 1H, ³J(PH) = 11.4, ⁴J(HH) = 5.6 Hz,

CH of coordinated part of CC₆H₅], 0.38 (s, 9H, SiCH₃),

ꢀ 0.81 [d, ³J(PH) = 13.6 Hz, CHSiMe₃]. ¹³C NMR

(C₆D₆, 100.6 MHz): d 139.4, 132.3, 126.2, 125.0, 124.2,

124.0, 122.5, 120.1 (all s, C^6–9of C₉H₇and 4C of unco-

Acknowledgements

We thank the Deutsche Forschungsgemeinschaft

(SFB 347) and the Fonds der Chemischen Industrie

1520

H. Werner et al. / Inorganica Chimica Acta 358 (2005) 1510–1520

(h) C.E. Garrett, G.C. Fu, J. Org. Chem. 63 (1998) 1370;

(i) M.J. Calhorda, C.A. Gamelas, I.S. Goncalves, E. Herdtweck,

C.C. Romao, L.F. Veiros, Organometallics 17 (1998) 2597;

(j) L.F. Veiros, Organometallics 19 (2000) 3127.

[10] E. Bleuel, M. Laubender, B. Weberndo¨rfer, H. Werner, Angew.

Chem., Int. Ed. 38 (1999) 156.

for ﬁnancial support. Moreover, we acknowledge sup-

port by Mrs. R. Schedl and Mr C. P. Kneis (elemental

analysis and DTA), Mrs M. L. Scha¨fer and Dr. W.

Buchner (NMR spectra), and Dr. C. Brandt and Dr.

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Article Doi

Synthesis, molecular structure, substitution and C-C coupling reactions of ruthenium complexes containing (g5-C9H7) Ru(PPh3) as a molecular unit

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