Diastereoselectivity at chiral metal center of half-sandwich-type ruthenium complexes with planar-chiral cyclopentadienyl ligands in multiple ligand transfer reaction

Journal of Organometallic Chemistry 691 (2006) 2245–2256

www.elsevier.com/locate/jorganchem

Diastereoselectivity at chiral metal center of

half-sandwich-type ruthenium complexes with planar-chiral

cyclopentadienyl ligands in multiple ligand transfer reaction

*

Taku Katayama, Kiyotaka Onitsuka , Shigetoshi Takahashi

The Institute of Scientiﬁc and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-047, Japan

Received 28 September 2005; received in revised form 7 November 2005; accepted 7 November 2005

Available online 19 December 2005

Abstract

The triple ligand transfer reaction between planar-chiral cyclopentadienyl–ruthenium complexes [Cp⁰Ru(NCMe)₃][PF₆] (1) (Cp⁰= 1-

(COOR²)-2-Me-4-R¹C₅H₂; R¹= Me, Ph, t-Bu) and iron complexes CpFe(CO)(L)X (2) (L = PMe₃, PMe₂Ph, PMePh₂, PPh₃; X = I, Br)

resulted in the formation of metal-centered chiral ruthenium complexes Cp⁰Ru(CO)(L)X (3) in moderate yields with diastereoselectivities

of up to 68% de. The conﬁgurations of some major diastereomers were determined to be S^ꢀ_CpR_R^ꢀ_uby X-ray crystallography. The diaste-

reoselectivity of 3 was under kinetic control and not aﬀected by the steric eﬀect of the substituents on the Cp⁰ring of 1 and the phosphine

of 2. Although the double ligand transfer reaction between [Cp⁰Ru{P(OMe)₃}(NCMe)₂][PF₆] (7) and CpFe(CO)₂X (8) produced

Cp⁰Ru{P(OMe)₃}(CO)X (9), the selectivity at the ruthenium center was low.

Keywords: Ruthenium; Iron; Ligand transfer; Planar chirality; Metal-centered chirality

1. Introduction

and showed that the metal-centered chirality is highly

controlled in some reactions of the planar-chiral cyclo-

pentadienyl–ruthenium complexes [4]. Recently, we found

Much attention has been paid to the synthesis and reac-

tivity of chiral organometallic complexes in order to obtain

useful information for the development of new asymmetric

catalysts and for understanding the mechanism of catalytic

asymmetric reactions [1]. Although organometallic com-

plexes with chiral ligands comprise the majority of such

chemistry, other types of chiral complexes have become

the focus of increasing interest in recent years. The metal-

centered chiral complexes belong to such category [2].

Although a signiﬁcant number of metal-centered chiral

complexes have been prepared so far, the control of the ste-

reochemistry at the metal center remains a challenging

task.

a

novel multiple ligand transfer reaction between

cyclopentadienyl–iron and cyclopentadienyl–ruthenium

complexes [5]. When three ligands other than the cyclo-

pentadienyl ligand are diﬀerent from each other, a

metal-centered chirality is generated on the resulting

ruthenium complexes. Thus, we examined control of ste-

reochemistry at the ruthenium center by planar-chiral

cyclopentadienyl ligands in the multiple ligand transfer

reaction. We present herein the full details of the diaste-

reoselectivity at the chiral metal center of the planar-

chiral cyclopentadienyl–ruthenium complexes in the

multiple ligand transfer reaction. The preliminary results

have appeared in a communication [6]. Although, we

performed this study using racemic mixtures of planar-

chiral cyclopentadienyl–ruthenium complexes as starting

materials, all structures are drawn with the planar chiral-

ity of S_Cpfor clarity.

We have examined the chemistry of planar-chiral

cyclopentadienyl complexes of late transition metals [3]

*

Corresponding author.

E-mail address: onitsuka@sanken.osaka-u.ac.jp (K. Onitsuka).

doi:10.1016/j.jorganchem.2005.11.010

2246

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

2. Results and discussion

Planar-chiral trisubstituted cyclopentadienyl–ruthenium

complex [Cp⁰Ru(NCMe)₃][PF₆] (1a) was treated with

cyclopentadienyl–iron complex CpFe(CO)(PMe₃)I (2a) in

CH₂Cl₂under reﬂux for 3 h to give Cp⁰Ru(CO)(PMe₃)I

(3a) along with other ruthenium complexes, Cp⁰Ru(CO)₂I

(4a) and Cp⁰CpRu (5), and ferrocene (6) (Scheme 1). These

complexes were isolated by column chromatography on sil-

ica gel, and fully characterized by spectral analyses. The ³¹

P

NMR spectrum of complex 3a showed two singlets at d

11.9 and 13.0 with an integral ratio of 16:84, indicating that

3a consists of two diastereomers in 68% de [7]. Consistent

1

data were obtained in the H NMR spectrum of 3a. Since

single crystals of the major diastereomer of 3a were

obtained by recrystallization of a diastereomeric mixture

from ether–hexane, the conﬁguration was determined by

X-ray analysis to be S^ꢀ_CpR_R^ꢀ_ubased on the priority sequence

I > Cp⁰> P > C (Fig. 1) [2,8]. When the diastereomerically

pure sample of ðS^ꢀ_CpR_R^ꢀ_uÞ-3a was heated in dichlorometh-

ane, no epimerization was observed.

Then, we examined the reactions of 1 with several iron

complexes 2, the representative results of which are given

in Table 1 together with the result mentioned above. The

yield of 3 was slightly decreased in the order of phosphine

ligands PMe₃, PMe₂Ph, PMePh₂and PPh₃on 2, and the

highest diastereoselectivity of 3 was observed in the reac-

Fig. 1. ORTEP diagram of ðS^ꢀ_CpR_R^ꢀ_uÞ-3a (major diastereomer). Hydrogen

atoms are omitted for clarity.

tion with 2a (entries 1–4). The reaction with 2e having a

bromide ligand gave 3d in 12% yield with 34% de (entry

5), although the reaction with analogous chloride complex

2d did not produce 3. Similar phosphine eﬀect on the yield

and diastereoselectivity of 3 was observed in the reactions

of 1b that possessed a phenyl group on the Cp⁰ring at 4-

position (entries 6–8). The reaction of t-butyl analogue 1c

+

R¹

CO₂R²

Me

reflux, 3 h

CH₂Cl₂

–

Fe

X

PF₆

+

Ru

OC

PR₃

MeCN

NCMe

MeCN

1

2

R¹

R²

X

Complex

1a

1b

1c

1d

Me

Ph

Et

2a

2b

2c

2d

2e

PMe₃

PMe₂Ph

PMePh₂

PPh₃

I

Bu^t

Me

adamantyl

I

PPh₃

Br

R¹

OC

CO₂R²

Me

R¹

CO₂R²

R¹

CO₂Et

Me

CO

+

Ru

Fe

OC

PR₃

X

3

4

5

6

R¹

R²

PR₃

X

R¹

R²

X

R¹

Complex

3a

3b

3c

3d

3e

3f

3g

3h

3i

Me

Ph

Bu^t

Me

Et

PMe₃

PMe₂Ph

PMePh₂

PPh₃

I

Br

I

4a

4b

4c

4d

4e

Me

Ph

Et

I

Br

I

5a

5b

Me

Ph

Bu^t

I

PMe₃

Me adamantyl

I

PMe₂Ph

PMePh₂

PMe₃

I

PMe₃

I

adamantyl

Scheme 1. Triple ligand transfer from iron complex to ruthenium complex.

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

2247

Table 1

Triple ligand transfer reactions between [Cp⁰Ru(NCMe)₃][PF₆] (1) and CpFe(CO)(L)X (2)

Entry

Substrates

Isolated yields of products (%)

Recovery of 2

Ru complex

Fe complex

Cp⁰Ru(CO)(L)X (3)^a

Cp⁰Ru(CO)₂X (4)^a

Cp⁰CpRu (5)^a

Cp₂Fe (6)^b

c

1

2

3

4

5

6

7

8

9

1a

1b

1c

1d

2a

2b

2c

2d

2e

2a

2b

2c

2a

49 ð68; S^ꢀ_CpR_R^ꢀ_uÞ (3a)

12 (4a)

22 (4a)

24 (4a)

35 (4a)

31 (4b)

17 (4c)

22 (4c)

26 (4c)

18 (4d)

12 (4e)

6 (5a)

5 (5a)

6 (5a)

2 (5a)

12 (5a)

2 (5b)

1 (5b)

9 (5b)

12

30

18

17

11

21

24

38 (22, not determined)^c(3b)

c

20 ð28; S^ꢀ_CpR_R^ꢀ_uÞ (3c)

c

12 ð34; S^ꢀ_CpR_R^ꢀ_uÞ (3d)

1

20

22

13

10

36 (22, not determined)^c(3e)

23

19

15

9

c

29 ð14; S^ꢀ_CpR_R^ꢀ_uÞ (3f)

16 (4, not determined)^c(3g)

c

48 ð40; S^ꢀ_CpR_R^ꢀ_uÞ (3h)

c

10

a

41 ð56; S^ꢀ_CpR_R^ꢀ_uÞ (3i)

Yields are based on ruthenium complex 1.

Yields are based on iron complex 2.

b

c

%De determined by ¹H and ³¹P NMR analyses and the conﬁguration of the major diastereomer are indicated in parentheses.

with 2a gave 3h in 48% yield with 40% de, whereas the reac-

tion of 1d that had a very bulky ester group with 2a pro-

duced 3i in 41% yield with 56% de. These results

suggested that the steric eﬀect of the substituents on the

Cp⁰ring on the diastereoselectivity of 3 was small.

The conﬁgurations of the major diastereomers of 3c, 3d,

3f, 3h and 3i were also determined by X-ray crystallogra-

phy. To our surprise, 3c formed single crystals with two

diastereomers in the ratio of 74:26. The structures of the

major diastereomers were conﬁrmed by measuring the ³¹P

NMR spectra of the single crystals of 3c as well as the other

compounds. The molecular structures of the major diaste-

reomers given in Figs. 2–6 are similar to each other and

clearly show that these major diastereomers have the

S^ꢀ_CpR^ꢀ_Ruconﬁguration. In these complexes, no epimerization

was observed even on reﬂuxing with CH₂Cl₂, suggesting

that the diastereoselectivity of the present reaction is under

kinetic control.

Fig. 3. ORTEP diagram of ðS^ꢀ_CpR_R^ꢀ_uÞ-3d (major diastereomer). Hydrogen

atoms are omitted for clarity.

On treatment of [Cp⁰Ru{P(OMe)₃}(NCMe)₂][PF₆] (7)

with CpFe(CO)₂X (8) in reﬂuxing CH₂Cl₂for 3 h, similar

multiple ligand transfer reactions took place to give

Cp⁰Ru{P(OMe)₃}(CO)X (9) in low to moderate yields

(Scheme 2). The results are summarized in Table 2.

Although no ruthenium complexes other than 9 were iso-

lated in these reactions, the diastereoselectivities of 9 were

low. Unfortunately, the conﬁgurations of the major diaste-

reomers of 9 could not be identiﬁed at all.

When the reaction of 1a with 2a was performed at 0 ꢁC,

dinuclear ruthenium complex (10a) was formed (Scheme 3).

Although we could not isolate 10a from the reaction mix-

ture due to low stability, the structure was conﬁrmed by

spectral analyses by comparing with the data of analogous

ruthenium complex [5]. Similar dinuclear ruthenium com-

plexes having double halide bridges have been prepared

Fig. 2. ORTEP diagram of ðS^ꢀ_CpR_R^ꢀ_uÞ-3c (major diastereomer). Hydrogen

atoms are omitted for clarity.

2248

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

Fig. 6. ORTEP diagram of ðS^ꢀ_CpR_R^ꢀ_uÞ-3i (major diastereomer). Hydrogen

atoms are omitted for clarity.

2 [10]. Cationic iron complex (13), which is unstable and

easily decomposed to give ferrocene 6 and free phosphine

ligand, is eliminated from 11 to form neutral ruthenium

complex 9 or 12. The dissociation of acetonitrile from

12 leads to dimerization to give 10, which is then con-

verted into 3 by reacting with phosphine and partially

into 4 by decomposition. In the reaction between 7 and

8, the conﬁguration at the ruthenium center in 9 is deter-

mined in the ﬁrst step where 11 is formed as the interme-

diate. From the results in Table 2, the diastereoselectivity

of this step should be low. On the other hand, the metal-

centered chirality is also generated in 12, but is lost in the

step forming 10. Thus, the conﬁguration at the ruthenium

center in 3 is determined in the last step, in which the dia-

stereoselectivity would be slightly higher than that in the

ﬁrst step. The small steric eﬀect of the substituents on

the Cp⁰ring of 1 and/or the phosphine of 2 on the diaste-

reoselectivity of 3 may be due to the free rotation of the

Cp⁰ring, generating suﬃcient space to coordinate the

ruthenium atom of 10. Since the highest selectivity was

achieved in the reaction between 1a and 2a, the electronic

eﬀect of the phosphine may be important for the diaste-

reoselective reaction of 10.

Fig. 4. ORTEP diagram of ðS^ꢀ_CpR_R^ꢀ_uÞ-3f (major diastereomer). Hydrogen

atoms are omitted for clarity.

In summary, we have shown the control of the stereo-

chemistry at the chiral metal center of planar-chiral cyclo-

pentadienyl–ruthenium complexes in the multiple ligand

transfer reaction. These results should provide useful infor-

mation to understand the mechanism of asymmetric reac-

tions using planar-chiral cyclopentadienyl–ruthenium

complexes. Further studies that focus on the application

to asymmetric catalysis are in progress.

Fig. 5. ORTEP diagram of ðS^ꢀ_CpR_R^ꢀ_uÞ-3h (major diastereomer). Hydrogen

atoms are omitted for clarity.

[9]. Since 1a was a racemic mixture, 10a consisted of two

diastereomers of dl and meso forms. Treatment of 10a with

PMe₃instantly produced 3a, inducing metal-centered chi-

rality, whereas 10a slowly decomposed in solution, generat-

ing 4a.

From the results described above, the reaction pathway

is proposed, as illustrated in Scheme 4. Heterodinuclear

complex (11) is generated by the dissociation of two ace-

tonitrile ligands from 1 and the subsequent reaction with

3. Experimental

All reactions were carried out under an argon atmo-

sphere, whereas the workup was performed in air. Dichlo-

romethane were dried over calcium hydride and distilled

before use. Other chemicals available from commercial

suppliers were used without further puriﬁcation. Ruthe-

nium complexes [g⁵-{C₅H₂(Me)(R)(COOEt)}Ru(NC-

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

2249

+

R¹

CO₂Et

Me

R¹

CO₂Et

Me

reflux, 3 h

CH₂Cl₂

–

+

Fe

PF₆

+

6

Ru

OC

CO

X

MeCN

OC

P(OMe)₃

X

MeCN

X

8

9

7

R¹

X

I

Br

I

Br

I

Complex

7a

7b

7C

Me

Ph

Bu^t

8a

8b

I

Br

9a

9b

9c

9d

9e

Me

Ph

Bu^t

Scheme 2. Double ligand transfer from iron complex to ruthenium complex.

Table 2

Double ligand transfer reactions between [Cp⁰Ru{P(OMe)₃}(NCMe)₂][PF₆] (7) and CpFe(CO)₂X (8)

Entry

Substrates

Isolated yields of products (%)

Recovery of 8

Ru complex

Fe complex

Cp⁰Ru{P(OMe)₃}(CO)X (9)^a

Cp₂Fe (6)^b

1

2

3

4

5

a

7a

7b

7c

8a

8b

8a

8b

8a

53 (0)^c(3a)

26 (12)^c(3b)

40 (8)^c(3c)

15 (0)^c(3c)

69 (14)^c(3d)

4

3

43

72

55

79

26

Yields are based on ruthenium complex 7.

Yields are based on iron complex 8.

%DeÕs determined by ¹H and ³¹P NMR analyses are indicated in parentheses.

b

c

2.54 (9H, s, CH₃CN), 4.15 (1H, s, Cp⁰), 4.75 (1H, s, Cp⁰),

5.01 (1H, broad s, Adm). ¹³C NMR (acetone-d₆): d 3.2,

12.5, 13.1, 27.8, 28.1, 32.4, 32.6, 32.7, 32.9, 36.8, 36.9,

37.9, 62.6, 67.0, 72.9, 77.4, 89.9, 98.1, 126.2, 169.7. Anal.

Calc. for C₂₄H₃₂F₆N₃O₂PRu: C, 45.00; H, 5.04; N, 6.56;

P, 4.84; F, 17.79. Found: C, 44.84; H, 5.11; N, 6.74; P,

5.01; F, 17.80%.

CO₂Et

CO

Ru

Me

X

PMe₃

0˚C

Me

+

Ru

OC

1a

2a

3a

Me

CH₂Cl₂

EtO₂C

10a

Scheme 3.

3.2. General procedure of triple ligand transfer reactions

between [{g⁵-C₅H₂(Me)(R)(COOEt)}Ru(NCMe)₃]-

[PF₆] (1) and (g⁵-C₅H₅)Fe(CO)(PR⁰₃)X (2)

Me)₃][PF₆] 1a–1c were prepared as reported previously

[3d], and iron complexes 2a [11], 2b–2d [12], 2e [13] were

prepared according to methods in the literature.

NMR spectra were measured on JEOL JNM-LA400

spectrometer using SiMe₄as an internal standard for H

A dichloromethane solution (30 mL) containing ruthe-

nium complex 1 (1.0 mmol) and iron complex 2 (1.0 mmol)

was reﬂuxed for 3 h. After removal of the solvent, the prod-

ucts were separated by silica gel column chromatography

using dichloromethane or a mixture of dichloromethane/

ethyl acetate.

1

and ¹³C NMR spectra and 85% H₃PO₄as an external ref-

erence for ³¹P NMR, respectively. IR and FAB mass spec-

tra were obtained on Perkin–Elmer system 2000 FT-IR and

JEOL JMS-600H instrument, respectively. Elemental anal-

yses were performed at The Material Analysis Center,

ISIR, Osaka University.

3.3. [g⁵-C₅H₂(Me)₂(COOEt)]Ru(CO)(PMe₃)I (3a)

3.1. [{g⁵-C₅H₂(Me)₂(COOAdm)}Ru(NCMe)₃][PF₆]

(1d)

The title complex was obtained as a mixture of two dia-

stereomers (68% de) in 49% yield. The major isomer

ðS^ꢀ_CpR^ꢀ_RuÞ-3a was isolated by recrystallization from diethyl

The title complex was prepared from 1a and 2-adamant-

ether–hexane as orange crystals. ðS^ꢀ_CpR_R^ꢀ_uÞ-3a: IR (cm^ꢁ1

,

1

anol by a similar method reported previously. IR (cm^ꢁ1

,

KBr): 1939 (m_CO), 1715 (m_C@O). H NMR (acetone-d₆): d

KBr): 1704 (m_C@O). ¹H NMR (acetone-d₆): d 1.63–1.70

(2H, m, Adm), 1.77 (3H, s, Cp⁰CH₃), 1.78–1.93 (8H, m,

Adm), 2.00 (3H, s, Cp⁰CH₃), 2.07–2.18 (4H, m, Adm),

1.27 (3H, t, J = 7.1 Hz, CH₂CH₃), 1.74 (9H, d, J_PH=

10.7 Hz, PCH₃), 1.94 (3H, s, Cp⁰CH₃), 2.45 (3H, d,

J = 2.0 Hz, Cp⁰CH₃), 4.16 (2H, m, CH₂CH₃), 5.14 (1H, s,

2250

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

CO₂R²

+

2 MeCN

+

R¹

CO₂R²

Me

R¹

CO₂R²

Me

L'

Fe

Me

X

–

PF₆

+

Ru

Fe

X

Ru

X

Ru

R¹

OC

MeCN

L'

OC

L

C

O

L

MeCN

2 MeCN

+

9: L = P(OMe)₃

12: L = NCMe

1: L = NCMe

7: L = P(OMe)₃

2: L' = PR₃

8: L = CO

11

Fe

–

PF₆

MeCN

L'

MeCN

13

+

L'

Fe

MeCN

CO₂R²

6

CO

Me

X

R¹

Ru

Me

Ru

R¹

X

OC

R²O₂C

10

dl and meso

R¹

CO₂R²

Me

PR₃

Ru

OC

CO

X

4

R¹

OC

CO₂R²

Me

Ru

PR₃

X

3

Scheme 4. Proposed reaction pathway.

Cp⁰), 5.45 (1H, d, J = 2.2 Hz, Cp⁰). ¹³C NMR (acetone-d₆):

d 14.2, 14.7, 16.0, 20.5 (d, J_PC= 35 Hz), 60.8, 82.3, 87.0 (d,

J_PC= 7 Hz), 87.2, 95.4, 115.6, 166.2, 204.4 (d,

J_PC= 22 Hz). ³¹P NMR (acetone-d₆): d 13.0. Mass: m/z

498 (M⁺). Anal. Calc. for C₁₄H₂₂IO₃PRu: C, 33.82; H,

4.46; P, 6.23; I, 25.52. Found: C, 33.64; H, 4.62; P, 6.46;

I, 25.57%. ðS^ꢀ_CpS_R^ꢀ_uÞ-3a: ¹H NMR (acetone-d₆): d 1.23

(3H, t, J = 7.1 Hz, CH₂CH₃), 1.71 (9H, d, J_PH= 10.5 Hz,

PCH₃), 2.11 (3H, s, Cp⁰CH₃), 2.31 (3H, s, Cp⁰CH₃), 4.16

(2H, m, CH₂CH₃), 5.08 (1H, s, Cp⁰), 5.58 (1H, s, Cp⁰).

³¹P NMR (acetone-d₆): d 11.9.

J_PC= 7 Hz), 90.4, 94.7, 114.5 (d, J_PC= 4 Hz), 129.3 (d,

J_PC= 10 Hz), 130.4 (d, J_PC= 10 Hz), 130.5 (d, J_PC

=

2 Hz), 139.9 (d, J_PC= 50 Hz), 165.9, 203.9 (d, J_PC

31

21 Hz). P NMR (acetone-d₆): d 22.2. ðS^ꢀ_CpS_R^ꢀ_uÞ-3b: ¹H

NMR (acetone-d₆): d 1.20 (3H, t, J = 7.1 Hz, CH₂CH₃),

1.76 (3H, s, Cp⁰CH₃), 1.92 (3H, d, J_PH= 10.0 Hz, PCH₃),

2.10 (3H, d, J_PH= 10.3 Hz, PCH₃), 2.15 (3H, d,

J = 1.2 Hz, Cp⁰CH₃), 4.17 (2H, m, CH₂CH₃), 4.90 (1H, s,

Cp⁰), 5.29 (1H, d, J = 2.0 Hz, Cp⁰), 7.46–7.53 (3H, m,

PC₆H₅), 7.68–7.70 (2H, m, PC₆H₅). ¹³C NMR (acetone-

d₆): d 13.5, 14.5, 15.7, 19.8 (d, J_PC= 34 Hz), 20.6 (d,

J_PC= 37 Hz), 60.7, 80.0, 88.7 (d, J_PC= 5 Hz), 90.7 (d,

J_PC= 3 Hz), 101.4, 109.0, 129.1 (d, J_PC= 10 Hz), 130.6

(d, J_PC= 3 Hz), 131.0 (d, J_PC= 10 Hz), 138.3 (d,

J_PC= 49 Hz), 166.4, 204.3 (d, J_PC= 21 Hz). ³¹P NMR

(acetone-d₆): d 23.0.

3.4. [g⁵-C₅H₂(Me)₂(COOEt)]Ru(CO)(PMe₂Ph)I (3b)

The title complex was obtained as a mixture of two dia-

stereomers (22% de) in 38% yield. Recrystallization from

dichloromethane–he_ꢀxane gave red crystals, in which the

minor isomer ðS^ꢀ_CpS_RuÞ-3b was enriched into 74% de. IR

(cm^ꢁ1, KBr): 1949 (m_CO), 1712 (m_C@O). Mass: m/z 560

(M⁺). Anal. Calc. for C₁₉H₂₄IO₃PRu: C, 40.80; H, 4.32;

P, 5.54; I, 22.69. Found: C, 41.00; H, 4.51; P, 5.67; I,

3.5. [g⁵-C₅H₂(Me)₂(COOEt)]Ru(CO)(PMePh₂)I (3c)

The title complex was obtained as a mixture of two dia-

stereomers (28% de) in 20% yield. Recrystallization from

dichloromethane–hexane gave red crystals, in which the

major isomer ðS^ꢀ_CpR_R^ꢀ_uÞ-3c was enriched into 48% de. IR

(cm^ꢁ1, KBr): 1940 (m_CO), 1712 (m_C@O). Mass: m/z 622

(M⁺). Anal. Calc. for C₂₄H₂₆IO₃PRu: C, 46.39; H, 4.22;

P, 4.98; I, 20.42. Found: C, 46.26; H, 4.21; P, 5.05; I,

20.38%. ðS^ꢀ_CpR_R^ꢀ_uÞ-3c: 1H NMR (acetone-d₆): d 1.10 (3H,

t, J = 7.1 Hz, CH₂CH₃), 1.67 (3H, s, Cp⁰CH₃), 2.34 (3H,

d, J_PH= 9.5 Hz, PCH₃), 2.48 (3H, d, J = 2.0 Hz, Cp⁰CH₃),

1

22.53%. ðS^ꢀ_CpR_R^ꢀ_uÞ-3b: H NMR (acetone-d₆): d 1.24 (3H,

t, J = 7.1 Hz, CH₂CH₃), 1.62 (3H, s, Cp⁰CH₃), 2.00 (3H,

d, J_PH= 10.3 Hz, PCH₃), 2.09 (3H, d, J = 10.7 Hz,

PCH₃), 2.39 (3H, d, J = 2.2 Hz, Cp⁰CH₃), 4.02 (2H, m,

CH₂CH₃), 4.74 (1H, d, J = 2.2 Hz, Cp⁰), 5.09 (1H, s,

Cp⁰), 7.46–7.53 (3H, m, PC₆H₅), 7.71–7.73 (2H, m,

PC₆H₅). ¹³C NMR (acetone-d₆): d 14.3, 14.6, 16.8 (d,

J_PC= 34 Hz), 20.4 (d, J_PC= 38 Hz), 60.8, 82.2, 86.9 (d,

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

2251

3.93 (2H, m, CH₂CH₃), 4.62 (1H, dd, J = 2.0, 1.7 Hz, Cp⁰),

5.07 (1H, d, J = 1.7 Hz, Cp⁰), 7.43–7.50 (6H, m, PC₆H₅),

7.54–7.72 (4H, m, PC₆H₅). ¹³C NMR (acetone-d₆): d

13.5, 14.2, 15.7, 20.0 (d, J_PC= 35 Hz), 60.6, 82.5, 85.1 (d,

J_PC= 7 Hz), 89.7, 91.5, 115.8, 128.3 (d, J_PC= 6 Hz),

J_PC= 36 Hz), 60.9, 83.3 (d, J_PC= 4 Hz), 86.1, 88.1, 96.5,

112.1 (d, J_PC= 3 Hz), 126.6, 128.9, 129.6, 133.2, 165.9,

204.0 (d, J_PC= 22 Hz). ³¹P NMR (acetone-d₆): d 13.3.

ðS_C^ꢀ_pS_R^ꢀ_uÞ-3e: ¹H NMR (acetone-d₆): d 1.31 (3H, t,

J = 7.1 Hz, CH₂CH₃), 1.60 (9H, d, J_PH= 10.5 Hz,

PCH₃), 2.51 (3H, d, J = 1.5 Hz, Cp⁰CH₃), 4.22 (2H, m,

CH₂CH₃), 5.82 (1H, s, Cp⁰), 6.25 (1H, dd, J = 2.0,

1.7 Hz, Cp⁰), 7.26–7.41 (3H, m, Cp⁰C₆H₅), 7.62–7.64 (2H,

m, Cp⁰C₆H₅). ¹³C NMR (acetone-d₆): d 14.7, 15.2, 20.3

(d, J_PC= 36 Hz), 60.8, 81.6, 83.4, 88.8 (d, J_PC= 3 Hz),

97.0, 111.4, 127.2, 128.7, 129.5, 133.5, 166.3, 203.17 (d,

J_PC= 21 Hz). ³¹P NMR (acetone-d₆): d 13.3.

128.5 (d, J_PC= 10 Hz), 130.2, 130.6, 132.1 (d, J_PC

=

10 Hz), 133.4 (d, J_PC= 11 Hz), 135.6 (d, J_PC= 47 Hz),

138.2 (d, J_PC= 51 Hz), 165.7, 203.7 (d, J_PC= 21 Hz). ³¹P

NMR (acetone-d₆): d 36.0. ðS^ꢀ_CpS_R^ꢀ_uÞ-3c: ¹H NMR (ace-

tone-d₆): d 1.15 (3H, t, J = 7.1 Hz, CH₂CH₃), 1.72 (3H, s,

Cp⁰CH₃), 2.29 (3H, d, J_PH= 11.6 Hz, PCH₃), 3.79 (3H, s,

Cp⁰CH₃), 3.93 (2H, m, CH₂CH₃), 4.91 (1H, s, Cp⁰), 5.18

(1H, d, J = 1.7 Hz, Cp⁰), 7.42–7.49 (6H, m, PC₆H₅),

7.54–7.69 (4H, m, PC₆H₅). ¹³C NMR (acetone-d₆): d

13.7, 14.2, 14.3, 21.3 (d, J_PC= 36 Hz), 60.7, 79.2, 87.4 (d,

J_PC= 6 Hz), 96.1, 103.5, 108.8, 128.4 (d, J_PC= 4 Hz),

128.5 (d, J_PC= 4 Hz), 130.4, 132.5 (d, J_PC= 11 Hz),

132.6 (d, J_PC= 11 Hz), 136.3 (d, J_PC= 51 Hz), 136.8 (d,

J_PC= 47 Hz), 166.4, 203.3 (d, J_PC= 20 Hz). ³¹P NMR

(acetone-d₆): d 36.5.

3.8. [g⁵-C₅H₂(Me)(Ph)(COOEt)]Ru(CO)(PMe₂Ph)I

(3f)

The title complex was obtained as a mixture of two

diastereomers (14% de) in 29% yield. The major isomer

ðS^ꢀ_CpR^ꢀ_RuÞ-3f was isolated by recrystallization from dichlo-

romethane-hexane as red crystals. ðS^ꢀ_CpR_R^ꢀ_uÞ-3f: IR (cm^ꢁ1

,

1

KBr): 1955 (m_CO), 1714 (m_C@O). H NMR (acetone-d₆): d

3.6. [g⁵-C₅H₂(Me)₂(COOEt)]Ru(CO)(PMePh₂)Br (3d)

1.29 (3H, t, J = 7.3 Hz, CH₂CH₃), 1.64 (3H, d, J_PH=

10.0 Hz, PCH₃), 1.96 (3H, d, J_PH= 10.5 Hz, PCH₃),

2.19 (3H, s, Cp⁰CH₃), 4.17 (2H, m, CH₂CH₃), 5.38

(1H, d, J = 1.7 Hz, Cp⁰), 6.09 (1H, d, J = 1.7 Hz, Cp⁰),

7.18–7.47 (8H, m, PC₆H₅), 7.54–7.59 (2H, m, PC₆H₅).

The title complex was obtained as a mixture of two dia-

stereomers (34% de) in 12% yield. The major isomer

ðS^ꢀ_CpR^ꢀ_RuÞ-3d was isolated by recrystallization from dichlo-

romethane–hexane as orange crystals. ðS^ꢀ_CpR_R^ꢀ_uÞ-3d: IR

(cm^ꢁ1, KBr): 1952 (m_CO), 1704 (m_C@O). ¹H NMR (ace-

tone-d₆): d 1.02 (3H, t, J = 7.1 Hz, CH₂CH₃), 1.69 (3H, s,

Cp⁰CH₃), 2.23 (3H, d, J = 2.0 Hz, Cp⁰CH₃), 3.97 (1H, d,

J = 2.0 Hz, Cp⁰), 3.98 (2H, m, CH₂CH₃), 5.02 (1H, d,

J = 2.0 Hz, Cp⁰), 7.41–7.50 (9H, m, PC₆H₅), 7.65–7.70

(6H, m, PC₆H₅). ³¹P NMR (acetone-d₆): d 50.0. Mass: m/

z 637 (M⁺). Anal. Calc. for C₂₉H₂₈BrO₃PRu: C, 54.73;

H, 4.43; P, 4.87; Br, 12.55. Found: C, 54.98; H, 4.14; P,

4.93; I, 12.32%. ðS^ꢀ_CpS_R^ꢀ_uÞ-3d: ¹H NMR (acetone-d₆): d

1.15 (3H, t, J = 7.1 Hz, CH₂CH₃), 1.53 (3H, s, Cp⁰CH₃),

2.20 (3H, d, J = 1.0 Hz, Cp⁰CH₃), 3.71 (2H, m, CH₂CH₃),

4.53 (1H, d, J = 2.0 Hz, Cp⁰), 4.93 (1H, d, J = 2.0 Hz, Cp⁰),

7.41–7.50 (9H, m, PC₆H₅), 7.55–7.60 (6H, m, PC₆H₅). ³¹P

NMR (acetone-d₆): d 54.5.

¹³C NMR (acetone-d₆): d 14.4, 14.7, 19.5 (d, J_PC

=

38 Hz), 19.7 (d, J_PC= 35 Hz), 60.8, 82.0 (d, J_PC= 3 Hz),

87.4 (d, J_PC= 3 Hz), 87.5, 99.0, 110.6, 126.8, 128.6, 129.0

(d, J_PC= 10 Hz), 129.3, 130.6 (d, J_PC= 3 Hz), 131.0 (d,

J_PC= 10 Hz), 132.4, 137.6 (d, J_PC= 47 Hz), 165.9,

203.4 (d, J_PC= 22 Hz). ³¹P NMR (acetone-d₆): d 23.3.

Mass: m/z 622 (M⁺). Anal. Calc. for C₂₄H₂₆IO₃PRu:

C, 46.39; H, 4.42; P, 4.98; I, 20.42. Found: C, 46.32;

1

H, 4.23; P, 4.76; I, 20.50%. ðS^ꢀ_CpS_R^ꢀ_uÞ-3f: H NMR (ace-

tone-d₆): d 1.30 (3H, t, J = 7.3 Hz, CH₂CH₃), 1.89 (3H,

d, J_PH= 10.3 Hz, PCH₃), 1.93 (3H, d, J_PH= 11.2 Hz,

PCH₃), 2.50 (3H, d, J = 1.7 Hz, Cp⁰CH₃), 4.20 (2H, m,

CH₂CH₃), 5.53 (1H, dd, J = 2.0, 1.7 Hz, Cp⁰), 5.56

(1H, s, Cp⁰), 7.05–7.07 (2H, m, C₆H₅), 7.18–7.47 (2H,

m, C₆H₅). ¹³C NMR (acetone-d₆): d 14.7, 15.8 (d,

J_PC= 34 Hz), 15.9, 20.4 (d, J_PC= 39 Hz), 61.0, 73.9,

83.8 (d, J_PC= 5 Hz), 89.8, 96.2, 113.0 (d, J_PC= 3 Hz),

126.4, 128.7, 129.3, 129.3 (d, J_PC= 9 Hz), 130.2 (d,

J_PC= 10 Hz), 130.4 (d, J_PC= 3 Hz), 132.3, 139.4 (d,

J_PC= 50 Hz), 165.8, 203.9 (d, J_PC= 22 Hz). ³¹P NMR

(acetone-d₆): d 22.4.

3.7. [g⁵-C₅H₂(Me)(Ph)(COOEt)]Ru(CO)(PMe₃)I (3e)

The title complex was obtained as a mixture of two dia-

stereomers (22% de) in 36% yield. Recrystallization from

dichloromethane–hexane gave red crystals, in which the

major isomer ðS^ꢀ_CpR_R^ꢀ_uÞ-3e was enriched into 74% de. IR

(cm^ꢁ1, KBr): 1940 (m_CO), 1714 (m_C@O). Mass: m/z 560

(M⁺). Anal. Calc. for C₁₉H₂₄IO₃PRu: C, 40.80; H, 4.32;

P, 5.54; I, 22.69. Found: C, 40.77; H, 4.27; P, 5.32; I,

3.9. [g⁵-C₅H₂(Me)(Ph)(COOEt)]Ru(CO)(PMePh₂)I

(3g)

1

22.87%. ðS^ꢀ_CpR_R^ꢀ_uÞ-3e: H NMR (acetone-d₆): d 1.30 (3H,

The title complex was obtained as a mixture of two dia-

stereomers (4% de) in 16% yield. IR (cm^ꢁ1, KBr): 1953

(m_CO), 1712 (m_C@O). ¹H NMR (CD₂Cl₂): d 1.18 (3H, t,

J = 7.1 Hz, CH₂CH₃), 1.33 (3H, t, J = 7.1 Hz, CH₂CH₃),

2.04 (3H, d, J_PH= 9.5 Hz, PCH₃), 2.16 (3H, d,

J_PH= 9.8 Hz, PCH₃), 2.35 (3H, s, Cp⁰CH₃), 2.61 (3H, s,

t, J = 7.1 Hz, CH₂CH₃), 1.49 (9H, d, J_PH= 10.7 Hz,

PCH₃), 2.49 (3H, s, Cp⁰CH₃), 4.22 (2H, m, CH₂CH₃),

5.84 (1H, d, J = 1.7 Hz, Cp⁰), 6.27 (1H, d, J = 1.7 Hz,

Cp⁰), 7.26–7.41 (3H, m, Cp⁰C₆H₅), 7.60–7.62 (2H, m,

Cp⁰C₆H₅). ¹³C NMR (acetone-d₆): d 14.8, 15.8, 20.1 (d,

2252

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

1

Cp⁰CH₃), 3.99 (2H, m, CH₂CH₃), 4.09 (2H, m, CH₂CH₃),

5.27 (1H, s, Cp⁰), 5.32 (1H, s, Cp⁰), 5.31 (1H, d, J = 1.7 Hz,

Cp⁰), 5.38 (1H, d, J = 1.7 Hz, Cp⁰), 6.96–6.98 (2H, m,

C₆H₅), 7.06–7.08 (2H, m, C₆H₅), 7.19–7.50 (13H, m,

C₆H₅). ¹³C NMR (CD₂Cl₂): d 14.3, 14.4, 14.5, 16.0, 19.3

(d, J_PC= 36 Hz), 20.4 (d, J_PC= 36 Hz), 60.9, 61.0, 80.9,

83.1, 82.2 (d, J_PC= 6 Hz), 86.7 (d, J_PC= 4 Hz), 88.5 (d,

J_PC= 2 Hz), 89.1, 97.3, 101.5, 109.5, 114.5, 126.3, 126.8,

128.4 (d, J_PC= 11 Hz), 128.5 (d, J_PC= 11 Hz), 128.5 (d,

J_PC= 11 Hz), 128.4, 128.5, 128.8, 129.0, 130.2 (d,

J_PC= 2 Hz), 130.4 (d, J_PC= 3 Hz), 130.5 (d, J_PC= 2 Hz),

130.7 (d, J_PC= 2 Hz), 131.6, 131.7, 132.0 (d, J_PC= 10 Hz),

132.4 (d, J_PC= 10 Hz), 132.6 (d, J_PC= 11 Hz), 133.4 (d,

5.23; P, 5.07; I, 20.85%. ðS^ꢀ_CpR_R^ꢀ_uÞ-3i: H NMR (CDCl₃):

d 1.55–1.61 (2H, m, Adm), 1.69–1.80 (3H, m, Adm), 1.72

(9H, d, J = 10.5 Hz, PCH₃), 1.85 (4H, m, Adm), 1.95

(3H, s, Cp⁰CH₃), 2.01–2.07 (3H, m, Adm), 2.17–2.20 (1H,

m, Adm), 2.75 (3H, s, Cp⁰CH₃), 4.99 (1H, s, Cp⁰), 5.03

(1H, broad s, Adm), 5.25 (1H, s, Cp⁰). ³¹P NMR (CDCl₃):

d 7.4. ðS^ꢀ_CpS_R^ꢀ_uÞ-3i: 6.0.

3.12. [g⁵-C₅H₂(Me)₂(COOEt)]Ru(CO)₂I (4a)

IR (cm^ꢁ1, KBr): 2048, 1990 (m_CO), 1715 (m_C@O). ¹H

NMR (acetone-d₆): d 1.29 (3H, t, J = 7.1 Hz, CH₂CH₃),

2.20 (3H, s, Cp⁰CH₃), 2.56 (3H, s, Cp⁰CH₃), 4.24 (2H, m,

CH₂CH₃), 5.52 (1H, d, J = 1.7 Hz, Cp⁰), 5.99 (1H, d,

J = 1.7 Hz, Cp⁰). ¹³C NMR (acetone-d₆): d 14.2, 14.5,

15.1, 61.7, 84.0, 88.5, 88.8, 106.7, 118.8, 164.5, 197.0,

197.2. Mass: m/z 450 (M⁺). Anal. Calc. for C₁₂H₁₃IO₄Ru:

C, 32.09; H, 2.92; I, 28.34. Found: C, 31.83; H, 2.66; I,

28.34%.

J_PC= 11 Hz), 135.3 (d, J_PC= 41 Hz), 135.8 (d, J_PC

=

42 Hz), 136.9 (d, J_PC= 48 Hz), 138.3 (d, J_PC= 51 Hz),

165.6, 166.1, 203.1 (d, J_PC= 22 Hz), 203.3 (d, J_PC

=

22 Hz). ³¹P NMR (acetone-d₆): d 36.0, 36.2. Mass: m/z

684 (M⁺). Anal. Calc. for C₂₉H₂₈IO₃PRu: C, 50.96; H,

4.13; P, 4.53; I, 18.57. Found: C, 50.71; H, 4.11; P, 4.29;

I, 18.82%.

3.13. [g⁵-C₅H₂(Me)₂(COOEt)]Ru(CO)₂Br (4b)

3.10. [g⁵-C₅H₂(Me)(Bu^t)(COOEt)]Ru(CO)(PMe₃)I

(3h)

IR (cm^ꢁ1, KBr): 2053, 2003 (m_CO), 1722 (m_C@O). ¹H

NMR (acetone-d₆): d 1.29 (3H, t, J = 7.1 Hz, CH₂CH₃),

2.08 (3H, s, Cp⁰CH₃), 2.32 (3H, s, Cp⁰CH₃), 4.24 (2H, m,

CH₂CH₃), 5.53 (1H, d, J = 1.7 Hz, Cp⁰), 5.90 (1H, d,

J = 1.7 Hz, Cp⁰). ¹³C NMR (acetone-d₆): d 13.7, 14.0,

14.5, 61.7, 83.5, 86.5, 88.6, 106.9, 121.5, 164.6, 197.0,

197.3. Mass: m/z 402 (M⁺). Anal. Calc. for

C₁₂H₁₃BrO₄Ru: C, 35.84; H, 3.26; Br, 19.87. Found: C,

36.12; H, 3.05; Br, 20.11%.

The title complex was obtained as a mixture of two dia-

stereomers (40% de) in 48% yield. The major isomer

ðS^ꢀ_CpR^ꢀ_RuÞ-3h was isolated by recrystallization from diethyl

ether as orange crystals. ðS^ꢀ_CpR_R^ꢀ_uÞ-3h: IR (cm^ꢁ1, KBr):

1940 (m_CO), 1683 (m_C@O). ¹H NMR (acetone-d₆): d 1.21

(9H, s, C(CH₃)₃), 1.28 (3H, t, J = 7.1 Hz, CH₂CH₃), 1.74

(9H, d, J_PH= 10.5 Hz, PCH₃), 2.54 (3H, d, J = 2.0 Hz,

Cp⁰CH₃), 4.17 (2H, m, CH₂CH₃), 5.10 (1H, d,

J = 2.0 Hz, Cp⁰), 5.37 (1H, dd, J = 2.7 , 2.0 Hz, Cp⁰). ¹³C

NMR (acetone-d₆): d 14.6, 16.8, 20.5 (d, J_PC= 36 Hz),

31.2, 31.4, 60.9, 81.4, 81.9, 82.3 (d, J_PC= 7 Hz), 114.8,

118.5 (d, J_PC= 3 Hz), 166.4, 204.9 (d, J_PC= 21 Hz). ³¹P

NMR (acetone-d₆): d 10.9. Mass: m/z 540 (M⁺). Anal.

Calc. for C₁₇H₂₈IO₃PRu: C, 37.86; H, 5.23; P, 5.74; I,

23.53. Found: C, 38.09; H, 5.25; P, 5.88; I, 23.38%.

ðS^ꢀ_CpS_R^ꢀ_uÞ-3h: 1H NMR (acetone-d₆): d 1.27 (3H, t,

J = 7.1 Hz, CH₂CH₃), 1.28 (9H, s, C(CH₃)₃), 1.69 (9H, d,

JPH = 10.5 Hz, P(CH₃)₃), 2.23 (3H, d, J = 2.7 Hz,

Cp⁰CH₃), 4.17 (2H, m, CH₂CH₃), 4.99 (1H, d,

J = 2.0 Hz, Cp⁰), 5.84 (1H, dd, J = 2.4, 2.0 Hz, Cp⁰). ¹³C

NMR (acetone-d₆): d 14.4, 15.0, 19.1 (d, J_PC= 36 Hz),

31.2, 32.0, 60.7, 74.9, 79.4, 94.1 (d, J_PC= 5 Hz), 106.2,

118.5 (d, J_PC= 5 Hz), 166.3, 204.8 (d, J_PC= 22 Hz). ³¹P

NMR (acetone-d₆): d 9.6.

3.14. [g⁵-C₅H₂(Me)(Ph)(COOEt)]Ru(CO)₂I (4c)

IR (cm^ꢁ1, KBr): 2040, 1999 (m_CO), 1704 (m_C@O). ¹H

NMR (acetone-d₆): d 1.32 (3H, t, J = 7.1 Hz, CH₂CH₃),

2.68 (3H, s, Cp⁰CH₃), 4.29 (2H, m, CH₂CH₃), 6.24 (1H,

d, J = 2.0 Hz, Cp⁰), 6.71 (1H, d, J = 2.0 Hz, Cp⁰), 7.37–

7.44 (3H, m, C₆H₅), 7.72–7.74 (2H, m, C₆H₅). ¹³C NMR

(acetone-d₆): d 14.7, 15.5, 61.8, 85.1, 85.7, 87.2, 105.3,

119.4, 127.4, 129.9, 130.4, 130.9, 164.4, 196.4, 197.0.

Mass: m/z 512 (M⁺). Anal. Calc. for C₁₇H₁₅IO₄Ru: C,

39.94; H, 2.96; I, 24.82. Found: C, 40.19; H, 3.09; I,

24.71%.

3.15. [g⁵-C₅H₂(Me)(Bu^t)(COOEt)]Ru(CO)₂I (4d)

IR (cm^ꢁ1, KBr): 2041, 1998 (m_CO), 1722 (m_C@O). ¹H

NMR (acetone-d₆): d 1.27 (9H, s, C(CH₃)₃), 1.28 (3H, t,

J = 7.3 Hz, CH₂CH₃), 2.58 (3H, s, Cp⁰CH₃), 4.23 (2H, m,

CH₂CH₃), 5.70 (1H, d, J = 1.7 Hz, Cp⁰), 6.16 (1H, d,

J = 1.7 Hz, Cp⁰). ¹³C NMR (acetone-d₆): d 14.6, 15.4,

31.3, 31.4, 61.5, 84.2, 87.8, 89.1, 117.6, 118.4, 164.2,

196.9, 197.7. Mass: m/z 492 (M⁺). Anal. Calcd for

C₁₅H₁₉IO₄Ru: C, 36.67; H, 3.90; I, 25.83. Found: C,

36.80; H, 4.11; I, 25.71%.

3.11. [g⁵-C₅H₂(Me)₂(COOAdm)]Ru(CO)(PMe₃)I (3i)

The title complex was obtained as a mixture of two dia-

stereomers (56% de) in 41% yield. ðS^ꢀ_CpR_R^ꢀ_uÞ-3i was isolated

by recrystallization from dichloromethane–hexane as

orange crystals. IR (cm^ꢁ1, KBr): 1941 (m_CO), 1714 (m_C@O).

Mass: m/z 604 (M⁺). Anal. Calc. for C₂₂H₃₂IO₃PRu: C,

43.79; H, 5.35; P, 5.13; I, 21.03. Found: C, 43.77, H,

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

2253

3.16. [g⁵-C₅H₂(Me)₂(COOAdm)]Ru(CO)₂I (4e)

3.20. [{g⁵-C₅H₂(Me)(Ph)(COOEt)}Ru(NCMe)₂-

{P(OMe)₃}] [PF₆] (7b).

IR (cm^ꢁ1, KBr): 2042, 1990 (m_CO), 1716 (m_C@O). ¹H

NMR (acetone-d₆): d 1.60–1.63 (2H, m, Adm), 1.77–1.91

(8H, m, Adm), 2.04 (2H, m, Adm), 2.14–2.18 (2H, m,

Adm), 2.20 (3H, s, Cp⁰CH₃), 2.61 (3H, s, Cp⁰CH₃), 5.04

(1H, broad, Adm), 5.54 (1H, s, Cp⁰), 6.09 (1H, s, Cp⁰).

¹³C NMR (acetone-d₆): d 14.1, 15.4, 27.8, 28.0, 32.5,

32.5, 32.7, 32.7, 36.8, 36.9, 37.9, 78.7, 84.4, 88.9, 89.0,

106.0, 118.7, 163.9, 197.0, 197.2. Mass: m/z 556 (M⁺).

Anal. Calc. for C₂₀H₂₃IO₄PRu: C, 43.25; H, 4.17; I,

22.85. Found: C, 43.46; H, 4.09; I, 22.82%.

The title complex was prepared by a similar method to

that for 7a in 98% yield. IR (cm^ꢁ1, KBr): 1714 (m_C@O).

¹H NMR (acetone-d₆): d 1.31 (3H, t, J = 7.1 Hz, CH₂CH₃),

2.14 (3H, d, J = 2.0 Hz, Cp⁰CH₃), 2.40 (3H, d, J = 1.2 Hz,

CH₃CN), 2.52 (3H, d, J = 1.0 Hz, CH₃CN), 3.51 (9H, d,

J = 11.7 Hz, OCH₃), 4.22 (2H, m, CH₂CH₃), 5.45 (1H, s,

Cp⁰), 5.73 (1H, d, J = 1.7 Hz, Cp⁰), 7.31–7.39 (3H, m,

C₆H₅), 7.57–7.59 (2H, m, C₆H₅). ¹³C NMR (acetone-d₆):

d 3.4, 3.5, 13.1, 14.6, 52.2 (d, J_PC= 3 Hz), 61.2, 70.5, 77.6

(d, J_PC= 8 Hz), 78.8, 93.4, 108.2, 127.5, 128.6 128.8,

129.1, 129.6, 133.1, 168.5. ³¹P NMR (acetone-d₆): d

154.0. Anal. Calc. for C₂₂H₃₀N₂O₅P₂F₆Ru: C, 38.89; H,

4.45; N, 4.12; P, 9.12; F, 16.78. Found: C, 38.77; H, 4.62;

N, 4.42; P, 9.23; F, 16.90%.

3.17. [g⁵-C₅H₂(Me)₂(COOEt)]Ru(C₅H₅) (5a)

1

IR (cm^ꢁ1, KBr): 1711(m_C@O). H NMR (acetone-d₆): d

1.23 (3H, t, J = 7.1 Hz, CH₂CH₃), 1.90 (3H, s, Cp⁰CH₃),

2.17 (3H, s, Cp⁰CH₃), 4.13 (2H, m, CH₂CH₃), 4.46 (5H,

s, C₅H₅), 4.76 (1H, s, Cp⁰), 4.99 (1H, s, Cp⁰). ¹³C NMR

(acetone-d₆): d 14.7, 15.0, 15.3, 60.0, 73.1, 74.0, 74.8,

78,5, 88.3, 89.3, 171.1. Mass: m/z 332 (M⁺). Anal. Calc.

for C₁₅H₁₈O₂Ru: C, 54.37; H, 5.48. Found: C, 54.21; H,

5.57%.

3.21. [{g⁵-C₅H₂(Me)(Bu^t)(COOEt)}Ru(NCMe)₂-

{P(OMe)₃}][PF₆] (7c)

The title complex was prepared by a similar method to

that for 7a in 99% yield. IR (cm^ꢁ1, KBr): 1716 (m_C@O).

¹H NMR (acetone-d₆): d 1.18 (9H, s, C(CH₃)₃), 1.28 (3H,

t, J = 7.1 Hz, CH₂CH₃), 2.05 (3H, d, J = 2.9 Hz, Cp⁰CH₃),

2.59 (3H, d, J = 1.5 Hz, CH₃CN), 2.63 (3H, d, J = 1.5 Hz,

CH₃CN), 3.69 (9H, d, J = 11.5 Hz, OCH₃), 4.15 (2H, m,

CH₂CH₃), 5.07 (1H, d, J = 1.7 Hz, Cp⁰), 5.14 (1H, dd,

J = 2.9, 1.7 Hz, Cp⁰). ¹³C NMR (acetone-d₆): d 3.5, 13.1,

14.6, 31.0, 31.4, 52.5 (d, J_PC= 4.1 Hz), 61.1, 67.5, 79.7,

80.5 (d, J_PC= 10 Hz), 106.0, 108.5, 128.7, 129.8, 169.2.

3.18. [g⁵-C₅H₂(Me)(Ph)(COOEt)]Ru(C₅H₅) (5b)

IR (cm^ꢁ1, KBr): 1713(m_C@O). ¹H NMR (CD₂Cl₂): d 1.31

(3H, t, J = 7.1 Hz, CH₂CH₃), 2.30 (3H, s, Cp⁰CH₃), 4.22

(2H, m, CH₂CH₃), 4.44 (5H, s, C₅H₅), 5.22 (1H, s, Cp⁰),

5.53 (1H, s, Cp⁰), 7.16 (1H, t, J = 7.3 Hz, C₆H₅), 7.23

(2H, t, J = 7.3 Hz, C₆H₅), 7.39 (2H, d, J = 7.3 Hz, C₆H₅).

¹³C NMR (CD₂Cl₂): d 14.6, 15.4, 60.3, 71.2, 73.7, 75.5,

75.8, 90.4, 90.6, 126.8, 126.9, 128.4, 137.7, 171.0. Mass:

m/z 394 (M⁺). Anal. Calc. for C₂₀H₂₀O₂Ru: C, 61.06; H,

5.12. Found: C, 61.03; H, 4.88%.

³¹P NMR (acetone-d₆):

d 153.3. Anal. Calc. for

C₂₀H₃₄N₂O₅P₂F₆Ru: C, 36.42; H, 5.20; N, 4.25; P, 9.39;

F, 17.28. Found: C, 36.24; H, 5.07; N, 4.07; P, 9.19; F,

17.33%.

3.19. Synthesis of [{g⁵-C₅H₂(Me)₂(COOEt)}Ru(NCMe)₂-

{P(OMe)₃}][PF₆] (7a)

3.22. General procedure of double ligand transfer reactions

between [{g⁵-C₅H₂(Me)(R)(COOEt)}Ru{P(OMe)₃}-

(NCMe)₂][PF₆] (7) and (g⁵-C₅H₅)Fe(CO)₂X (8)

To an acetonitrile solution (20 mL) of 1a (2.67 g,

5.0 mmol) was added trimethylphosphite (0.8 mL,

6.1 mmol). After stirring at room temperature for 5 min,

the solvent was evaporated. The residue was washed with

diethyl ether, and dried under reduced pressure to give

yellow powder (3.05 g, 99%). IR (cm^ꢁ1, KBr): 1712

Ruthenium complex 7 (1.0 mmol) and iron complex 8

(1.0 mmol) was dissolved in A dichloromethane (30 mL),

and the reaction mixture was stirred for 3 h under

reﬂux. After removal of the solvent, the products were

separated by silica gel column chromatography using

dichloromethane or a mixture of dichloromethane/ethyl

acetate.

1

(m_C@O). H NMR (acetone-d₆): d 1.28 (3H, t, J = 7.1 Hz,

CH₂CH₃), 1.79 (3H, s, Cp⁰CH₃), 2.02 (3H, d,

J = 1.7 Hz, Cp⁰CH₃), 2.60 (3H, d, J = 1.2 Hz, CH₃CN),

2.61 (3H, d, J = 1.2 Hz, CH₃CN), 3.67 (9H, d,

J = 11.7 Hz, OCH₃), 4.19 (2H, m, CH₂CH₃), 4.71 (1H,

s, Cp⁰), 4.98 (1H, d, J = 1.7 Hz, Cp⁰). ¹³C NMR (ace-

tone-d₆): d 3.6, 12.6, 12.8, 14.6, 52.2 (d, J_PC= 3 Hz),

60.9, 71.3, 78.2 (d, J_PC= 7 Hz), 80.1, 94.6, 108.2, 128.5,

168.4. ³¹P NMR (acetone-d₆): d 156.2. Anal. Calc. for

C₁₇H₂₈N₂O₅P₂F₆Ru: C, 33.07; H, 4.57; N, 4.54; P,

10.03; F, 18.46. Found: C, 33.33; H, 4.32; N, 4.52; P,

10.23; F, 18.22%.

3.23. [g⁵-C₅H₂(Me)₂(COOEt)]Ru[P(OMe)₃](CO)I

(9a)

This complex was obtained as a mixture of two diaste-

reomers (0% de) in 53% yield. IR (cm^ꢁ1, KBr): 1965

1

(m_CO), 1714 (m_C@O). H NMR (acetone-d₆): d 1.27 (3H, t,

J = 7.1 Hz, CH₂CH₃), 1.28 (3H, t, J = 7.1 Hz, CH₂CH₃),

2.04 (3H, s, Cp⁰CH₃), 2.44 (3H, d, J = 2.0 Hz, Cp⁰CH₃),

3.66 (9H, d, J = 12.0 Hz, OCH₃), 3.67 (9H, d,

2254

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

J = 12.0 Hz, OCH₃), 4.17 (2H, m, CH₂CH₃), 5.06 (1H, s,

Cp⁰), 5.13 (1H, s, Cp⁰), 5.45 (1H, d, J = 1.7 Hz, Cp⁰), 5.53

(1H, s, Cp⁰). ¹³C NMR (acetone-d₆): d 13.9, 14.0, 14.5,

14.6, 53.8 (d, J_PC= 5 Hz), 53.9 (d, J_PC= 4 Hz), 60.8,

61.0, 81.7 (d, J_PC= 7 Hz), 83.2, 86.9 (d, J_PC= 3 Hz), 87.2,

87.8, 88.3 (d, J_PC= 5 Hz), 100.7, 102.7, 114.2, 115.1,

165.7, 165.8, 202.9 (d, J_PC= 29 Hz), 203.1 (d, J_PC= 28 Hz).

³¹P NMR (acetone-d₆): d 155.0, 155.5. Mass: m/z 545 (M⁺).

Anal. Calc. for C₁₄H₂₂IO₆PRu: C, 30.84; H, 4.07; P, 5.68; I,

23.27. Found: C, 30.69; H, 4.32; P, 5.48; I, 23.53%.

Cp⁰), 6.29 (1H, dd, J = 2.0, 1.7 Hz, Cp⁰), 7.27–7.38 (3H,

m, C₆H₅), 7.58–7.60 (2H, m, C₆H₅). ¹³C NMR (acetone-

d₆): d 14.7, 14.8, 53.5 (d, J_PC= 5 Hz), 60.8, 83.1 (d,

J_PC= 7 Hz), 85.3, 86.9 (d, J_PC= 3 Hz), 100.5, 113.9,

127.0, 128.8, 129.0, 132.1, 165.4, 202.2 (d, J_PC= 30 Hz).

³¹P NMR (acetone-d₆): d 153.3.

3.26. [g⁵-C₅H₂(Me)(Ph)(COOEt)]Ru[P(OMe)₃](CO)-

Br (9d)

This complex was obtained as a mixture of two diaste-

reomers (0% de) in 15% yield. IR (cm^ꢁ1, KBr): 1952

(m_CO), 1715 (m_C@O). H NMR (acetone-d₆): d 1.30 (3H, t,

3.24. [g⁵-C₅H₂(Me)₂(COOEt)]Ru[P(OMe)₃](CO)Br

(9b)

1

J = 7.1 Hz, CH₂CH₃), 1.31 (3H, t, J = 7.1 Hz, CH₂CH₃),

2.31 (3H, d, J = 2.7 Hz, Cp⁰CH₃), 2.33 (3H, s, Cp⁰CH₃),

3.49 (9H, d, J = 12.2 Hz, OCH₃), 3.58 (9H, d,

J = 12.0 Hz, OCH₃), 4.23 (2H, m, CH₂CH₃), 5.83 (1H, d,

J = 1.7 Hz, Cp⁰), 5.88 (1H, dd, J = 2.0, 1.7 Hz, Cp⁰), 6.03

(1H, d, J = 2.0 Hz, Cp⁰), 6.25 (1H, dd, J = 2.0, 2.0 Hz,

Cp⁰), 7.26–7.38 (3H, m, C₆H₅), 7.56–7.59 (2H, m, C₆H₅),

7.59–7.61 (2H, m, C₆H₅). ¹³C NMR (acetone-d₆): d 14.1,

14.6, 14.7, 53.2 (d, J_PC= 5 Hz), 53.4 (d, J_PC= 5 Hz), 60.9,

61.0, 82.6 (d, J_PC= 10 Hz), 84.2, 83.8 (d, J_PC= 9 Hz),

84.8, 85.3, 85.9 (d, J_PC= 3 Hz), 98.5, 99.8, 116.8, 118.3,

127.0, 127.4, 129.0, 129.1, 129.3, 129.5, 132.5, 132.6,

165.7, 202.6 (d, J_PC= 30 Hz), 202.9 (d, J_PC= 31 Hz).

³¹P NMR (acetone-d₆): d 150.5, 151.0. Mass: m/z 561

(M⁺). Anal. Calc. for C₁₄H₂₂O₆PIRu: C, 40.73; H, 4.32;

P, 5.53; Br, 14.26. Found: C, 40.51; H, 4.36; P, 5.49; Br,

14.14%.

This complex was obtained as a mixture of two diaste-

reomers (12% de) in 26% yield. IR (cm^ꢁ1, KBr): 1965

(m_CO), 1714 (m_C@O). Mass: m/z 499 (M⁺). Anal. Calc.

for C₁₄H₂₂BrO₆PRu: C, 33.75; H, 4.45; P, 6.22; Br,

16.04. Found: C, 33.95; H, 4.56; P, 6.04; Br, 15.92.

1

Major isomer of 9b: H NMR (acetone-d₆): d 1.27 (3H,

t, J = 7.1 Hz, CH₂CH₃), 1.88 (3H, s, Cp⁰CH₃), 2.23

(3H, s, Cp⁰CH₃), 3.69 (9H, d, J = 12.2 Hz, OCH₃),

4.17 (2H, m, CH₂CH₃), 5.10 (1H, s, Cp⁰), 5.44 (1H, d,

J = 1.7 Hz, Cp⁰). 13C NMR (acetone-d₆): d 13.4, 14.0,

14.6, 53.5 (d, J_PC= 5 Hz), 60.8, 80.9, 84.9, 88.4 (d,

J_PC= 5 Hz), 102.8, 116.7, 165.9, 202.1 (d, J_PC= 30 Hz).

³¹P NMR (acetone-d₆): d 153.4. Minor isomer of 9b:

¹H NMR (acetone-d₆):

d 1.27 (3H, t, J = 7.1 Hz,

CH₂CH₃), 1.94 (3H, s, Cp⁰CH₃), 2.20 (3H, d,

J = 2.9 Hz, Cp⁰CH₃), 3.68 (9H, d, J = 12.2 Hz, OCH₃),

4.17 (2H, m, CH₂CH₃), 5.18 (1H, d, J = 2.2 Hz, Cp⁰),

5.34 (1H, s, Cp⁰). ¹³C NMR (acetone-d₆): d 13.7, 13.8,

14.5, 53.4 (d, J_PC= 5 Hz), 60.9, 82.9, 85.4, 86.8 (d,

J_PC= 9 Hz), 100.2, 118.4, 166.0, 203.3 (d, J_PC= 30 Hz).

³¹P NMR (acetone-d₆): d 153.0.

3.27. [g⁵-C₅H₂(Me)(Bu^t)(COOEt)]Ru[P(OMe)₃]-

(CO)I (9e)

This complex was obtained as a mixture of two diaste-

reomers (14% de) in 69% yield. IR (cm^ꢁ1, KBr): 1972

(m_CO), 1695 (m_C@O). Mass: m/z 588 (M⁺). Anal. Calc. for

C₁₇H₂₆O₆PIRu: C, 34.76; H, 4.81; P, 5.27; I, 21.61. Found:

C, 34.98; H, 4.67; P, 5.17; I, 21.34. Major isomer of 9e: ¹H

NMR (acetone-d₆): d 1.27 (9H, s, C(CH₃)₃), 1.27 (3H, t,

J = 7.1 Hz, CH₂CH₃), 2.20 (3H, d, J = 3.7 Hz, Cp⁰CH₃),

3.64 (9H, d, J = 12.0 Hz, OCH₃), 4.17 (2H, m, CH₂CH₃),

5.07 (1H, d, J = 2.0 Hz, Cp⁰), 5.85 (1H, dd, J = 3.7,

2.0 Hz, Cp⁰). ¹³C NMR (acetone-d₆): d 13.8, 14.8, 31.5,

31.7, 53.7 (d, J_PC= 5 Hz), 60.6, 81.1, 83.3, 94.1 (d,

J_PC= 7 Hz), 108.9, 117.4 (d, J_PC= 5 Hz), 165.5, 203.5 (d,

J_PC= 31 Hz). ³¹P NMR (acetone-d₆): d 153.9. Minor iso-

mer of 9e: ¹H NMR (acetone-d₆): d 1.20 (9H, s,

C(CH₃)₃), 1.28 (3H, t, J = 7.1 Hz, CH₂CH₃), 2.55 (3H,

d, J = 3.2 Hz, Cp⁰CH₃), 3.66 (9H, d, J = 11.7 Hz,

OCH₃), 4.17 (2H, m, CH₂CH₃), 5.23 (1H, dd, J = 3.7,

2.0 Hz, Cp⁰), 5.43 (1H, s, Cp⁰). ¹³C NMR (acetone-d₆): d

14.4, 16.0, 31.2, 31.3, 54.0 (d, J_PC= 5 Hz), 60.8, 82.7,

83.7, 84.6 (d, J_PC= 12 Hz), 114.8, 117.9 (d, J = 7 Hz),

165.7, 203.6 (d, J_PC= 29 Hz). ³¹P NMR (acetone-d₆): d

151.7.

3.25. [g⁵-C₅H₂(Me)(Ph)(COOEt)]Ru[P(OMe)₃](CO)I

(9c)

This complex was obtained as a mixture of two diastereo-

mers (8% de) in 40% yield. The major isomer was isolated by

recrystallization from diethyl ether as orange needles.

Major isomer of 9c: IR (cm^ꢁ1, KBr): 1972 (m_CO), 1695

1

(m_C@O). H NMR (acetone-d₆): d 1.31 (3H, t, J = 7.1 Hz,

CH₂CH₃), 2.54 (3H, s, J_PH= 2.2 Hz, Cp⁰CH₃), 3.51 (9H,

d, J = 12.0 Hz, OCH₃), 4.22 (2H, m, CH₂CH₃), 5.81 (1H,

d, J = 2.0 Hz, Cp⁰), 6.15 (1H, d, J = 2.0 Hz, Cp⁰), 7.27–

7.38 (3H, m, C₆H₅), 7.59–7.61 (2H, m, C₆H₅). ¹³C NMR

(acetone-d₆): d 14.6, 15.3, 53.7 (d, J_PC= 5.0 Hz), 60.9,

84.0, 84.1 (d, J_PC= 7 Hz), 87.8, 99.1, 113.4, 126.8, 129.0,

129.3, 132.2, 165.3, 202.6 (d, J_PC= 31 Hz). ³¹P NMR (ace-

tone-d₆): d 152.9. Mass: m/z 608 (M⁺). Anal. Calc. for

C₁₉H₂₄O₆PIRu: C, 37.58; H, 3.98; P, 5.10; I, 20.89. Found:

C, 37.87; H, 4.11; P, 5.29; I, 20.70%. Minor isomer of 9c: ¹H

NMR (acetone-d₆): d 1.31 (3H, t, J = 7.1 Hz, CH₂CH₃),

2.49 (3H, s, J = 1.5 Hz, Cp⁰CH₃), 3.49 (9H, d, J = 12 Hz,

OCH₃), 4.22 (2H, m, CH₂CH₃), 5.77 (1H, d, J = 2.0 Hz,

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

2255

Table 3

Crystallographic data

Complex

3a

3c

3d

3f

3h

3i

Chemical formula

Formula weight

Crystal size (mm)

Crystal system

Space group

C₁₄H₂₂IO₃PRu

497.27

C₂₄H₂₆IO₃PRu

621.42

C₂₉H₂₈BrO₃PRu

636.49

C₂₄H₂₆IO₃PRu

621.42

0.70 · 0.55 · 0.25

Triclinic

C₁₇H₂₈IO₃PRu

539.35

C₂₂H₃₂IO₃PRu

603.44

0.65 · 0.50 · 0.50

Monoclinic

P2₁/n (no. 14)

10.067(2)

9.951(2)

18.322(1)

90

100.410(8)

90

1805.2(4)

4

0.40 · 0.35 · 0.35

Monoclinic

P2₁/n (no. 14)

9.547(3)

17.797(4)

14.607(3)

90

103.62(2)

90

2412.2(10)

4

0.40 · 0.25 · 0.20

Monoclinic

Cc (no. 9)

10.144(3)

18.353(2)

14.689(2)

90

93.96(2)

90

2728.1(8)

4

0.30 · 0.30 · 0.25

Monoclinic

C2/c (no. 15)

31.548(4)

7.955(2)

17.899(2)

90

111.442(10)

90

4180(1)

8

0.50 · 0.35 · 0.35

Monoclinic

P2₁/c (no. 14)

13.568(2)

16.115(2)

10.733(3)

90

99.70(1)

90

2313.3(7)

4

ꢀ

P1 ðno.2Þ

˚

a (A)

9.502(2)

16.434(3)

8.420(3)

98.93(3)

103.98(2)

103.73(2)

1207.5(6)

2

˚

b (A)

˚

c (A)

a (ꢁ)

b (ꢁ)

c (ꢁ)

3

˚

V (A )

Z

D_calc(g cm^ꢁ3

)

1.830

26.71

1.711

20.19

1.550

21.30

1.709

20.16

1.714

23.14

1.733

21.02

l (Mo Ka) (cm^ꢁ1

)

Reﬂections collected

Unique reﬂections [R_int

Observed reﬂections

Variables

4352

5849

3298

5884

4895

5586

]

4122 [0.023]

2889 (I > 3.0r(I))

181

5526 [0.023]

4611 (I > 2.0r(I))

293

3127 [0.063]

2815 (I > 2.0r(I))

316

5548 [0.013]

4932 (I > 2.0r(I))

271

4810 [0.008]

4432 (I > 2.0r(I))

208

5303 [0.024]

4630 (I > 2.0r(I))

248

R

R_w

0.029

0.069

0.065

0.122

0.039

0.052

0.030

0.050

0.030

0.064

0.051

0.100

Goodness-of-ﬁt

1.78

1.64

1.41

1.09

1.24

1.58

3.28. X-ray diﬀraction analyses

References

[1] E.N. Jacobsen, A. Pﬂatz, H. Yamamoto (Eds.), Comprehensive

Asymmetric Catalysis, vols. I–III, Springer-Verlag, Berlin, 1999.

[2] For recent reviews, see: (a) H. Brunner, Angew. Chem., Int. Ed. 38

(1999) 1195;

(b) H. Brunner, Eur. J. Inorg. Chem. (2001) 905;

(c) C. Ganter, Chem. Soc. Rev. 32 (2003) 130.

[3] (a) M. Uno, K. Ando, N. Komatsuzaki, T. Tsuda, T. Tanaka, M.

Sawada, S. Takahashi, J. Organomet. Chem. 473 (1994) 303;

(b) N. Komatsuzaki, M. Uno, H. Kikuchi, S. Takahashi, Chem.

Lett. (1996) 677;

Crystals suitable for X-ray diﬀraction were mounted on

a glass ﬁber with epoxy resin. All measurements were

performed on a Rigaku AFC5R or AFC7R automated

four-circles diﬀractometer using graphite monochromated

˚

Mo Ka radiation (k = 0.71069 A) at ꢁ75 ꢁC. The struc-

tures were solved by Patterson methods and reﬁned by

full-matrix least-squares using the ^TEXSANcrystallographic

software package. Crystallographic data are listed in

Table 3.

(c) T. Katayama, Y. Morimoto, M. Yuge, M. Uno, S. Takahashi,

Organometallics 18 (1999) 3087;

(d) Y. Matsushima, N. Komatsuzaki, Y. Ajioka, M. Yamamoto, H.

Kikuchi, Y. Takata, N. Dodo, K. Onitsuka, M. Uno, S. Takahashi,

Bull. Chem. Soc. Jpn. 74 (2001) 527.

4. Supplementary material

[4] (a) Y. Morimoto, K. Ando, M. Uno, S. Takahashi, Chem. Commun.

(1997) 1795;

Crystallographic data for structural analysis have

been deposited with the Cambridge Crystallographic

Data Centre, CCDC Nos. 142961 and 285029–285033

for complexes 3a, 3c, 3d, 3f, 3h and 3i, respectively.

Copies of this information may be obtained free of

charge from The Director, CCDC, 12 Union Road,

Cambridge, CB2 1EZ UK (fax: +44 1223 336033; email:

deposit@ccdc.cam.ac.uk. or www: http://www.ccdc.cam.

ac.uk).

(b) Y. Matsushima, K. Onitsuka, S. Takahashi, Chem. Lett. (2000)

760;

(c) K. Onitsuka, N. Dodo, Y. Matsushima, S. Takahashi, Chem.

Commun. (2001) 521;

(d) K. Onitsuka, Y. Ajioka, Y. Matsushima, S. Takahashi, Organo-

metallics 20 (2001) 3274;

(e) Y. Matsushima, K. Onitsuka, S. Takahashi, Dalton Trans. (2004)

547;

(f) Y. Matsushima, K. Onitsuka, S. Takahashi, Organometallics 23

(2004) 2439;

(g) Y. Matsushima, K. Onitsuka, S. Takahashi, Organometallics 23

(2004) 3763;

Acknowledgements

(h) Y. Matsushima, K. Onitsuka, S. Takahashi, Organometallics 24

(2005) 2747.

[5] T. Katayama, K. Onitsuka, S. Takahashi, J. Organomet. Chem. 610

(2000) 31.

[6] T. Katayama, Y. Matsushima, K. Onitsuka, S. Takahashi, Chem.

Commun. (2000) 2337.

[7] G. Consiglio, F. Morandini, Chem. Rev. 87 (1987) 761.

[8] R.L. Halterman, Chem. Rev. 92 (1992) 965.

This work was supported in part by a Grant-in-Aid for

Scientiﬁc Research from the Ministry of Education, Cul-

ture, Sports, Science and Technology. We thank the techni-

cal staﬀ of the Material Analysis Center, ISIR, Osaka

University, for spectral measurements, X-ray diﬀraction,

and microanalyses.

2256

T. Katayama et al. / Journal of Organometallic Chemistry 691 (2006) 2245–2256

[9] (a)U. Koelle, B.-S. Kang, U. Englert, J. Organomet. Chem. 420(1991) 227;

(b) O.J. Curnow, R.P. Hughes, E.N. Mairs, A.L. Rheingold, Organomet-

allics 12 (1993) 3102.

[11] P.M. Treichel, D.A. Komar, J. Organomet. Chem. 206 (1981) 77.

[12] N.J. Coville, E.A. Darling, A.W. Hearn, P. Johnston, J. Organomet.

Chem. 328 (1987) 375.

´

[10] M. Jimez-Tenorio, M.D. Palacios, M.C. Puerta, P. Valerga, Organo-

[13] P.M. Treichel, R.L. Shubkin, K.W. Barnett, D. Reichard, Inorg.

Chem. 5 (1966) 1177.

metallics 23 (2004) 504.

Article Doi

Diastereoselectivity at chiral metal center of half-sandwich-type ruthenium complexes with planar-chiral cyclopentadienyl ligands in multiple ligand transfer reaction

DOI: 10.1016/j.jorganchem.2005.11.010

Source and publish data:

Authors:

Article abstract of DOI:10.1016/j.jorganchem.2005.11.010

Full text of DOI:10.1016/j.jorganchem.2005.11.010

Products guided by the article

R&D Labs maybe for 340269-24-1

Relevant to this article

Hot Product