Synthesis and characterization of planar-chiral cyclopentadienylruthenium-vinylidene complexes

www.elsevier.nl/locate/jorganchem

Journal of Organometallic Chemistry 617–618 (2001) 601–615

Synthesis and characterization of planar-chiral

cyclopentadienylruthenium–vinylidene complexes

Yoshiki Ajioka ^a, Yuji Matsushima ^a, Kiyotaka Onitsuka ^a, Hiroshi Yamazaki ^b,

Shigetoshi Takahashi ^a,*

^aThe Institute of Scientiﬁc and Industrial Research, Osaka Uni6ersity, Mihogaoka, Ibaraki, Osaka 567-0047, Japan

^bDepartment of Chemistry, Faculty of Science and Engineering, Chuo Uni6ersity, Kasuga, Bunkyo-ku, Tokyo 112-0003, Japan

Abstract

Enantiopure planar-chiral cyclopentadienylruthenium–vinylidene complexes, (S_Cl)- and (R_C1)-[(h⁵-C₅H₂-1-COR¹-2-Me-4-

R²)Ru(PPh₃)₂(ꢀCꢀCHR³)][PF₆] (4: R¹=O-(l)- and O-(d)-menthyl; 8: R¹=NH^tBu. R²=Me, Ph; R³=Ph, H), were synthesized

1

starting from [(h⁵-C₅H₂-1-COR¹-2-Me-4-R²)Ru(h⁶-C₆H₆)][PF₆], and characterized by optical and spectra methods including H,

¹³C, and ³¹P-NMR, and CD spectra. The reaction rate of [(h⁵-C₅H₂-1-CO₂Et-2,4-Me₂)Ru(PPh₃)₂(MeCN)₃][PF₆] with pheny-

lacetylenes leading to vinylidene complexes increases in the order: HCCC₆H₄NO₂BHCCC₆H₅BHCCC₆H₄OMe. Analysis by

t

cyclic voltammetry showed that trisubstituted cyclopentadienyl ligands C₅H₂-1-CO₂Et-2-Me-4-R²(R²=Me, Ph, Bu, Naph etc.)

act as a weak electron-donor compared with non-substituted cyclopentadienyl one in ruthenium–phenylacetylide complexes.

Keywords: Planar chiral; Enantiomer; Cyclopentadienyl; Vinylidene complexes; Ruthenium

oraganometallic complexes from neutral compounds

like phosphines. The efﬁciency of planar-chiral cyclo-

pentadienyl complexes has proved particularly valuable

in the asymmetric Diels–Alder reactions and the poly-

merization of oleﬁns by early transition metal catalysts

[3,6]. In contrast to early transition metals few studies

on planar-chiral cyclopentadienyl complexes of late

transition metals have been made [4], except extremely

stable planar-chiral ferrocene [2] and ruthenocene [7]

derivatives. Half-sandwich complexes of such late tran-

sition metals having a piano-stool structure, however,

may be expected to show high catalytic activities. In-

deed, some cyclopentadieyl-iron and -ruthenium com-

plexes of a half-sandwich structure are known to

behave as an effective catalyst in organic reactions [8].

Among reactive ruthenium complexes we were inter-

ested in ruthenium vinylidene complexes, carbene re-

lated species, since they have been proposed as key

intermediates in a number of catalytic transformations

involving terminal alkynes [9]. Previously we have

shown synthetic methods [10] for planar-chiral cy-

clopentadienyl complexes of late transition metals such

as iron, cobalt, rhodium, and ruthenium. Now we have

expanded the method to the synthesis of planar-chiral

1. Introduction

Most of optically active organometallic catalysts con-

ventionally used in asymmetric organic syntheses con-

tain, as their chiral sources, chiral ligands in which the

chirality is based mainly on carbon-centered or axial

chirality as seen in many examples of chiral phosphine,

amine, acid, and alcohol ligands [1]. However, there

have been few applications of planar chirality as a

chiral source to optically active catalysts [2–4] although

planar chirality is characteristic of organometallic p-

complexes [5] such as p-oleﬁn, -cyclopentadienyl, and

-arene complexes. In particular, planar-chiral cyclopen-

tadienyl–metal complexes may be a promising candi-

date as a novel chiral catalyst for asymmetric organic

syntheses because racemization arising from a change

in coordination mode from h⁵into h¹or dissociation of

the cyclopentadienyl ligand is unlikely to occur, there-

fore, rigid asymmetric environment can be kept at the

metal center. In addition a cyclopentadienyl ligand is

an anionic one and forms a different family of chiral

* Corresponding author.

E-mail address: takahashi@sanken.osaka-u.ac.jp (S.Takahashi).

PII: S0022-328X(00)00736-1

602

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

cyclopentadienylruthenium–vinylidene complexes, and

successfully obtained them as an enantiopure form.

Herein we report the synthesis and characterization of

enantiopure planar-chiral (trisubstituted cyclopentadi-

enyl)ruthenium complexes bearing a vinylidene ligand

as well as the electronic property of the trisubstituted

cyclopentadienyl ligand in comparison with non-substi-

tuted- (Cp) and pentamethyl-cyclopentadienyl (CMe₅)

ones.

2. Results and discussion

Scheme 1.

The planar-chiral cyclopentadienylruthenium–vinyli-

dene complexes (4 and 8) have been synthesized from

the reactions outlined in Scheme 1.

Since separation of a diastereo mixture as well as

optical resolution of a racemic mixture of planar-chiral

cyclopentadienylruthenium–vinylidene complexes was

difﬁcult mainly due to low crystallinity and stability, we

choose stepwise transformation to the optically active

ruthenium-vinylidene complexes starting from (S_Cl)- or

(R_C1)-planar-chiral (h⁵-trisubstituted cyclopentadi-

enyl)ruthenium(h⁶-benzene) hexaﬂuorophosphate [(h⁵-

C₅H₂-1-COR¹-2-Me-4-R²)Ru(h⁶-C₆H₆)][PF₆] (1) which

was prepared in an optically pure form by a convenient

method developed previously [10c]. According to the

synthetic route, irradiation to enantiopure complex 1a-

1 (S_Cl, R¹=O-(l)-menthyl, R²=Me) with UV light in

acetonitrile caused the dissociation of a benzene ligand

to give an acetonitrile-coordinated complex, (S_Cl)-[(h⁵-

C₅H₂-1-COR¹-2,4-Me₂)Ru(MeCN)₃][PF₆] (2a-1: R¹=

O-(l)-menthyl) [11]. During this ligand exchange

reaction, dissociation and re-coordination of the pla-

nar-chiral cyclopentadienyl ligand resulting in a racem-

ization of planar chirality did not occur at all, and

optically pure complex 2a-1 was isolated in an almost

quantitative yield (Scheme 2). Similar treatment of

(R_C1)-[(h⁵-C₅H₂-1-COR¹-2,4-Me₂)Ru(h⁶-C₆H₆)][PF₆]

(1a-2: R¹=O-(d)-menthyl) gave (R_C1)-[(h⁵-C₅H₂-1-

COR¹-2,4-Me₂)Ru(MeCN)₃][PF₆] (2a-2), and tris(ace-

tonitrile) complexes 2a-1 and 2a-2 were conﬁrmed to be

a pair of enanitomers by optical and spectral analyses.

Then, we reacted tris(acetonitrile) complex 2a-1 with

two equivalents of triphenylphosphine in dichloro-

methane to afford bis(triphenylphosphine) complex,

(S_Cl)-[(h⁵-C₅H₂-1-COR¹-2,4-Me₂)Ru(PPh₃)₂(MeCN)]-

[PF₆] (3a-1: R¹=O-(l)-menthyl), in a good yield, in

which two molecules of acetonitrile ligands were re-

placed by triphenylphosphine, and even use of a large

excess of the phosphine did not give tris(triphenylphos-

phine)

derivative

[(h⁵-C₅H₂-1-COR¹-2,4-Me₂)Ru-

(PPh₃)₃][PF₆], but formed bis(triphenylphosphine) one

(3) as a sole product, in which one acetonitrile ligand

remains on the ruthenium. An R isomer, (R_C1)-[(h⁵-

Scheme 2.

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

603

Table 1

It is well known that neutral and cationic cyclopenta-

dienylruthenium(II) complexes are converted to ruthe-

nium-vinylidene complexes by treatment of terminal

acetylenes [9a,b,12]. The conversion of the neutral com-

plexes requires a scavenger for removing halogen lig-

ands, however cationic ruthenium complexes produce

vinylidene complexes by simply mixing with acetylenes

in an appropriate solvent. We performed the reaction

of 3 with the acetylenes to obtain the ﬁrst planar-chiral

Optical rotation, melting point and CꢀC stretching of vinylidene

complexes

Entry Complex Optically

rotation (°) ^a

Melting point

(°C)

w_CꢀC

b

(cm⁻¹

)

1

2

3

4

5

6

7

8

4a-1

4a-2

4b-1

4b-2

8a-1

8a-2

9a-1

9a-2

9b-1

9b-2

10a-1

10a-2

15

−46.4 (c 0.347)

+46.4 (c 0.300)

−42.5 (c 0.258)

+42.5 (c 0.283)

+10.5 (c 0.418)

−10.4 (c 0.431)

−76.9 (c 0.200)

+76.5 (c 0.200)

−34.3 (c 0.255)

+34.8 (c 0.287)

+22.3 (c 0.235)

−22.3 (c 0.200)

138–139

137–138

119–120

142–143

152–153

113–114

105–110 (dec.)

1626

1650

1624

1626

1627

1624

1623

1622,

1640

1616

cyclopentadienylruthenium–vinylidene

complexes.

Thus, complex 3a-1 was reacted with ten equivalents of

phenylacetylene in dichlomethane at room temperature

for 18 h. The solution turned from yellow to red in

color suggesting the formation of a vinylidene complex.

Addition of hexane to the dichloromethane solution

caused precipitation of vinylidene complex 4a-1, (S_Cl)-

[(h⁵-C₅H₂-1-COR¹-2,4-Me₂)Ru(PPh₃)₂(ꢀCꢀCHPh)][PF₆]

(R¹=O-(l)-menthyl), as red solids. Similarly, R_C1iso-

mer 4a-2 was prepared from 3a-2 (Scheme 2). Optically

active vinylidene complexes 4a-1 and 4a-2 were charac-

terized by optical and spectral methods. The IR and

NMR spectra of 4a-1 were identical with those of 4a-2

(Tables 1 and 2). They showed the CꢀC stretching

vibration in the IR spectra at 1626 cm⁻¹which is

within the normal region reported for ruthenium vinyli-

dene complexes [12,13]. In the ¹³C-NMR spectra, 4a-1

9

10

11

12

13 ^c

14 ^d

190 (dec.)

d

^aIn CH₃CN.

^bKBr disc.

^cSee Ref. [12].

^dComplex: [(h⁵-C₅Me₅)Ru(PPh₃)₂(ꢀCꢀCH₂)][PF₆]. See Ref. [13].

C₅H₂-1-COR¹-2,4-Me₂)Ru(PPh₃)₂(MeCN)][PF₆] (3a-2:

R¹=O-(d)-menthyl), was similarly prepared from 2a-2.

Complexes 3a were identiﬁed by means of optical and

spectral analyses. They showed optical rotations with

the same absolute value, but with an opposite sign each

other. Enantiomer 3a-1 exhibited the same ³¹P-NMR

spectrum as 3a-2, showing two sets of doublet signals at

37.6 and 43.2 ppm due to diastereotopic phosphorus

ligands (see Section 3).

and 4a-2 exhibited an apparent triplet signal (J_PꢁC

=

15.1 Hz) attributable to the a–C of vinylidene ligand at

356.9 ppm in a very low ﬁeld. It is well recognized that

the carbon resonance due to RuꢀC appears at such a

low ﬁeld and this strongly deshielded resonance for

a–C is a characteristic feature of vinylidene complexes

[14,15d], clearly indicating that 4a contains a vinylidene

moiety.

Table 2

¹³C Chemical shift of vinylidene a-carbon and ³¹P chemical shift of vinylidene complexes

^aEntry

Complex

¹³C Chemical shift (ppm)

³¹P Chemical shift (ppm)

1

2

3

4

5

6

7

8

4a-1

4a-2

4b-1

4b-2

8a-1

8a-2

9a-1

9a-2

9b-1

9b-2

10a-1

10a-2

356.90 (t, J_PꢁC=15.1 Hz)

356.95 (t, J_PꢁC=15.1 Hz)

363.66 (t, J_PꢁC=17.1 Hz)

363.68 (t, J_PꢁC=18.2 Hz)

358.54 (t, J_PꢁC=15.3 Hz)

352.31 (t, J_PꢁC=17.1 Hz)

352.33 (t, J_PꢁC=17.1 Hz)

355.90 (t, J_PꢁC=19.2 Hz)

355.99 (t, J_PꢁC=18.1 Hz)

352.85 (t, J_PꢁC=17.0 Hz)

358.9 (t, J_PꢁC=24.0 Hz) ^b

349.94 (t, J_PꢁC=15.2 Hz)

37.56 (d, J_PꢁP=27.9 Hz), 43.16 (d, J_PꢁP=27.8 Hz)

37.54 (d, J_PꢁP=27.9 Hz), 43.16 (d, J_PꢁP=27.9 Hz)

31.87 (d, J_PꢁP=26.6 Hz), 45.58 (bs)

31.80 (d, J_PꢁP=26.0 Hz), 45.55 (bs)

42.40 (d, J_PꢁP=27.3 Hz), 44.91 (d, J_PꢁP=28.1 Hz)

42.38 (d, J_PꢁP=27.3 Hz), 44.89 (d, J_PꢁP=28.3 Hz)

38.43 (d, J_PꢁP=28.1 Hz), 45.61 (d, J_PꢁP=28.2 Hz)

38.43 (d, J_PꢁP=28.1 Hz), 45.62 (d, J_PꢁP=28.1 Hz)

35.17 (d, J_PꢁP=26.3 Hz), 44.51 (bs)

9

10

11

12

13

14 ^c

35.17 (d, J_PꢁP=25.9 Hz), 44.50 (bs)

36.78 (d, J_PꢁP=28.4 Hz), 46.20 (d, J_PꢁP=28.8 Hz)

36.75 (d, J_PꢁP=28.9 Hz), 46.21 (d, J_PꢁP=28.8 Hz)

43.00 (s)

15

c

49.37 (s)

^aIn CDCl₃.

^bSee Ref. [12].

^cComplex: [(h⁵-C₅Me₅)Ru(PPh₃)₂(ꢀCꢀCH₂)][PF₆], in CD₃CN. See reference [13].

604

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

Fig. 1. CD spectra of ruthenium complexes 4a and 9a.

Complexes 4a-1 and 4a-2 showed the same melting

phine to give bis(triphenylphosphine)(acetonitrile)

complexes 7a-1 and 7a-2, respectively. Treatment of

these complexes with phenylacetylene yielded planar-

chiral vinylidene complexes (S_Cl)- and (R_C1)-[(h⁵-C₅H₂-

1-CONH^tBu-2,4-Me₂)Ru(ꢀCꢀCHPh)][PF₆] 8a, which

have fully been identiﬁed by optical and spectral analy-

ses (Tables 1 and 2, Fig. 2).

point at 138–139°C, and the same absolute value in

optical rotation with an opposite sign: [h]_D: −46.3° for

4a-1, +46.4° for 4a-2 in an acetonitrile solution. The

circular dichroisum (CD) spectra of them are mirror

symmetrical each other in all ranges (Fig. 1). A careful

NMR experiment showed that the samples of 4a-1 and

4a-2 were not contaminated with impurities such as

their diastereomers (R_C1)-[(h⁵-C₅H₂-1-COR¹-2,4-Me₂)-

Ru(PPh₃)₂(ꢀCꢀCHPh)][PF₆] (R¹=O-(l)-menthyl) and

(S_Cl)-[(h⁵-C₅H₂-1-COR¹-2,4-Me₂)Ru(PPh₃)₂(ꢀCꢀCH-

Ph)][PF₆] (R¹=O-(d)-menthyl), unequivocally indicat-

ing that 4a-1 and 4a-2 are a pair of enantiomers.

Optically active phenyl-substituted analogs (S_Cl)- and

(R_C1)-4b (R²=Ph) were similarly prepared from (S_Cl)-

and (R_C1)-[(h⁵-C₅H₂-1-COR¹-2-Me-4-Ph)Ru(h⁶-C₆H₆)]-

[PF₆] (1b: R¹=O-(l)- and O-(d)-menthyl), respectively,

via tris(acetonitrile) complex 2b (R²=Ph) and then

There have appeared several papers dealing with

mechanistic studies on the transformation of vinylide-

nes from terminal acetylenes [15], but a few reporting

the effect of acetylene substituents on the transforma-

tion reaction [15d]. The reaction of 3a-1 with

trimethylsilylacetylene, HCCSiMe₃, caused the cleavage

of the CꢁSi bond to form a non-substituted vinylidene

complex, (S_Cl)-[(h⁵-C₅H₂-1-COR¹-2,4-Me₂)Ru(PPh₃)₂-

(ꢀCꢀCH₂)][PF₆] (9a-1: R¹=O-(l)-menthyl), as often ob-

served in some cases [13]. Similarly, planar-chiral vinyl-

idene complexes 9a-2, 9b-1, and 9b-2 were obtained in

an enantiopure form from the reactions of 3a-2, 3b-1,

and 3b-2, respectively, with trimethylsilylacetylene.

Complexes 7a bearing an amide group on a cyclopenta-

dienyl ligand underwent the same reaction with

trimethylsilylacetylene as 3a and formed optically pure

10a (Fig. 3). Methyl propionate, HCCCO₂Me, which is

a strong electron-acceptor, reacted with 3a to give a

complex mixture, from which no deﬁnite product was

isolated. To know the substituent effect of acetylenes in

somewhat details, the reaction rates of [(h⁵-C₅H₂-1-

COR¹-2,4-Me₂)Ru(PPh₃)₂(MeCN)][PF₆] (11a: R¹=

bis(triphenylphosphine)(acetonitrile)

complexes

3b

(R²=Ph).

Vinylidene complexes 4a and 4b carry two chiral

elements, i.e. a planar chirality and a carbon-centered

chirality in the menthyl group, in a molecule. We have

also synthesized optically active cyclopentadienylruthe-

nium–vinylidene complexes possessing only planar chi-

rality. In this case we used, as a starting material,

planar-chiral (S_Cl)- and (R_C1)-[(h⁵-C₅H₂-1-CONH^tBu-

2-Me-4-R²)Ru(h⁶-C₆H₆)][PF₆] (5) (Scheme 1). Enan-

tiomers, (S_Cl)-5a-1 (R²=Me) and (R_C1)-5a-2 (R²=Me)

were prepared from (S_Cl)-1a-1 and (R_C1)-1a-2, respec-

tively, via hydrolysis of the menthyl groups followed by

condensation with tert-butylamine as reported previ-

ously [10b,c]. Enantiopure [(h⁵-C₅H₂-1-CONH^tBu-2,4-

Me₂)Ru(h⁶-C₆H₆)][PF₆] (5a-1) (S_Clisomer) and 5a-2

(R_C1isomer) were irradiated with UV light in acetoni-

trile [11], followed by the reaction of triphenylphos-

OEt) with phenylacetylene derivatives bearing

a

substituent at the 4-position of the phenyl ring were

monitored by a ³¹P-NMR spectroscopy Eq. (1). The

experiment was performed using a racemic mixture of

11a at 25°C and the formation rate of vinylidene com-

plexes 12a was traced by ³¹P-NMR.

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

605

Fig. 2. CD spectra of ruthenium complexes 8a and 10a.

(trisubstituted cyclopentadienyl)ruthenium-vinylidene

complexes can be dissolved in warm methanol, but do

not show any reactivities toward methanol. Even with

oxygen gas these complexes do not react, although a

cyclopentadienylruthenium–vinylidene complex is con-

verted to a cyclopentadienylruthenium(carbonyl) com-

plex by the action of O₂[18].

(1)

The result (Fig. 4) showed that among phenylacetylene

derivatives 4-RC₆H₄CCH (R=H, OMe, and NO₂) em-

ployed in this experiment, 4-methoxyphenylacetylene

reacted with 11a faster than phenylacetylene to give

vinylidene complex 12a, whereas the reaction of 4-ni-

trophenylacetylene proceeded slower than that of

phenylacetylene. These results suggest that acetylenes

having an electron-donating substituent show a higher

reactivity toward 11a giving vinylidene complexes 12a,

and the same order in the reactivity of acetylenes was

observed in the reactions of non-substituted cyclopenta-

dienylruthenium analog 14 [16]. This is a reverse ten-

dency in the substituent effect as compared with the

case of cobalt complexes [15b]. The trisubstituted cy-

clopentadienylruthenium complexes react with phenyl-

acetylene slower than non-substituted cyclopenta-

dienylruthenium analog, implying that steric bulkiness

and/or weaker electron-donating nature (vide infra) of

the trisubstituted cyclopentadienyl ligand causes a

slower reaction leading to vinylidene complexes.

Previously we reported a novel catalysis of cationic

[CpRu(MeCN)₃]⁺, by which norbornene undergoes a

cyclopropanation with propargyl alcohol [19]. Toward

this novel transformation of propargyl alcohol, the

trisubstituted cyclopentadienylruthenium catalysts, for

example, [(h⁵-C₅H₂-1-COR¹-2,4-Me₂)Ru(MeCN)₃][PF₆]

(2a) exhibited a higher activity than both C₅H₅Ru and

C₅Me₅Ru analogs. The reaction was thought to pro-

ceed via ruthenium-alkylidene or ruthenacyclopentene

as a key intermediate. In this connection, we attempted

to evaluate the effect of trisubstituted cyclopentadienyl

ligand on the RuꢀCꢀC moiety in [(h⁵-C₅H₂-1-COR¹-

The planar-chiral vinylidene complexes prepared in

the present work are thermally stable and show a

deﬁnite melting point without decomposition (Table 1),

although C₅H₅and C₅Me₅analogs are known to melt

being accompanied with decomposition [12,13]. Our

trisubstituted cyclopentadienylruthenium complexes are

soluble in polar organic solvents such as dichloro-

methane, acetone, and acetonitrile, but insoluble in

hexane, benzene, and diethylether. Ruthenium-vinyli-

dene complexes commonly react with methanol to give

methoxycarbene complexes [17], whereas the present

Fig. 3. A pair of enantiopore planar-chiral cyclopentadienylruthe-

nium–vinyliedene compleces 8 and 10.

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Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

Fig. 4. Reaction rates of ruthenium complexes 11a with phenylacetylene derivatives HCCC₆H₄R. —ꢀ—: R=MeO; —"—: R=H; —ꢁ—:

R=NO₂; — —: The reaction of complex 14 with HCCC₆H₅.

2,4-Me₂)Ru(PPh₃)₂(ꢀCꢀCHR)][PF₆] (4 and 8). The

donor-acceptor properties of the trisubstituted cyclo-

pentadienyl ligand were estimated in comparison with

C₅H₅and C₅Me₅, by means of spectral analyses; for

example, the CꢀC stretching vibration of vinylidene was

measured by IR, and the P and C chemical shifts of

phosphine ligand and a-C in the alkylidene ligand by

NMR. The data obtained are summarized in Tables 1

and 2 along with those of C₅H₅and C₅Me₅analogs.

The CꢀC stretching vibration of the complexes ap-

peared around 1625 cm⁻¹in the IR spectra and is

almost unaffected by the substituents on cyclopentadi-

enyl ligand except 4b and even by those on the vinyli-

dene ligand. The C₅Me₅complex showed the

absorption at 1616 cm⁻¹, suggesting that increase in

the electron-donating property of C₅Me₅causes a slight

shift of the absorption to a lower wavenumber in the

comparison with a C₅H₅analog. In ¹³C-NMR spectra

all the complexes listed in Table 2 showed the charac-

teristic low-ﬁeld resonances (352–364 ppm) attributable

to the a–C of RuꢀCꢀC species. However, no signiﬁcant

inﬂuence by the substituents on the a–C chemical shift

were observed and even the C₅Me₅complex exhibited

the resonance at 350 ppm. In ³¹P-NMR spectra the

planar-chiral complexes showed two doublets due to

diastereotopic phosphorus ligands in the region of

36.8–46.2 ppm except 4b and 9b. Complexes 4b and 9b,

both of which bear a phenyl group on the cyclopentadi-

enyl ligand, similarly showed two phosphorus reso-

nances, but one of the two appeared as an apparent

broad signal. This anomaly would presumably be due

to an inﬂuence of the p-electron system of the phenyl

group on a cyclopentadienyl ligand, and some unsuc-

cessful attempts to determine the stereo structure of the

complexes were made. The C₅H₅and C₅Me₅complexes

exhibited resonance at 43 and 49 ppm, respectively. On

the basis of such a little difference in phosphorus

chemical shifts as well as the through-space inﬂuence of

a phenyl group the substitutent effect on the metal can

not be discussed. The spectral analyses chosen here

seem to be obtuse for estimating the electronic property

of the trisubstituted cyclopentadienyl ligands. Therefore

we electrochemically analyzed the central metal, Ru,

directly bound to a cyclopentadienyl ligand. Unfortu-

nately the cyclic voltamograms of the vinylidene com-

plexes did not show a deﬁnite oxidation potential, and

the Ru-vinylidene complexes were transformed into

stable Ruꢁacetylide complexes 13 by treatment with

alumina Eq. (2). Complexes 13 showed quasi-reversible

waves in cyclic voltamograms and the results are sum-

marized in Table 3 along with the data obtained from

(h⁵-C₅H₅)Ru(PPh₃)₂(CCPh) (16) and (h⁵-C₅Me₅)Ru-

(PPh₃)₂(CCPh) (17).

The oxidation potential (E_pa) of complex 13a was

observed at a potential higher than those of complexes

16 and 17, indicating that the trisubstituted cyclopenta-

(2)

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

607

1

dienyl ligand bearing one ethoxycarbonyl and two

methyl groups has an weaker electron-donating poperty

than a C₅H₅ligand. To examine in somewhat detail the

effect of substituents, we also prepared complexes 13b–

e bearing phenyl, tert-butyl, a-naphthyl and 4-bro-

LA600 and Bruker ARX400 spectrometers. In H and

¹³C-NMR, SiMe₄was used as an internal standard, and

an external 85% H₃PO₄reference was used for ³¹P-

NMR. IR spectra were obtained on Perkin-Elmer sys-

tem 2000 FT-IR, FAB mass spectra on a JEOL

JMS-600H instrument. Optical rotations and CD spec-

tra were measured on JASCO DIP-1000 and JASCO

J-725 instruments, respectively. Cyclic voltammograms

were recorded on BAS 100 B/W (CV-50) in CH₂Cl₂

solutions of 0.1 M n-Bu₄NPF₆, and the scan rate was

0.1 V s⁻¹. CV cells were ﬁtted with Pt working elec-

trodes, Pt wire counter electrodes, and Ag/Ag⁺refer-

ence electrodes. All potentials were represented versus

Cp₂Fe/Cp₂Fe⁺(+0.19 V vs. Ag/Ag⁺), which were

obtained by the measurement of ferrocene under the

same conditions. Elemental analyses were performed by

the Material Analysis Center, ISIR, Osaka University.

mophenyl groups on

a

cyclopentadienyl ligand.

Complexes 13b–e showed similar voltamograms (Table

3), and among complexes 13a–e the highest oxidation

potential was observed for 13e having a 4-BrC₆H₄

group, whereas the lowest potential for a t-butyl group.

The same tendency was also observed for the reduction

potentials (E_pc). Based on these results, we may esti-

mate the donor-acceptor properties of cyclopentadienyl

ligands in the ruthenium complexes, that is, the elec-

tron-donating property increases in the order, 4-(4-

BrC₆H₄)-Cp%B4-a-Naphthyl-Cp%

ꢀ

4-Ph-Cp%B4-

Me-Cp%B4-^tBu-Cp%ꢁC₅H₅ꢁC₅Me₅(Cp%=1-CO₂Et-

2-MeC₅H₂). It should be noted that the delicate control

of electron-donating property of 1-COR¹-2-Me-4-R²-

C₅H₂ligands may be attained by the choice of sub-

stituent R².

3.2. Syntheses of planar-chiral trisubstituted

cyclopentadienylrutheniumtris(acetonitrile) complexes

(2)

3.2.1. (S_Cl)-[{p⁵-C₅H₂-1-(CO₂-(l)-menthyl)-

2,4-Me₂}Ru(MeCN)₃][PF₆] (2a-1)

Table 3

Redox potentials of complexes 13a–e, 16 and 17 ^a

Ruthenium complex (S_Cl)-[{h⁵-C₅H₂-1-(CO₂-(l)-men-

thyl)-2,4-Me₂}Ru(h⁵-C₆H₆)][PF₆] (1a-1) (0.19 g, 0.32

mmol) was dissolved in MeCN (50 ml) under an argon

atmosphere and the solution was irradiated with ultra-

violet light for 18 h. Removal of the solvent under

reduced pressure gave ruthenium complex 2a-1 (0.20 g,

99% yield) as an orange powder. IR (cm⁻¹, KBr): 839

Entry

Complex

E_pc(V)

E_pa(V)

1

2

3

4

5

6

7

13a

13b

13c

13d

13e

16

0.24

0.25

0.21

0.26

0.30

0.14

−0.05

0.32

0.36

0.30

0.34

0.38

0.23

0.03

1

(w_PꢁF), 1705 (w_CꢀO). H-NMR (CD₃CN, 400 MHz): l

17

0.76 (d, J=6.8 Hz, 3H, menthylꢁCH₃), 0.89 (d, J=5.9

Hz, 6H, menthylꢁCH₃), 0.93–1.12 (m, 2H, menthyl),

1.38–1.54 (m, 2H, menthyl), 1.65–1.69 (m, 2H, men-

thyl), 1.70 (s, 3H, CpꢁCH₃), 1.89 (s, 3H, CpꢁCH₃), 1.93

(s, 9H, NCCH₃), 4.07 (s, 1H, CpꢁH), 4.66 (s, 1H,

CpꢁH), 4.72 (dt, J=4.4, 10.8 Hz, 1H, menthyl). ¹³C-

NMR (CD₃CN, 100 MHz): l 12.51 (s), 13.26 (s), 16.68

(s), 21.30 (s), 22.37 (s), 24.06 (s), 27.12 (s), 32.21 (s),

34.97 (s), 41.77 (s), 48.06 (s), 62.57 (s), 68.63 (s), 74.53

(s), 74.97 (s), 88.14 (s), 97.70 (s), 126.20 (s), 170.57 (s).

FAB MS: m/z 500 (M⁺ꢁPF₆). Mp: 120–121°C. [h]²_D⁰:

−63.3° (c 0.453, MeCN). Calc. for C₂₄H₃₆F₆N₃O₂PRu:

C, 44.64; H, 5.62; N, 6.51. Anal. Found: C, 44.71; H,

5.41; N, 6.60.

^aIn 0.1 M ⁿBu₄NPF₆ꢁCH₂Cl₂at 0.1 V s⁻¹. Ferrocene: DE_1/2=+

0.19, I_pa¥2I_pc

.

3. Experimental

3.1. General

All reactions were carried out under an argon atmo-

sphere, but the work up was performed in air. CH₂Cl₂

was dried over calcium hydride and then distilled.

Other chemicals commercially available were used with-

out further puriﬁcation. Planar-chiral [(h⁵-trisubstituted

cyclopentadienyl)ruthenium(h⁶-benzene)][PF₆]

com-

plexes, (S_Cl)- and (R_C1)-[(h⁵-C₅H₂-1-COR¹-2-Me-4-R²)-

Ru(h⁶-C₆H₆)][PF₆], (R¹=O-(l)-menthyl, O-(d)-men-

thyl, NH^tBu; R²=Me, Ph) [10b,c], [(h⁵-C₅H₅)Ru-

(PPh₃)₂(MeCN)][PF₆] [16], (h⁵-C₅H₅)Ru(PPh₃)₂(CCPh)

[12], and (h⁵-C₅Me₅)Ru(PPh₃)₂(CCPh) [13] were pre-

pared according to the methods reported by us and

others.

3.2.2. (R_C1)-[{p⁵-C₅H₂-1-(CO₂-(d)-menthyl)-

2,4-Me₂}Ru(MeCN)₃][PF₆] (2a-2)

This compound was prepared from 1a-2 by the

method similar to that for 2a-1 (99%, orange powder).

IR (cm⁻¹, KBr): 840 (w_PꢁF), 1706 (w_CꢀO). ¹H-NMR

(CD₃CN, 400 MHz): l 0.76 (d, J=7.1 Hz, 3H, men-

thylꢁCH₃), 0.89 (d, J=6.0 Hz, 6H, menthylꢁCH₃),

0.94–1.14 (m, 2H, menthyl), 1.38–1.54 (m, 2H, men-

thyl), 1.65–1.69 (m, 2H, menthyl), 1.70 (s, 3H,

Melting points were measured on Yamato melting

point apparatus mode MP 21 and are corrected. NMR

spectra were taken on JEOL JNM-LA400, JEOL JNM-

608

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

CpꢁCH₃), 1.89 (s, 3H, CpꢁCH₃), 1.93 (s, 9H, NCCH₃),

4.07 (s, 1H, CpꢁH), 4.66 (s, 1H, CpꢁH), 4.72 (dt,

J=4.4, 10.9 Hz, 1H, menthyl). ¹³C-NMR (CD₃CN,

100 MHz): l 12.51 (s), 13.25 (s), 16.64 (s), 21.28 (s),

22.35 (s), 24.02 (s), 27.09 (s), 32.19 (s), 34.95 (s), 41.75

(s), 48.04 (s), 62.55 (s), 68.60 (s), 74.51 (s), 74.94 (s),

88.15 (s), 97.72 (s), 126.21 (s), 170.56 (s). FAB MS: m/z

500 (M⁺ꢁPF₆). Mp: 120–121°C. [h]²_D⁰: +64.0° (c 0.371,

MeCN). Calc. for C₂₄H₃₆F₆N₃O₂PRu: C, 44.64; H,

5.62; N, 6.51. Anal. Found: C, 44.85; H, 5.41; N, 6.54.

3.3. Syntheses of planar-chiral trisubstituted

cyclopentadienylrutheniumtris(acetonitrile)

bis(triphenylphosphine) complexes (3)

3.3.1. (S_Cl)-[{p⁵-C₅H₂-1-(CO₂-(l)-menthyl)-

2,4-Me₂}Ru(PPh₃)₂(MeCN)][PF₆] (3a-1)

A

mixture of 2a-1 (0.20 g, 0.32 mmol) and

triphenylphosphine (0.16 g, 0.64 mmol) in CH₂Cl₂(30

ml) was stirred at room temperature for 12 h. After

concentration of the reaction mixture under reduced

pressure, the solution was chromatographed on Al₂O₃

with CH₂Cl₂:acetone=3:1. The eluent was evaporated

and dried in vacuo to give 3a-1 (0.33 g, 98% yield) as a

yellow powder. IR (cm⁻¹, KBr): 840 (w_PꢁF), 1702

3.2.3. (S_Cl)-[{p⁵-C₅H₂-1-(CO₂-(l)-menthyl)-2-

Me-4-Ph}Ru(MeCN)₃][PF₆] (2b-1)

1

(w_CꢀO). H-NMR (CDCl₃, 400 MHz): l 0.73 (d, J=6.8

This compound was prepared from 1b-1 by the

method similar to that for 2a-1 (99%, orange powder).

IR (cm⁻¹, KBr): 840 (w_PꢁF), 1712 (w_CꢀO). ¹H-NMR

(CD₃CN, 600 MHz): l 0.78 (d, J=7.0 Hz, 3H, men-

thylꢁCH₃), 0.91 (d, J=7.0 Hz, 6H, menthylꢁCH₃),

1.02–1.15 (m, 2H, menthyl), 1.44–1.51 (m, 2H, men-

thyl), 1.67–1.71 (m, 2H, menthyl), 1.93 (s, 9H,

NCCH₃), 2.03 (s, 3H, CpꢁCH₃), 4.68 (s, 1H, CpꢁH),

4.80–4.84 (m, 1H, menthyl), 5.35 (d, J=1.6 H, 1H,

CpꢁH), 7.34–7.36 (m, 3H, Ph), 7.45–7.46 (m, 2H, Ph).

¹³C-NMR (CD₃CN, 150 MHz): l 13.43 (s), 16.74 (s),

21.24 (s), 22.34 (s), 24.06 (s), 27.29 (s), 32.23 (s), 34.96

(s), 42.11 (s), 48.21 (s), 62.91 (s), 64.98 (s), 74.88 (s),

88.99 (s), 99.72 (s), 126.47 (s), 127.94 (s), 129.27 (s),

129.73 (s), 133.94 (s), 170.16 (s). FAB MS: m/z 562

(M⁺ꢁPF₆). Mp: 82–83°C. [h]²_D⁰: −220.1° (c 0.186,

MeCN). Calc. for C₂₉H₃₈F₆N₃O₂PRu: C, 49.21; H,

5.42; N, 5.94. Anal. Found: C, 49.48; H, 5.21; N, 5.75.

Hz, 3H, menthylꢁCH₃), 0.81 (d, J=6.8 Hz, 3H, men-

thylꢁCH₃), 0.85–1.10 (m, 2H, menthyl), 0.96 (d, J=6.3

Hz, 3H, menthylꢁCH₃), 1.24 (s, 3H, CpꢁCH₃), 1.23–

1.33 (m, 2H, menthyl), 1.42–1.61 (m, 1H, menthyl),

1.66–1.73 (m, 3H, menthyl), 1.94 (d, J=2.0 Hz, 3H,

CpꢁCH₃), 1.94–2.00 (m, 1H, menthyl), 2.27 (s, 3H,

NCCH₃), 4.13 (s, 1H, CpꢁH), 4.56 (s, 1H, CpꢁH), 4.79

(dt, J=4.6, 10.7 Hz, 1H, menthyl), 6.80 (t, J=9.3 Hz,

6H, Ph), 7.10–7.45 (m, 24H, Ph). ¹³C-NMR (CDCl₃,

100 MHz): l 4.91 (s), 11.93 (s), 13.14 (s), 15.76 (s),

20.90 (s), 22.00 (s), 22.74 (s), 25.69 (s), 31.50 (s), 33.94

(s), 41.41 (s), 46.58 (s), 70.45 (s), 75.87 (s), 85.24 (s),

96.89 (d, J=3.3 Hz), 107.34 (s), 127.80–134.19 (m),

169.89 (s). ³¹P-NMR (CDCl₃, 160 MHz): l 39.63 (d,

J_PꢁP=32.8 Hz), 42.40 (d, J_PꢁP=32.7 Hz). FAB MS:

m/z 942 (M⁺ꢁPF₆). Mp: 120–121°C. [h]²_D⁰: −27.1° (c

0.360, MeCN). Calc. for C₅₆H₆₀F₆NO₂P₃Ru: C, 61.81;

H, 5.56; N, 1.29. Anal. Found: C, 61.79; H, 5.31; N,

1.35.

3.2.4. (R_C1)-[p⁵-C₅H₂-1-(CO₂-(d)-menthyl)-2-

3.3.2. (R_C1)-[{p⁵-C₅H₂-1-(CO₂-(d)-menthyl)-

Me-4-Ph}Ru(MeCN)₃][PF₆] (2b-2)

2,4-Me₂}Ru(PPh₃)₂(MeCN)][PF₆] (3a-2)

This compound was prepared from 1b-2 by the

method similar to that for 2a-1 (99%, orange powder).

IR (cm⁻¹, KBr): 840 (w_PꢁF), 1711 (w_CꢀO). ¹H-NMR

(CD₃CN, 600 MHz): l 0.78 (d, J=7.0 Hz, 3H, men-

thylꢁCH₃), 0.91 (d, J=6.8 Hz, 6H, menthylꢁCH₃),

1.01–1.15 (m, 2H, menthyl), 1.44–1.51 (m, 2H, men-

thyl), 1.67–1.71 (m, 2H, menthyl), 1.93 (s, 9H,

NCCH₃), 2.03 (s, 3H, CpꢁCH₃), 4.68 (s, 1H, CpꢁH),

4.80ꢁ4.84 (m, 1H, menthyl), 5.35 (d, J=1.6 H, 1H,

CpꢁH), 7.34–7.36 (m, 3H, Ph), 7.45–7.46 (m, 2H, Ph).

¹³C-NMR (CD₃CN, 150 MHz): l 13.43 (s), 16.80

(s), 21.27 (s), 22.38 (s), 24.12 (s), 27.32 (s), 32.26 (s),

35.00 (s), 42.14 (s), 48.25 (s), 62.99 (s), 64.98 (s),

74.88 (s), 88.99 (s), 99.69 (s), 126.46 (s), 127.98 (s),

129.29 (s), 129.74 (s), 134.00 (s), 170.12 (s). FAB MS:

m/z 562 (M⁺ꢁPF₆). Mp: 82–83°C. [h]²_D⁰: +220.2° (c

0.109, MeCN). Calc. for C₂₉H₃₈F₆N₃O₂PRu: C, 49.21;

H, 5.42; N, 5.94. Anal. Found: C, 49.38; H, 5.24; N,

5.68.

This compound was prepared from 3a-2 by the

method similar to that for 3a-1 (95%, yellow powder).

IR (cm⁻¹, KBr): 840 (w_PꢁF), 1702 (w_CꢀO). ¹H-NMR

(CDCl₃, 400 MHz): l 0.73 (d, J=6.8 Hz, 3H, men-

thylꢁCH₃), 0.81 (d, J=6.8 Hz, 3H, menthylꢁCH₃),

0.86–1.09 (m, 2H, menthyl), 0.96 (d, J=6.3 Hz, 3H,

menthylꢁCH₃), 1.24 (s, 3H, CpꢁCH₃), 1.23–1.33 (m,

2H, menthyl), 1.42–1.61 (m, 1H, menthyl), 1.66–1.73

(m, 3H, menthyl), 1.94 (d, J=2.2 Hz, 3H, CpꢁCH₃),

1.94–2.00 (m, 1H, menthyl), 2.27 (s, 3H, NCCH₃), 4.13

(s, 1H, CpꢁH), 4.56 (s, 1H, CpꢁH), 4.79 (dt, J=4.4,

10.9 Hz, 1H, menthyl), 6.80 (t, J=8.9 Hz, 6H, Ph),

7.09–7.45 (m, 24H, Ph). ¹³C-NMR (CDCl₃, 100 MHz):

l 5.00 (s), 11.97 (s), 13.20 (s), 15.79 (s), 20.94 (s), 22.05

(s), 22.78 (s), 25.72 (s), 31.55 (s), 34.00 (s), 41.45 (s),

46.63 (s), 70.48 (s), 75.91 (s), 85.23 (s), 96.91 (d, J=4.2

Hz), 107.36 (s), 127.81–134.15 (m), 170.00 (s). ³¹P-

NMR (CDCl₃, 160 MHz): l 39.67 (d, J_PꢁP=32.7 Hz),

42.46 (d, J_PꢁP=32.7 Hz). FAB MS: m/z 942 (M⁺ꢁPF₆).

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

609

M.p.: 120–121°C. [h]²_D⁰: +27.8° (c 0.304, MeCN). Calc.

for C₅₆H₆₀F₆NO₂P₃Ru: C, 61.81; H, 5.56; N, 1.29. Anal.

Found: C, 62.03; H, 5.63; N, 1.33.

7a-1. A solution of 5a-1 (0.35 g, 0.68 mmol) in MeCN

(50 ml) under an argon atmosphere was irradiated with

ultraviolet light for 18 h. After removal of the solvent

under reduced pressure, the residue was dissolved in

CH₂Cl₂. To the solution triphenylphosphine (0.36 g, 1.36

mmol) was added, and stirred at room temperature for

12 h. After concentration of the reaction mixture under

reduced pressure, the residue was chromatographed on

Al₂O₃with CH₂Cl₂:acetone=3:1. The eluate was evap-

orated and dried in vacuo to give 7a-1 (0.66 g, 97% yield)

as a yellow powder. IR (cm⁻¹, KBr): 842 (w_PꢁF), 1657

(w_CꢀO), 3416 (w_N–H). ¹H-NMR (CDCl₃, 400 MHz): l 1.27

(dd, J=1.5, 3.4 Hz, 3H, CpꢁCH₃), 1.33 (s, 9H,

ꢁC(CH₃)₃), 1.99 (d, J=2.0 Hz, 3H, CpꢁCH₃), 2.30 (s,

3H, NCCH₃), 3.71 (s, 1H, ꢁCONHꢁ), 4.44 (s, 1H,

CpꢁH), 4.85 (s, 1H, CpꢁH), 6.73 (t, J=18.2 Hz, 6H, Ph),

7.11–7.45 (m, 24H, Ph). ¹³C-NMR (CDCl₃, 100 MHz):

l 5.03 (s), 11.94 (s), 13.39 (s), 28.79 (s), 51.97 (s), 72.22

(s), 83.26 (d, J_PꢁC=7.4 Hz), 93.84 (d, J_PꢁC=5.8 Hz),

98.84 (d, J_PꢁC=4.0 Hz), 108.84 (d, J_PꢁC=2.5 Hz),

128.04–134.44 (m), 167.92 (s). ³¹P-NMR (CDCl₃, 160

MHz): l 39.53 (d, J_PꢁP=33.1 Hz), 42.54 (d, J_PꢁP=33.2

Hz). FAB MS: m/z 859 (M⁺ꢁPF₆). Mp: 135–136°C.

[h]²_D⁰: +12.1° (c 0.463, MeCN). Calc. for

C₅₀H₅₁F₆N₂OP₃Ru: C, 59.82; H, 5.12; N, 2.79. Anal.

Found: C, 59.90; H, 5.12; N, 2.90.

3.3.3. (S_Cl)-[{p⁵-C₅H₂-1-(CO₂-(l)-menthyl)-2-

Me-4-Ph}Ru(PPh₃)₂(MeCN)][PF₆] (3b-1)

This compound was prepared from 3b-1 by the method

similar to that for 3a-1 (97%, yellow powder). IR (cm⁻¹

,

1

KBr): 839 (w_PꢁF), 1700 (w_CꢀO). H-NMR (CDCl₃, 600

MHz): l 0.66 (d, J=7.1 Hz, 3H, menthylꢁCH₃), 0.81 (d,

J=7.1 Hz, 3H, menthylꢁCH₃), 0.90–0.96 (m, 2H, men-

thyl), 0.97 (d, J=6.4 Hz, 3H, menthylꢁCH₃), 1.05–1.10

(m, 2H, menthyl), 1.16–1.21 (m, 1H, menthyl), 1.40 (s,

3H, CpꢁCH₃), 1.52ꢁ1.75 (m, 4H, menthyl), 4.69ꢁ4.73 (m,

1H, menthyl), 4.72 (s, 1H, CpꢁH), 4.96 (s, 1H, CpꢁH),

6.57 (t, J=9.1 Hz, 6H, Ph), 7.06 (t, J=7.0 Hz, 6H, Ph),

7.22–7.55 (m, 23H, Ph). ¹³C-NMR (CDCl₃, 150 MHz):

l 4.83 (s), 13.10 (s), 16.47 (s), 20.50 (s), 22.15 (s), 23.60

(s), 26.40 (s), 31.46 (s), 31.70 (s), 41.52 (s), 46.46 (s), 69.50

(s), 75.87 (s), 80.80 (s), 92.84 (s), 109.83 (s), 127.68–

134.30 (m), 169.70 (s). ³¹P-NMR (CDCl₃, 160 MHz): l

38.62 (d, J_PꢁP=32.5 Hz), 42.04 (bs). FAB MS: m/z 1004

(M⁺ꢁPF₆). Mp: 132–133°C. [h]²_D⁰: −165.9° (c 0.300,

MeCN). Calc. for C₆₁H₆₂F₆NO₂P₃Ru: C, 63.69; H, 5.44;

N, 1.22. Anal. Found: C, 63.97; H, 5.48; N, 1.18.

3.3.4. (R_C1)-[{p⁵-C₅H₂-1-(CO₂-(d)-menthyl)-2-

Me-4-Ph}Ru(PPh₃)₂(MeCN)][PF₆] (3b-2)

3.3.6. (R_Cl)-[{p⁵-C₅H₂-1-(CONH^tBu)-2,4-

Me₂}Ru(PPh₃)₂(MeCN)][PF₆] (7a-2)

This compound was prepared from 3b-2 by the method

similar to that for 3a-1 (99%, yellow powder). IR (cm⁻¹

,

This compound was prepared from 5a-2 by the method

1

KBr): 839 (w_PꢁF), 1700 (w_CꢀO). H-NMR (CDCl₃, 600

MHz): l 0.67 (d, J=7.0 Hz, 3H, menthylꢁCH₃), 0.82 (d,

J=7.0 Hz, 3H, menthylꢁCH₃), 0.90–0.96 (m, 2H, men-

thyl), 0.98 (d, J=6.4 Hz, 3H, menthylꢁCH₃), 1.03–1.10

(m, 2H, menthyl), 1.19–1.22 (m, 1H, menthyl), 1.42 (s,

3H, CpꢁCH₃), 1.53–1.78 (m, 4H, menthyl), 4.70–4.75

(m, 1H, menthyl), 4.75 (s, 1H, CpꢁH), 4.94 (s, 1H,

CpꢁH), 6.58 (t, J=9.1 Hz, 6H, Ph), 7.08 (t, J=7.0 Hz,

6H, Ph), 7.22–7.56 (m, 23H, Ph). ¹³C-NMR (CDCl₃, 150

MHz): l 4.81 (s), 13.09 (s), 16.46 (s), 20.49 (s), 22.13 (s),

23.59 (s), 26.38 (s), 31.44 (s), 31.69 (s), 34.16 (s), 41.50

(s), 46.45 (s), 69.78 (s), 75.85 (s), 80.78 (s), 92.83 (s),

109.83 (s), 127.65–134.28 (m), 169.67 (s). ³¹P-NMR

(CDCl₃, 160 MHz): l 38.59 (d, J_PꢁP=32.5 Hz), 42.09

(bs). FAB MS: m/z 1004 (M⁺ꢁPF₆). Mp: 132–133°C.

[h]²_D⁰: +165.1° (c 0.312, MeCN). Calc. for

C₆₁H₆₂F₆NO₂P₃Ru: C, 63.69; H, 5.44; N, 1.22. Anal.

Found: C, 63.64; H, 5.41; N, 1.17.

similar to that for 7a-1 (97%, yellow powder). IR (cm⁻¹

,

1

KBr): 841 (w_PꢁF), 1657 (w_CꢀO), 3417 (w_N–H). H-NMR

(CDCl₃, 400 MHz): l 1.28 (dd, J=1.7, 3.4 Hz, 3H,

CpꢁCH₃), 1.33 (s, 9H, ꢁC(CH₃)₃), 1.99 (d, J=2.4 Hz,

3H, CpꢁCH₃), 2.30 (s, 3H, NCCH₃), 3.72 (s, 1H,

ꢁCONHꢁ), 4.44 (s, 1H, CpꢁH), 4.85 (s, 1H, CpꢁH), 6.73

(t, J=17.8 Hz, 6H, Ph), 7.12–7.44 (m, 24H, Ph).

¹³C-NMR (CDCl₃, 100 MHz): l 4.99 (s), 11.92 (s), 13.36

(s), 28.76 (s), 51.96 (s), 72.25 (s), 83.23 (d, J_PꢁC=7.4 Hz),

93.84 (d, J_PꢁC=5.8 Hz), 98.80 (d, J_PꢁC=3.3 Hz), 108.80

(d, J_PꢁC=3.3 Hz), 128.03–134.41 (m), 167.89 (s). ³¹P-

NMR (CDCl₃, 160 MHz): l 39.55 (d, J_PꢁP=33.1 Hz),

42.54 (d, J_PꢁP=33.2 Hz). FAB MS: m/z 859 (M⁺ꢁPF₆).

Mp: 135–136°C. [h]²_D⁰: −12.1° (c 0.493, MeCN). Calc.

for C₅₀H₅₁F₆N₂OP₃Ru: C, 59.82; H, 5.12; N, 2.79. Anal.

Found: C, 59.94; H, 5.24; N, 2.80.

3.4. Syntheses of planar-chiral trisubstituted

cyclopentadienylruthenium–6inylidene complexes (4)

3.3.5. (S_Cl)-[{p⁵-C₅H₂-1-(CONH^tBu)-2,4-Me₂}-

Ru(PPh₃)₂(MeCN)][PF₆] (7a-1)

(S_Cl)-[{h⁵-C₅H₂-1-(CONH^tBu)-2,4-Me₂}Ru(h⁵-C₆H₆)]-

[PF₆] 5a-1 was prepared from 1a-1 via hydrolysis and

then treatment with tert-butylamine according to the

method reported previously [10b,c]. Thus obtained 5a-1

was used as a starting material for the preparation of

3.4.1. (S_Cl)-[{p⁵-C₅H₂-1-(CO₂-(l)-menthyl)-2,4-

Me₂}Ru(PPh₃)₂(ꢀCꢀCHPh)][PF₆] (4a-1)

To a solution of ruthenium complex 3a-1 (86.0 mg,

0.08 mmol) in CH₂Cl₂(5 ml) was added phenylacetylene

(80.7 mg, 0.79 mmol) and stirred at room temperature

610

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

for 18 h. After removal of the solvent under reduced

pressure, the residue was dissolved with CH₂Cl₂(2 ml),

and to the CH₂Cl₂solution addition of hexane (10 ml)

resulted in the precipitation of 4a-1. Puriﬁcation of the

complex was performed by repeating re-precipitation

from CH₂Cl₂, giving 4a-1 (82 mg, 90% yield) as a

reddish–brown powder. IR (cm⁻¹, KBr): 839 (w_PꢁF),

3.4.3. (S_Cl)-[{p⁵-C₅H₂-1-(CO₂-(l)-menthyl)-2-Me-

4-Ph}Ru(PPh₃)₂(ꢀCꢀCHPh)][PF₆] (4b-1)

This compound was prepared from 3b-1 by the

method similar to that for 4a-1 (74%, reddish–brown

powder). IR (cm⁻¹, KBr): 840 (w_PꢁF), 1650 (w_CꢀC), 1704

1

(w_CꢀO). H-NMR (CDCl₃, 600 MHz): l 0.69 (d, J=6.8

Hz, 3H, menthylꢁCH₃), 0.85 (d, J=7.0 Hz, 3H, men-

thylꢁCH₃), 0.96–1.01 (m, 1H, menthyl), 0.99 (d, J=6.2

Hz, 3H, menthylꢁCH₃), 1.05–1.13 (m, 1H, menthyl),

1.20–1.33 (m, 1H, menthyl), 1.60–1.78 (m, 4H, men-

thyl), 1.66 (s, 3H, CpꢁCH₃), 2.26–2.28 (m, 1H, men-

thyl), 4.82 (dt, J=4.1, 10.8 Hz, 1H, menthyl), 5.26 (s,

1H, ꢀCHPh), 5.65 (s, 1H, CpꢁH), 5.84 (s, 1H, CpꢁH),

6.07 (d, J=7.1 Hz, 2H, Ph), 6.57 (t, J=9.2 Hz, 1H,

Ph), 6.65–6.71 (m, 8H, Ph), 6.76 (t, J=7.2 Hz, 1H,

Ph), 6.94–7.00 (m, 6H, Ph), 7.05–7.15 (m, 5H, Ph),

7.18–7.25 (m, 6H, Ph), 7.29–7.42 (m, 6H, Ph), 7.45–

7.53 (m, 5H, Ph). ¹³C-NMR (CDCl₃, 150 MHz): l

13.39 (s), 14.00 (s), 16.60 (s), 20.52 (s), 22.16 (s), 22.27

(s), 23.74 (s), 26.64 (s), 31.51 (s), 34.07 (s), 34.17 (s),

41.63 (s), 46.74 (s), 76.60 (s), 89.54 (s), 90.75 (s), 99.75

(s), 111.12 (s), 118.99 (s), 125.39 (s), 126.28–134.17 (m),

1

1626 (w_CꢀC), 1704 (w_CꢀO). H-NMR (CDCl₃, 600 MHz):

l 0.78 (d, J=6.6 Hz, 3H, menthylꢁCH₃), 0.82 (t,

J=6.0 Hz, 3H, menthylꢁCH₃), 0.92–0.98 (m, 1H, men-

thyl), 1.03–1.09 (m, 1H, menthyl), 1.28–1.38 (m, 2H,

menthyl), 1.48 (s, 3H, CpꢁCH₃), 1.68–1.74 (m, 3H,

menthyl), 1.80–1.84 (m, 1H, menthyl), 1.98–2.00 (m,

1H, menthyl), 4.90 (dt, J=4.4, 10.8 Hz, 1H, menthyl),

4.99 (s, 1H, ꢀCHPh), 5.23 (s, 1H, CpꢁH), 5.60 (s, 1H,

CpꢁH), 6.93 (d, J=7.7 Hz, 2H, Ph), 7.00–7.09 (m,

13H, Ph), 7.16–7.19 (m, 8H, Ph), 7.25–7.27 (m, 6H,

Ph), 7.35 (t, J=7.3 Hz, 3H, Ph), 7.41 (d, J=7.4 Hz,

3H, Ph). ¹³C-NMR (CDCl₃, 150 MHz): l 11.65 (s),

13.42 (s), 15.79 (s), 20.90 (s), 21.88 (s), 22.23 (s), 25.88

(s), 33.82 (s), 34.02 (s), 41.29 (s), 46.86 (s), 93.30 (s),

98.87 (s), 99.24 (s), 110.00 (s), 113.50 (s), 118.92 (s),

127.04–133.89 (m), 164.99 (s), 356.90 (t, J_PꢁC=15.1

165.72 (s), 363.66 (t,

J

_PꢁC=17.1 Hz). ³¹P-NMR

(CDCl₃, 160 MHz): l 31.87 (d, J_PꢁP=26.6 Hz), 45.58

(bs). FAB MS: m/z 1065 (M⁺ꢁPF₆). Mp: 137–138°C.

[h]²_D⁰: −42.5° (c 0.258, MeCN). Calc. for

C₆₇H₆₅F₆O₂P₃Ru: C, 66.43; H, 5.41. Anal. Found: C,

66.20; H, 5.34.

Hz). ³¹P-NMR (CDCl₃, 160 MHz): l 37.56 (d, J_PꢁP

=

27.9 Hz), 43.16 (d, J_PꢁP=27.8 Hz). FAB MS: m/z 1003

(M⁺ꢁPF₆). Mp: 138–139°C. [h]²_D⁰: −46.4° (c 0.347,

MeCN). Calc. for C₆₂H₆₃F₆O₂P₃Ru: C, 64.79; H, 5.53.

Anal. Found: C, 64.52; H, 5.59.

3.4.4. (R_C1)-[{p⁵-C₅H₂-1-(CO₂-(d)-menthyl)-2-

Me-4-Ph}Ru(PPh₃)₂(ꢀCꢀCHPh)][PF₆] (4b-2)

3.4.2. (R_Cl)-[{p⁵-C₅H₂-1-(CO₂-(d)-menthyl)-2,4-

Me₂}Ru(PPh₃)₂(ꢀCꢀCHPh)][PF₆] (4a-2)

This compound was prepared by the method from

3b-2 similar to that for 4a-1 (80%, reddish–brown

powder). IR (cm⁻¹, KBr): 840 (w_PꢁF), 1650 (w_CꢀC), 1704

This compound was prepared from 3a-2 by the

method similar to that for 4a-1 (89%, reddish–brown

powder). IR (cm⁻¹, KBr): 839 (w_PꢁF), 1626 (w_CꢀC), 1703

1

(w_CꢀO). H-NMR (CDCl₃, 600 MHz): l 0.69 (d, J=6.8

Hz, 3H, menthylꢁCH₃), 0.85 (d, J=7.0 Hz, 3H, men-

thylꢁCH₃), 0.96–1.02 (m, 1H, menthyl), 0.99 (d, J=6.0

Hz, 3H, menthylꢁCH₃), 1.05–1.14 (m, 1H, menthyl),

1.21–1.33 (m, 1H, menthyl), 1.60–1.78 (m, 4H, men-

thyl), 1.67 (s, 3H, CpꢁCH₃), 2.26ꢁ2.28 (m, 1H, men-

thyl), 4.82 (dt, J=4.1, 10.8 Hz, 1H, menthyl), 5.26 (s,

1H, ꢀCHPh), 5.65 (s, 1H, CpꢁH), 5.83 (s, 1H, CpꢁH),

6.07 (d, J=7.3 Hz, 2H, Ph), 6.57 (t, J=9.2 Hz, 1H,

Ph), 6.65–6.71 (m, 8H, Ph), 6.76 (t, J=7.0 Hz, 1H,

Ph), 6.93–7.00 (m, 6H, Ph), 7.05–7.15 (m, 5H, Ph),

7.18–7.25 (m, 6H, Ph), 7.30–7.42 (m, 6H, Ph), 7.45–

7.53 (m, 5H, Ph). ¹³C-NMR (CDCl₃, 150 MHz): l

13.38 (s), 14.00 (s), 16.59 (s), 20.52 (s), 22.15 (s), 22.28

(s), 23.75 (s), 26.65 (s), 31.50 (s), 34.07 (s), 34.17 (s),

41.63 (s), 46.74 (s), 76.61 (s), 89.52 (s), 90.76 (s), 99.76

(s), 111.12 (s), 118.99 (s), 125.39 (s), 126.27–134.16 (m),

1

(w_CꢀO). H-NMR (CDCl₃, 600 MHz): l 0.78 (d, J=6.9

Hz, 3H, menthylꢁCH₃), 0.82 (t, J=6.4 Hz, 3H, men-

thylꢁCH₃), 0.92–0.98 (m, 1H, menthyl), 1.02–1.09 (m,

1H, menthyl), 1.28–1.38 (m, 2H, menthyl), 1.48 (s, 3H,

CpꢁCH₃), 1.68–1.72 (m, 3H, menthyl), 1.79–1.84 (m,

1H, menthyl), 1.98–2.00 (m, 1H, menthyl), 4.90 (dt,

J=4.4, 10.4 Hz, 1H, menthyl), 4.99 (s, 1H, ꢀCHPh),

5.23 (s, 1H, CpꢁH), 5.60 (s, 1H, CpꢁH), 6.93 (d, J=7.1

Hz, 2H, Ph), 7.00ꢁ7.09 (m, 13H, Ph), 7.16–7.18 (m,

8H, Ph), 7.25–7.27 (m, 6H, Ph), 7.35 (t, J=7.4 Hz, 3H,

Ph), 7.42 (d, J=7.4 Hz, 3H, Ph). ¹³C-NMR (CDCl₃,

150 MHz): l 11.70 (s), 13.45 (s), 15.82 (s), 20.92 (s),

21.91 (s), 22.25 (s), 25.90 (s), 33.84 (s), 34.04 (s), 41.32

(s), 46.89 (s), 93.33 (s), 98.90 (s), 99.20 (s), 110.00 (s),

113.55 (s), 118.95 (s), 126.84–133.92 (m), 164.99 (s),

356.95 (t, J_PꢁC=15.1 Hz). ³¹P-NMR (CDCl₃, 160

MHz): l 37.54 (d, J_PꢁP=27.9 Hz), 43.16 (d, J_PꢁP=27.9

Hz). FAB MS: m/z 1003 (M⁺ꢁPF₆). Mp: 138–139°C.

[h]²_D⁰: +46.4° (c 0.300, MeCN). Calc. for

C₆₂H₆₃F₆O₂P₃Ru: C, 64.79; H, 5.53. Anal. Found: C,

64.99; H, 5.79.

165.71 (s), 363.67 (t,

J

_PꢁC=19.2 Hz). ³¹P-NMR

(CDCl₃, 160 MHz): l 31.80 (d, J_PꢁP=26.6 Hz), 45.55

(bs). FAB MS: m/z 1065 (M⁺ꢁPF₆). Mp: 137–138°C.

[h]²_D⁰: +42.5° (c 0.283, MeCN). Calc. for

C₆₇H₆₅F₆O₂P₃Ru: C, 66.43; H, 5.41. Anal. Found: C,

66.50; H, 5.36.

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

611

3.4.5. (S_Cl)-[{p⁵-C₅H₂-1-(CONH^tBu)-2,4-Me₂}-

Ru(PPh₃)₂(ꢀCꢀCHPh)][PF₆] (8a-1)

menthylꢁCH₃), 1.07–1.18 (m, 2H, menthyl), 1.28–1.33

(m, 1H, menthyl), 1.39 (s, 3H, CpꢁCH₃), 1.40–1.44 (m,

1H, menthyl), 1.72–1.83 (m, 3H, menthyl), 1.76 (s, 3H,

CpꢁCH₃), 2.16ꢁ2.18 (m, 1H, menthyl), 4.41 (s, 2H,

ꢀCH₂), 4.55 (s, 1H, CpꢁH), 4.86 (s, 1H, CpꢁH), 4.90

(dt, J=4.4, 10.9 Hz, 1H, menthyl), 7.01–7.04 (m, 6H,

Ph), 7.10–7.13 (m, 6H, Ph), 7.20–7.23 (m, 6H, Ph),

7.30–7.33 (m, 6H, Ph), 7.36–7.38 (m, 3H, Ph), 7.43–

7.45 (m, 3H, Ph). ¹³C-NMR (CDCl₃, 150 MHz): l

11.85 (s), 13.09 (s), 15.93 (s), 20.98 (s), 22.06 (s), 22.26

(s), 25.92 (s), 33.96 (s), 34.06 (s), 41.68 (s), 47.01 (s),

76.55 (s), 91.74 (s), 95.33 (s), 97.82 (s), 101.05 (s),

109.07 (s), 115.07 (s), 128.29—134.05 (m), 165.32 (s),

352.31 (t, J_PꢁC=17.1 Hz). ³¹P-NMR (CDCl₃, 160

MHz): l 38.43 (d, J_PꢁP=28.1 Hz), 45.61 (d, J_PꢁP=28.2

Hz). FAB MS: m/z 927 (M⁺ꢁPF₆). Mp: 142–143°C.

[h]²_D⁰: −76.9° (c 0.200, MeCN). Calc. for

C₅₆H₅₉F₆O₂P₃Ru: C, 62.67; H, 5.55. Anal. Found: C,

62.92; H, 5.81.

This compound was prepared from 7a-1 by the

method similar to that for 4a-1 (93%, reddish–brown

powder). IR (cm⁻¹, KBr): 842 (w_PꢁF), 1624 (w_CꢀC), 1657

(w_CꢀO). ¹H-NMR (CDCl₃, 400 MHz): l 1.36 (s, 9H,

ꢁC(CH₃)₃), 1.52 (s, 3H, CpꢁCH₃), 1.81 (s, 3H,

CpꢁCH₃), 4.67 (s, 1H, ꢀCHPh), 4.81 (s, 1H, CpꢁH),

5.62 (s, 1H, CpꢁH), 5.65 (s, 1H, ꢁCONHꢁ), 6.70–7.43

(m, 35H, Ph). ¹³C-NMR (CDCl₃, 100 MHz): l 12.41

(s), 13.19 (s), 28.47 (s), 52.35 (s), 93.87 (d, J_PꢁC=1.6

Hz), 95.95 (s), 97.51 (s), 110.63 (d, J_PꢁC=2.1 Hz),

117.49 (s), 118.07 (s), 126.58–134.15 (m), 163.34 (s),

358.54 (t, J_PꢁC=15.3 Hz). ³¹P-NMR (CDCl₃, 160

MHz): l 42.40 (d, J_PꢁP=27.3 Hz), 44.91 (d, J_PꢁP=28.1

Hz). FAB MS: m/z 920 (M⁺ꢁPF₆). Mp: 119–120°C.

[h]²_D⁰: +10.5° (c 0.418, MeCN). Calc. for

C₅₆H₅₄F₆NOP₃Ru: C, 63.15; H, 5.11; N, 1.32. Anal.

Found: C, 63.29; H, 4.92; N, 1.20.

3.4.6. (R_Cl)-[{p⁵-C₅H₂-1-(CONH^tBu)-2,4-Me₂}-

Ru(PPh₃)₂(ꢀCꢀCHPh)][PF₆] (8a-2)

3.4.8. (R_Cl)-[{p⁵-C₅H₂-1-(CO₂-(d)-menthyl)-

2,4-Me₂}Ru(PPh₃)₂(ꢀCꢀCH₂)][PF₆] (9a-2)

This compound was prepared from 7a-2 by the

method similar to that for 4a-1 (99%, reddish–brown

powder). IR (cm⁻¹, KBr): 841 (w_PꢁF), 1624 (w_CꢀC), 1657

(w_CꢀO). ¹H-NMR (CDCl₃, 400 MHz): l 1.35 (s, 9H,

ꢁC(CH₃)₃), 1.52 (s, 3H, CpꢁCH₃), 1.81 (s, 3H,

CpꢁCH₃), 4.67 (s, 1H, ꢀCHPh), 4.81 (s, 1H, CpꢁH),

5.61 (s, 1H, CpꢁH), 5.64 (s, 1H, ꢁCONHꢁ), 6.70–7.43

(m, 35H, Ph). ¹³C-NMR (CDCl₃, 100 MHz): l 12.43

(s), 13.20 (s), 28.47 (s), 52.36 (s), 93.87 (d, J_PꢁC=1.7

Hz), 95.97 (s), 97.51 (s), 110.63 (d, J_PꢁC=2.5 Hz),

117.50 (s), 118.07 (s), 126.60–134.16 (m), 163.35 (s),

358.54 (t, J_PꢁC=15.3 Hz). ³¹P-NMR (CDCl₃, 160

MHz): l 42.38 (d, J_PꢁP=27.3 Hz), 44.89 (d, J_PꢁP=28.3

Hz). FAB MS: m/z 920 (M⁺ꢁPF₆). Mp: 119–120°C.

[h]²_D⁰: −10.4° (c 0.431, MeCN). Calc. for

C₅₆H₅₄F₆NOP₃Ru: C, 63.15; H, 5.11; N, 1.32. Anal.

Found: C, 63.47; H, 4.99; N, 1.41.

This compound was prepared from 3a-2 by the

method similar to that for 9a-1 (61%, mustard–yellow

powder). IR (cm⁻¹, KBr): 839 (w_PꢁF), 1626 (w_CꢀC), 1703

1

(w_CꢀO). H-NMR (CDCl₃, 600 MHz): l 0.79 (d, J=6.8

Hz, 3H, menthylꢁCH₃), 0.84 (d, J=7.0 Hz, 3H, men-

thylꢁCH₃), 0.93–0.99 (m, 1H, menthyl), 1.02 (d, J=6.6

Hz, 3H, menthylꢁCH₃), 1.08–1.17 (m, 2H, menthyl),

1.27–1.32 (m, 1H, menthyl), 1.39 (s, 3H, CpꢁCH₃),

1.40–1.44 (m, 1H, menthyl), 1.72–1.83 (m, 3H, men-

thyl), 1.76 (s, 3H, CpꢁCH₃), 2.16–2.18 (m, 1H, men-

thyl), 4.41 (s, 2H, ꢀCH₂), 4.55 (s, 1H, CpꢁH), 4.86 (s,

1H, CpꢁH), 4.90 (dt, J=4.3, 10.8 Hz, 1H, menthyl),

7.01–7.04 (m, 6H, Ph), 7.10–7.13 (m, 6H, Ph), 7.20–

7.22 (m, 6H, Ph), 7.30–7.32 (m, 6H, Ph), 7.36–7.38 (m,

3H, Ph), 7.42–7.45 (m, 3H, Ph). ¹³C-NMR (CDCl₃, 150

MHz): l 11.85 (s), 13.08 (s), 15.94 (s), 20.99 (s), 22.06

(s), 22.26 (s), 25.92 (s), 33.97 (s), 34.05 (s), 41.69 (s),

47.02 (s), 76.55 (s), 91.74 (s), 95.33 (s), 97.82 (s), 101.07

(s), 109.09 (s), 115.10 (s), 128.29–134.05 (m), 165.34 (s),

352.33 (t, J_PꢁC=17.1 Hz). ³¹P-NMR (CDCl₃, 160

MHz): l 38.43 (d, J_PꢁP=28.1 Hz), 45.62 (d, J_PꢁP=28.1

Hz). FAB MS: m/z 927 (M⁺ꢁPF₆). Mp: 142–143°C.

[h]²_D⁰: +76.5° (c 0.200, MeCN). Calc. for

C₅₆H₅₉F₆O₂P₃Ru: C, 62.67; H, 5.55. Anal. Found: C,

62.91; H, 5.68.

3.4.7. (S_Cl)-[{p⁵-C₅H₂-1-(CO₂-(l)-menthyl)-

2,4-Me₂}Ru(PPh₃)₂(ꢀCꢀCH₂)][PF₆] (9a-1)

To a solution of ruthenium complex 3a-1 (80.0 mg,

0.07 mmol) in CH₂Cl₂(5 ml) was added trimethylsilyl-

acetylene (0.14 g, 1.47 mmol) and stirred at room

temperature for 18 h. After removal of the solvent

under reduced pressure, the residue was dissolved with

CH₂Cl₂(2 ml), and to the CH₂Cl₂solution addition of

hexane (10 ml) resulted in a reddish–brown precipita-

tion. Puriﬁcation of the complex was performed by

repeating re-precipitation from CH₂Cl₂, giving 9a-1 (52

3.4.9. (S_Cl)-[{p⁵-C₅H₂-1-(CO₂-(l)-menthyl)-2-

Me-4-Ph}Ru(PPh₃)₂(ꢀCꢀCH₂)][PF₆] (9b-1)

This compound was prepared from 3b-1 by the

method similar to that for 9a-1 (81%, mustard–yellow

powder). IR (cm⁻¹, KBr): 840 (w_PꢁF), 1627 (w_CꢀC), 1705

mg, 75% yield) as a reddish–brown powder. IR (cm⁻¹

,

KBr): 839 (w_PꢁF), 1626 (w_CꢀC), 1703 (w_CꢀO). ¹H-NMR

(CDCl₃, 600 MHz): l 0.79 (d, J=6.8 Hz, 3H, men-

thylꢁCH₃), 0.84 (d, J=7.0 Hz, 3H, menthylꢁCH₃),

0.93–0.99 (m, 1H, menthyl), 1.02 (d, J=6.4 Hz, 3H,

1

(w_CꢀO). H-NMR (CDCl₃, 600 MHz): l 0.73 (d, J=6.6

Hz, 3H, menthylꢁCH₃), 0.87 (d, J=7.3 Hz, 3H, men-

thylꢁCH₃), 0.98 (d, J=5.8 Hz, 3H, menthylꢁCH₃),

612

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

1.08–1.14 (m, 1H, menthyl), 1.27–1.34 (m, 2H, men-

thyl), 1.56 (s, 3H, CpꢁCH₃), 1.64–1.81 (m, 2H, men-

thyl), 2.15–2.17 (m, 1H, menthyl), 4.20 (s, 2H, ꢀCH₂),

4.82 (dt, J=3.4, 10.4 Hz, 1H, menthyl), 5.04 (s, 1H,

CpꢁH), 5.22 (s, 1H, CpꢁH), 6.71–6.74 (m, 6H, Ph),

7.06–7.14 (m, 13H, Ph), 7.36–7.49 (m, 16H, Ph). ¹³C-

NMR (CDCl₃, 150 MHz): l 13.00 (s), 14.00 (s), 16.56

(s), 20.65 (s), 22.10 (s), 22.27 (s), 23.62 (s), 26.56 (s),

31.51 (s), 34.14 (s), 41.62 (s), 47.09 (s), 76.39 (s), 89.94

(s), 91.49 (d, J_PꢁC=8.5 Hz), 97.69 (s), 99.29 (s), 110.23

(s), 115.99 (s), 126.23–134.17 (m), 165.41 (s), 355.90 (t,

(d, J_PꢁP=28.4 Hz), 46.20 (d, J_PꢁP=28.8 Hz). FAB MS:

m/z 844 (M⁺ꢁPF₆). Mp: 113–114°C. [h]²_D⁰: +22.3° (c

0.235, MeCN). Calc. For C₅₀H₅₀F₆NOP₃Ru: C, 60.73;

H, 5.10; N, 1.42. Anal. Found: C, 60.85; H, 4.94; N,

1.62.

3.4.12. (R_C1)-[{p⁵-C₅H₂-1-(CONH^tBu)-2,4-Me₂}-

Ru(PPh₃)₂(ꢀCꢀCH₂)][PF₆] (10a-2)

This compound was prepared from 7a-2 by the

method similar to that for 9a-1 (92%, mustard–yellow

powder). IR (cm⁻¹, KBr): 841 (w_PꢁF), 1623 (w_CꢀC), 1657

(w_CꢀO). ¹H-NMR (CDCl₃, 400 MHz): l 1.42 (s, 3H,

CpꢁCH₃), 1.45 (s, 9H, ꢁC(CH₃)₃), 1.81 (s, 3H,

CpꢁCH₃), 4.21 (s, 1H, CpꢁH), 4.33 (s, 2H, ꢀCH₂), 4.49

(s, 1H, CpꢁH), 5.54 (s, 1H, ꢁCONHꢁ), 6.89–7.69 (m,

30H, Ph). ¹³C-NMR (CDCl₃, 100 MHz): l 12.02 (s),

J

_PꢁC=19.2 Hz). ³¹P-NMR (CDCl₃, 160 MHz): l 35.17

(d, J_PꢁP=26.3 Hz), 44.51 (bs). FAB MS: m/z 989

(M⁺ꢁPF₆). Mp: 152–153°C. [h]²_D⁰: −34.3° (c 0.255,

MeCN). Calc. for C₆₁H₆₁F₆O₂P₃Ru: C, 64.53; H, 5.42.

Anal. Found: C, 64.36; H, 5.23.

3.4.10. (R_C1)-[{p⁵-C₅H₂-1-(CO₂-(d)-menthyl)-2-

Me-4-Ph}Ru(PPh₃)₂(ꢀCꢀCH₂)][PF₆] (9a-2)

12.92 (s), 28.45 (s), 28.75 (s), 52.49 (s), 92.71 (d, J_PꢁC

3.9 Hz), 97.06 (s), 98.54 (d, J_PꢁC=4.3 Hz), 108.39 (s),

=

116.46 (s), 128.23–134.70 (m), 163.67 (s), 352.85 (t,

This compound was prepared from 3b-2 by the

method similar to that for 9a-1 (86%, mustard–yellow

powder). IR (cm⁻¹, KBr): 840 (w_PꢁF), 1626 (w_CꢀC), 1704

J

_PꢁC=17.0 Hz). ³¹P-NMR (CDCl₃, 160 MHz): l 36.75

(d, J_PꢁP=28.9 Hz), 46.21 (d, J_PꢁP=28.8 Hz). FAB MS:

m/z 844 (M⁺ꢁPF₆). Mp: 113–114°C. [h]²_D⁰: −22.3° (c

0.263, MeCN). Calc. For C₅₀H₅₀F₆NOP₃Ru: C, 60.73;

H, 5.10; N, 1.42. Anal. Found: C, 60.63; H, 5.24; N,

1.70.

1

(w_CꢀO). H-NMR (CDCl₃, 600 MHz): l 0.73 (d, J=7.0

Hz, 3H, menthylꢁCH₃), 0.89 (d, J=7.1 Hz, 3H, men-

thylꢁCH₃), 0.98 (d, J=6.4 Hz, 3H, menthylꢁCH₃),

1.08–1.15 (m, 1H, menthyl), 1.28–1.34 (m, 2H, men-

thyl), 1.55 (s, 3H, CpꢁCH₃), 1.65–1.80 (m, 2H, men-

thyl), 2.17–2.19 (m, 1H, menthyl), 4.22 (s, 2H, ꢀCH₂),

4.82 (dt, J=3.6, 10.4 Hz, 1H, menthyl), 5.02 (s, 1H,

CpꢁH), 5.24 (s, 1H, CpꢁH), 6.70–6.74 (m, 6H, Ph),

7.07–7.14 (m, 13H, Ph), 7.35–7.49 (m, 16H, Ph). ¹³C-

NMR (CDCl₃, 150 MHz): l 13.01 (s), 13.99 (s), 16.55

(s), 20.65 (s), 22.11 (s), 22.28 (s), 23.60 (s), 26.56 (s),

31.51 (s), 34.14 (s), 41.62 (s), 47.08 (s), 76.39 (s), 89.93

(s), 91.47 (d, J_PꢁC=8.5 Hz), 97.70 (s), 99.29 (s), 110.23

(s), 115.99 (s), 126.21–134.17 (m), 165.41 (s), 355.99 (t,

3.5. Other cyclopentadienylruthenium complexes

3.5.1. [(p⁵-C₅H₂-1-CO₂Et-2-Me-4-R²)Ru(PPh₃)_2-

t

(MeCN)][PF₆] (11: R²=Me, Ph, Bu, h-Naph, and

4-BrC₆H₄)

These compounds were prepared as a racemic mix-

ture from the corresponding [(h⁵-C₅H₂-1-CO₂Et-2-Me-

4-R²)Ru(h⁶-C₆H₆)][PF₆] [10c] by the method similar of

that for 3a–1.

Complex 11a (R²=Me): 99% yield, yellow powder.

IR (cm⁻¹, KBr): 841 (w_PꢁF), 1703 (w_CꢀO). ¹H-NMR

(CDCl₃, 400 MHz): l 1.17 (t, J=7.2 Hz, 3H,

ꢁOCH₂CH₃), 1.31 (s, 3H, CpꢁCH₃), 1.92 (s, 3H,

CpꢁCH₃), 2.34 (s, 3H, NCCH₃), 3.94–4.02 (m, 1H,

ꢁOCH₂CH₃), 4.12 (s, 1H, CpꢁH), 4.13–4.21 (m, 1H,

ꢁOCH₂CH₃), 4.53 (s, 1H, CpꢁH), 6.79 (t, J=8.9 Hz,

6H, Ph), 7.11–7.44 (m, 24H, Ph). ¹³C-NMR (CDCl₃,

100 MHz): l 5.06 (s), 12.00 (s), 12.80 (s), 14.15 (s),

60.72 (s), 65.83 (s), 69.40 (s), 84.84 (d, J_PꢁC=6.5 Hz),

94.72 (d, J_PꢁC=3.3 Hz), 99.24 (s), 109.25 (s), 127.80–

134.50 (m), 169.68 (s). ³¹P-NMR (CDCl₃, 160 MHz): l

38.88 (d, J_PꢁP=33.0 Hz), 44.15 (d, J_PꢁP=33.0 Hz).

FAB MS: m/z 832 (M⁺ꢁPF₆). Calc. for

C₄₈H₄₆F₆NO₂P₃Ru: C, 59.02; H, 4.75; N, 1.43. Anal.

Found: C, 59.20; H, 4.83; N, 1.25.

J

_PꢁC=18.1 Hz). ³¹P-NMR (CDCl₃, 160 MHz): l 35.17

(d, J_PꢁP=25.9 Hz), 44.50 (bs). FAB MS: m/z 989

(M⁺ꢁPF₆). Mp: 152–153°C. [h]²_D⁰: +34.8° (c 0.287,

MeCN). Calc. for C₆₁H₆₁F₆O₂P₃Ru: C, 64.53; H, 5.42.

Anal. Found: C, 64.25; H, 5.62.

3.4.11. (S_Cl)-[{p⁵-C₅H₂-1-(CONH^tBu)-2,4-Me₂}-

Ru(PPh₃)₂(ꢀCꢀCH₂)][PF₆] (10a-1)

This compound was prepared from 7a-1 by the

method similar to that for 9a-1 (95%, mustard–yellow

powder). IR (cm⁻¹, KBr): 842 (w_PꢁF), 1624 (w_CꢀC), 1657

(w_CꢀO). ¹H-NMR (CDCl₃, 400 MHz): l 1.42 (s, 3H,

CpꢁCH₃), 1.45 (s, 9H, ꢁC(CH₃)₃), 1.81 (s, 3H,

CpꢁCH₃), 4.22 (s, 1H, CpꢁH), 4.33 (s, 2H, ꢀCH₂), 4.48

(s, 1H, CpꢁH), 5.55 (s, 1H, ꢁCONHꢁ), 6.89–7.69 (m,

30H, Ph). ¹³C-NMR (CDCl₃, 100 MHz): l 12.06 (s),

Complex 11b (R²=Ph): 97% yield, yellow powder.

IR (cm⁻¹, KBr): 840 (w_PꢁF), 1711 (w_CꢀO). ¹H-NMR

(CDCl₃, 400 MHz): l 1.22 (t, J=7.2 Hz, 3H,

ꢁOCH₂CH₃), 1.51 (s, 3H, CpꢁCH₃), 2.09 (s, 3H,

NCCH₃), 3.97–4.05 (m, 1H, ꢁOCH₂CH₃), 4.18–4.26

12.94 (s), 28.49 (s), 28.76 (s), 52.44 (s), 92.71 (d, J_PꢁC

3.3 Hz), 97.08 (s), 98.55 (d, J_PꢁC=4.2 Hz), 108.43 (s),

=

116.47 (s), 128.24–134.69 (m), 163.66 (s), 352.85 (t,

J

_PꢁC=17.0 Hz). ³¹P-NMR (CDCl₃, 160 MHz): l 36.78

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

613

(m, 1H, ꢁOCH₂CH₃), 4.73 (s, 1H, CpꢁH), 4.83 (s, 1H,

CpꢁH), 6.67 (t, J=8.9 Hz, 6H, Ph), 6.83 (t, J=9.0 Hz,

1H, Ph), 7.08–7.52 (m, 28H, Ph). ¹³C-NMR (CDCl₃, 100

MHz): l 4.52 (s), 12.87 (s), 14.06 (s), 61.18 (d, J_PꢁC=13.3

Hz), 71.74 (s), 82.43 (d, J_PꢁC=10.7 Hz), 89.29 (d,

3.5.2. [(p⁵-C₅H₂-1-CO₂Et-2-Me-4-R²)Ru(PPh₃)₂-

t

(CCPh)][PF₆] (13: R²=Me, Ph, Bu, h-Naph, and

4-BrC₆H₄)

These compounds were prepared as a racemic mixture

from the corresponding [(h⁵-C₅H₂-1-CO₂Et-2-Me-4-

R²)Ru(PPh₃)₂(MeCN)][PF₆] 11.

J

_PꢁC=3.3 Hz), 99.01 (d, J_PꢁC=4.9 Hz), 108.57 (s),

127.47–134.23 (m), 168.69 (s). ³¹P-NMR (CDCl₃, 160

MHz): l 37.78 (d, J_PꢁP=33.1 Hz), 41.12 (d, J_PꢁP=33.2

Hz). FAB MS: m/z 894 (M⁺ꢁPF₆). Calc. for

C₅₃H₄₈F₆NO₂P₃Ru: C, 61.27; H, 4.66; N, 1.35. Anal.

Found: C, 61.50; H, 4.76; N, 1.25.

Complex 13a (R²=Me): To a solution of ruthenium

complex 11a 0.49 g (0.50 mmol) in CH₂Cl₂(20 ml) was

added phenylacetylene (0.51 g, 5.00 mmol) and stirred at

room temperature for 18 h. After removal of the solvent

under reduced pressure, the residual oil was chro-

matographed on alumina using benzene as an eluent.

The solvents were evaporated and the resulting yellow

solid was dried in vacuo, giving a yellow powder of 12a

in 96% yield. IR (cm⁻¹, KBr): 1694 (w_CꢀO), 2076 (w_CꢂC).

¹H-NMR (CDCl₃, 400 MHz): l 1.19 (t, J=7.1 Hz, 3H,

ꢁOCH₂CH₃), 1.26 (s, 3H, CpꢁCH₃), 1.99 (s, 3H,

CpꢁCH₃), 3.76 (s, 1H, CpꢁH), 3.98–4.11 (m, 2H,

ꢁOCH₂CH₃), 4.11 (s, 1H, CpꢁH), 7.00–7.38 (m, 29H,

Ph), 7.55(t, J=17.5 Hz, 3H, Ph). ¹³C-NMR (CDCl₃, 100

MHz): l 12.90 (s), 13.09 (s), 14.19 (s), 59.76 (s), 79.71 (s),

85.57 (d, J_PꢁC=8.2 Hz), 93.06 (d, J_PꢁC=5.7 Hz), 101.22

(d, J_PꢁC=4.9 Hz), 109.09 (d, J_PꢁC=2.4 Hz), 111.72 (s),

123.12 (s), 126.87–138.88 (m), 168.54 (s). ³¹P-NMR

(CDCl₃, 160 MHz): l 44.37 (d, J_PꢁP=34.2 Hz), 52.60 (d,

Complex 11c (R²=^tBu): 98% yield, yellow powder. IR

(cm⁻¹, KBr): 839 (w_PꢁF), 1708 (w_CꢀO). ¹H-NMR (CDCl₃,

400 MHz): l 1.11 (t, J=9.3 Hz, 3H, ꢁOCH₂CH₃), 1.27

(s, 9H, CpꢁC(CH₃)₃), 1.56 (s, 3H, CpꢁCH₃), 2.22 (s, 3H,

NCCH₃), 3.63–3.71 (m, 1H, ꢁOCH₂CH₃), 3.86 (s, 1H,

CpꢁH), 4.22–4.30 (m, 1H, ꢁOCH₂CH₃), 4.37 (d, J=4.9

Hz, 1H, CpꢁH), 6.69 (t, J=8.9 Hz, 6H, Ph), 7.13–7.48

(m, 24H, Ph). ¹³C-NMR (CDCl₃, 100 MHz): l 5.23 (s),

13.45 (s), 13.90 (s), 30.65 (s), 32.03 (s), 61.07 (s), 70.32

(s), 77.90 (d, J_PꢁC=9.9 Hz), 84.04 (d, J_PꢁC=6.6 Hz),

107.23 (s), 124.78 (s), 127.83–134.67 (m), 169.37 (s).

³¹P-NMR (CDCl₃, 160 MHz): l 35.62 (d, J_PꢁP=31.5

Hz), 41.26 (d, J_PꢁP=31.4 Hz). FAB MS: m/z 874

(M⁺ꢁPF₆). Calc. for C₅₁H₅₂F₆NO₂P₃Ru: C, 60.12; H,

5.14; N, 1.37. Anal. Found: C, 60.03; H, 4.88; N, 1.48.

Complex 11d (R²=a-naphthyl): 88% yield, yellow

J

_PꢁP=34.2 Hz). FAB MS: m/z 892 (M⁺). Calc. for

C₅₄H₄₈O₂P₂Ru: C, 72.72; H, 5.42. Anal. Found: C, 72.35;

H, 5.50.

1

powder. IR (cm⁻¹, KBr): 841 (w_PꢁF), 1711 (w_CꢀO). H-

NMR (CDCl₃, 400 MHz): l 1.27 (t, J=13.4 Hz, 3H,

ꢁOCH₂CH₃), 1.57 (s, 3H, CpꢁCH₃), 2.10 (s, 3H,

NCCH₃), 4.03–4.11 (m, 1H, ꢁOCH₂CH₃), 4.21–4.29 (m,

1H, ꢁOCH₂CH₃), 4.89 (s, 1H, CpꢁH), 4.96 (s, 1H,

CpꢁH), 6.63 (t, J=9.0 Hz, 6H, Ar), 7.05 (dt, J=2.0 Hz,

7.7 Hz, 6H, Ar), 7.24–7.99 (m, 25H, Ar). ¹³C-NMR

(CDCl₃, 100 MHz): l 4.56 (s), 12.98 (s), 14.11 (d,

Complex 13b (R²=Ph): 89%, yellow powder. IR

(cm⁻¹, KBr): 1695 (w_CꢀO), 2078 (w_CꢂC). ¹H-NMR

(CDCl₃, 400 MHz): l 1.09 (t, J=7.1 Hz, 3H,

ꢁOCH₂CH₃), 1.74 (s, 3H, CpꢁCH₃), 3.65–3.74 (m, 1H,

ꢁOCH₂CH₃), 3.90–4.04 (m, 1H, ꢁOCH₂CH₃), 4.04 (d,

J=1.2 Hz, 1H, CpꢁH), 5.10 (s, 1H, CpꢁH), 6.91 (t,

J=6.7 Hz, 6H, Ph), 7.00–7.59 (m, 28H, Ph), 7.65 (t,

J=9.0, 6H, Ph). ¹³C-NMR (CDCl₃, 100 MHz): l 13.43

(s), 14.05 (s), 59.86 (s), 79.90 (s), 86.31 (s), 88.94 (s),

100.44 (d, J_PꢁC=4.2 Hz), 107.96 (s), 112.55 (s), 123.12

(s), 126.63–138.14 (m), 167.56 (s). ³¹P-NMR (CDCl₃,

J

_PꢁC=5.8 Hz), 61.16 (s), 71.75 (s), 83.13 (s), 90.30 (s),

97.77 (s), 108.73 (d, J_PꢁC=2.4 Hz), 124.92 (s), 126.40–

134.24 (m), 168.78 (s). ³¹P-NMR (CDCl₃, 160 MHz): l

37.96 (d, J_PꢁP=33.1 Hz), 40.38 (bs). FAB MS: m/z 944

(M⁺ꢁPF₆). Calc. For C₅₇H₅₀F₆NO₂P₃Ru: C, 62.87; H,

4.63; N, 1.29. Anal. Found: C, 63.01; H, 4.58; N, 1.41.

Complex 11e (R²=4-BrC₆H₄): 93% yield, yellow pow-

160 MHz): l 45.34 (d, J_PꢁP=35.1 Hz), 49.84 (d, J_PꢁP

=

35.1 Hz). FAB MS: m/z 954 (M⁺). Calc. for

C₅₉H₅₀O₂P₂Ru: C, 74.28; H, 5.28. Anal. Found: C, 73.99;

H, 5.33.

1

der. IR (cm⁻¹, KBr): 840 (w_PꢁF), 1711 (w_CꢀO). H-NMR

(CDCl₃, 400 MHz): l 1.23 (t, J=7.2 Hz, 3H,

ꢁOCH₂CH₃), 1.47 (s, 3H, CpꢁCH₃), 2.15 (s, 3H,

NCCH₃), 4.02–4.11 (m, 1H, ꢁOCH₂CH₃), 4.19–4.27 (m,

1H, ꢁOCH₂CH₃), 4.77 (s, 1H, CpꢁH), 4.84 (s, 1H,

CpꢁH), 6.65 (t, J=8.9 Hz, 6H, Ph), 7.00–7.61 (m, 28H,

Ph). ¹³C-NMR (CDCl₃, 100 MHz): l 4.70 (s), 12.85 (s),

14.03 (s), 61.13 (s), 71.09 (s), 81.95 (d, J_PꢁC=3.3 Hz),

90.88 (s), 96.98 (d, J_PꢁC=4.1 Hz), 109.20 (s), 123.11 (s),

127.83–134.10 (m), 168.72 (s). ³¹P-NMR (CDCl₃, 160

MHz): l 37.49 (d, J_PꢁP=33.1 Hz), 40.80 (d, J_PꢁP=33.2

Hz). FAB MS: m/z 972 (M⁺ꢁPF₆). Calc. for

C₅₃H₄₇BrF₆NO₂P₃Ru: C, 56.95; H, 4.24; N, 1.25. Anal.

Found: C, 57.08; H, 4.48; N, 1.27.

Complex 13c (R²=^tBu): 24% yield, yellow powder. IR

(cm⁻¹, KBr): 1689 (w_CꢀO), 2075 (w_CꢂC). ¹H-NMR

(CDCl₃, 400 MHz): l 1.16 (t, J=7.1 Hz, 3H,

ꢁOCH₂CH₃), 1.18 (s, 9H, CpꢁC(CH₃)₃), 3.44 (s, 1H,

CpꢁH), 3.56–3.64 (m, 1H, ꢁOCH₂CH₃), 4.02–4.10 (m,

1H, ꢁOCH₂CH₃), 4.22 (s, 1H, CpꢁH), 7.01–7.57 (m,

35H, Ph). ¹³C-NMR (CDCl₃, 100 MHz): l 13.77 (s),

14.45 (d, J_PꢁC=5.0 Hz), 30.91 (s), 32.31 (s), 60.02 (s),

66.16 (s), 79.39 (s), 80.34 (d, J_PꢁC=9.1 Hz), 85.75 (d,

J

_PꢁC=7.4 Hz), 107.92 (d, J_PꢁC=2.5 Hz), 115.09 (s),

123.37 (s), 126.62–141.58 (m), 169.25 (s). ³¹P-NMR

(CDCl₃, 160 MHz): l 39.52 (d, J_PꢁP=32.5 Hz), 51.96 (d,

J

_PꢁP=32.3 Hz). FAB MS: m/z 934 (M⁺). Calc. for

614

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

C₅₇H₅₄O₂P₂Ru: C, 73.29; H, 5.83. Anal. Found: C,

73.22; H, 5.87.

from planar chirality. In addition the redox property of

ruthenium in the complexes can be ﬁnely tunable by the

type of substituents on the cyclopentadienyl ligand.

Complex 13d (R²=a–naphthyl): 97% yield, yellow

powder. IR (cm⁻¹, KBr): 1698 (w_CꢀO), 2079 (w_CꢂC).

¹H-NMR (CDCl₃, 400 MHz): l 1.11 (t, J=7.2 Hz, 3H,

ꢁOCH₂CH₃), 1.90 (s, 3H, CpꢁCH₃), 3.67–3.76 (m, 1H,

ꢁOCH₂CH₃), 3.92–4.00 (m, 1H, ꢁOCH₂CH₃), 4.14 (s,

1H, CpꢁH), 5.20 (d, J=2.2 Hz, 1H, CpꢁH), 6.84 (t,

J=6.8 Hz, 6H, Ar), 7.00–7.77 (m, 36H, Ar). ¹³C-NMR

(CDCl₃, 100 MHz): l 13.56 (s), 14.05 (s), 59.86 (s),

79.61 (d, J_PꢁC=5.0 Hz), 87.02 (d, J_PꢁC=5.7 Hz), 90.07

(s), 99.39 (s), 107.99 (d, J_PꢁC=1.7 Hz), 112.88 (s),

123.17 (s), 124.91–137.99 (m), 167.66 (s). ³¹P-NMR

(CDCl₃, 160 MHz): l 45.48 (d, J_PꢁP=34.1 Hz), 48.88

(d, J_PꢁP=34.1 Hz). FAB MS: m/z 1004 (M⁺). Calc. for

C₆₃H₅₂O₂P₂Ru: C, 75.36; H, 5.22. Anal. Found: C,

74.88; H, 5.28.

Acknowledgements

This work was supported by Grant-in-Aid for Scien-

tiﬁc Research from the Ministry of Education, Science,

Sports and Culture. We are grateful to The Material

Analysis Center, ISIR, Osaka University, for support

of spectral measurements and microanalyses.

References

[1] (a) S.G. Davies, Organotransition Metal Chemistry: Application

to Organic Synthesis, Pergamon, Oxford 1982. (b) I. Ojima,

Catalytic Asymmetric Synthesis, VCH, New York, 1993. (c) R.

Noyori, Asymmetric Catalysis in Organic Synthesis, Wiley, New

York, 1994.

[2] (a) A. Togni, T. Hayashi, Ferrocenes, VCH, Weinheim, 1995. (b)

Y. Nishibayashi, K. Segawa, K. Ohe, S. Uemura, Organometal-

lics 14 (1995) 5486. (c) A. Togni, Angew. Chem. Int. Ed. Engl.

35 (1996) 1475. (d) Y. Nishibayashi, I. Takei, M. Hidai,

Organometallics 16 (1997) 3091. (e) G.C. Fu, Acc. Chem. Res.

33 (2000) 412.

[3] A.H. Hoveyda, J.P. Morken, Angew. Chem. Int. Ed. Engl. 36

(1997) 550.

[4] (a) A. Shibahara, Chem. Lett. (1997) 621. (b) T.A. Mobley, R.G.

Bergman, J. Am. Chem. Soc. 120 (1998) 3253. (c) Y. Kataoka,

A. Shibahara, Y. Saito, T. Yamagata, K. Tani, Organometallics

17 (1998) 4338.

Complex 13e (R²=4-BrC₆H₄): 90% yield, yellow

powder. IR (cm⁻¹, KBr): 1695 (w_CꢀO), 2079 (w_CꢂC).

¹H-NMR (CDCl₃, 400 MHz): l 1.10 (t, J=7.1 Hz, 3H,

ꢁOCH₂CH₃), 1.73 (s, 3H, CpꢁCH₃), 3.70–3.78 (m, 1H,

ꢁOCH₂CH₃), 3.92–4.00 (m, 1H, ꢁOCH₂CH₃), 4.02 (s,

1H, CpꢁH), 5.04 (s, 1H, CpꢁH), 6.85–7.42 (m, 33H,

Ph), 7.61 (t, J=17.6 Hz, 6H, Ph). ¹³C-NMR (CDCl₃,

100 MHz): l 13.40 (s), 14.03 (s), 59.91 (s), 80.16 (s),

85.89 (s), 89.76 (s), 98.70 (s), 108.30 (s), 112.74 (s),

120.28 (s), 123.32 (s), 126.88–137.91 (m), 167.51 (s).

³¹P-NMR (CDCl₃, 160 MHz): l 44.91 (d, J_PꢁP=34.0

Hz), 49.47 (d, J_PꢁP=32.2 Hz). FAB MS: m/z 1032

(M⁺ꢁPF₆). Calc. for C₅₉H₄₉BrO₂P₂Ru: C, 68.60; H,

4.78. Anal. Found: C, 68.85; H, 4.88.

[5] (a) R.L. Halterman, Chem. Rev. 92 (1992) 965. (b) M. Uemura,

H. Nishimura, T. Hayashi, Tetrahedron Lett. 34 (1993) 1043. (c)

H.-J. Kno¨lker, Chem. Soc. Rev. 28 (1999) 151.

3.6. NMR trace experiments on the reactions of

[(p⁵-C₅H₂-1-CO₂Et-2,4-Me₂)Ru(PPh₃)₂(MeCN)][PF₆]

(11a) with phenylacetylenes 4-RC₆H₄CCH (R=H,

OMe, and NO₂).

[6] (a) H.H. Brintzinger, D. Fischer, R. Mu¨lhaupt, B. Rieger, R.M.

Waymouth, Angew. Chem. Int. Ed. Engl. 34 (1995) 1143. (b)

A.L. McKnight, R.M. Waymouth, Chem. Rev. 98 (1998) 2587.

[7] C.E. Garrett, G.C. Fu, J. Am. Chem. Soc. 120 (1998) 7497.

[8] (a) W.J. Seitz, A.K. Saha, M.M. Hossain, Organometallics 12

(1993) 2604. (b) B.M. Trost, Angew. Chem. Int. Ed. Engl. 34

(1995) 259. (c) B.M. Trost, Chem. Ber. 129 (1996) 1313.

[9] (a) M.I. Bruce, Chem. Rev. 91 (1991) 197. (b) M.I. Bruce, Chem.

Rev. 98 (1998) 2797. (c) C. Bruneau, P.H. Dixneuf, Acc. Chem.

Res. 32 (1999) 311.

[10] (a) M. Uno, K. Ando, N. Komatsuzaki, S. Takahashi, J. Chem.

Soc. Chem. Commun. (1992) 964. (b) N. Komatsuzaki, M. Uno,

K. Shirai, Y. Takai, T. Tanaka, M. Sawada, S. Takahashi, Bull.

Chem. Soc. Jpn. 69 (1996) 17. (c) N. Komatsuzaki, M. Uno, H.

Kikuchi, S. Takahashi, Chem. Lett. (1996) 677. (d) T.

Katayama, Y. Morimato, M. Yuge, M. Uno, S. Takahashi,

Organometallics 18 (1999) 3087.

[11] T.P. Gill, K.R. Mann, Organometallics 1 (1982) 485.

[12] M.I. Bruce, R.C. Wallis, Aust. J. Chem. 32 (1979) 1471.

[13] Y. Kawata, M. Sato, Organometallics 16 (1997) 1093.

[14] P.T. Czech, X.-Q. Ye, R.F. Fenske, Organometallics 9 (1990)

2016.

[15] (a) J. Silvestre, R. Hoffmann, Helv. Chim. Acta 68 (1985) 1461.

(b) C. Bianchini, M. Peruzzini, A. Vacca, F. Zanobini,

Organometallics 10 (1991) 3697. (c) Y. Wakatsuki, N. Koga, H.

To a solution of ruthenium complex 11a (0.06 mmol)

in CH₂Cl₂(0.5m l) was added ten equivalents of phenyl-

acetylenes in an-NMR tube at 25°C. The rate of forma-

tion of the vinylidene complexes were traced by ³¹P-

NMR. In this reaction, any ruthenium complexes other

than the starting material and vinylidene complex were

not observed.

4. Conclusions

A new family of enantiopure planar-chiral cyclopen-

tadienylruthenium–vinylidene complexes, (S_Cl)- and

(R_C1)-[(h⁵-C₅H₂-1-COR¹-2-Me-4-R²)Ru(PPh₃)₂(ꢀCꢀ

CHR³)][PF₆], reported here may provide the ﬁrst exam-

ples of chiral cyclopentadienylruthenium-alkylidene

complexes which have the potential use as reactive

chiral ruthenium complexes possessing an asymmetric

environment around the central ruthenium atom arising

Y. Ajioka et al. / Journal of Organometallic Chemistry 617–618 (2001) 601–615

615

Yamazaki, K. Morokuma, J. Am. Chem. Soc. 116 (1994) 8105.

(d) I. de los R´ıos, M.J. Tenorio, M.C. Puerta, P Valerga, J. Am.

Chem. Soc. 119 (1997) 6529.

[17] M.I. Bruce, A.G. Swincer, Aust. J. Chem. 33 (1980) 1471.

[18] M.I. Bruce, A.G. Swincer, R.C. Wallis, J. Organomet. Chem.

171 (1979) C5.

[16] T. Blackmore, M.I. Bruce, F.G.A. Stone, J. Chem. Soc. A (1971)

2376.

[19] Y. Matsushima, H. Kikuchi, M. Uno, S. Takahashi, Bull. Chem.

Soc. Jpn. 72 (1999) 2475.

.

Article Doi

Synthesis and characterization of planar-chiral cyclopentadienylruthenium-vinylidene complexes

DOI: 10.1016/S0022-328X(00)00736-1

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