Diastereoselective formation of ruthenium-isocyanide and -acetylide complexes with planar-chiral cyclopentadienyl-phosphine ligands

Article abstract of DOI:10.1021/om0500523

The reaction of ruthenium complexes [(η⁵:η¹- 2-Me-4-R-C₅H₂CO₂CH₂CH ₂PPh₂)Ru(PR′₃)(NCMe)] [PF₆] (R = Me, Ph, Bu^t; R′ = Ph, Me, OPh) pos

Full text of DOI:10.1021/om0500523

Organometallics 2005, 24, 2747-2754
2747
Diastereoselective Formation of Ruthenium-Isocyanide
and -Acetylide Complexes with Planar-Chiral
Cyclopentadienyl-Phosphine Ligands
Yuji Matsushima, Kiyotaka Onitsuka,* and Shigetoshi Takahashi
The Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki,
Osaka 567-0047, Japan
Received January 25, 2005
The reaction of ruthenium complexes [(η5:η1-2-Me-4-R-C5H2CO2CH2CH2PPh2)Ru(PR′3)-
(NCMe)][PF6] (R ) Me, Ph, But; R′ ) Ph, Me, OPh) possessing planar-chiral cyclopentadienyl-
phosphine ligands with tert-butyl isocyanide resulted in the diastereoselective formation of
ruthenium-isocyanide complexes (up to >99% de) under kinetic control. The reaction with
phenylacetylene followed by treatment with alumina gave acetylide complexes diastereo-
selectively (up to >99% de). The configuration of the products was determined by X-ray
analyses as well as NOE measurements. In both reactions, the stereochemistry of the
ruthenium atom in the substrate did not influence the diastereoselectivity of the products,
although the substituent on the cyclopentadienyl ring and the phosphorus ligands on the
ruthenium atom showed steric effects on the selectivity.
Introduction
phosphine ligand have the ability to control stereochem-
istry in stoichiometric and catalytic reactions.4 For
example, the reactions of the planar-chiral Cp′Ru
complexes with phosphine resulted in the highly selec-
tive induction of the metal-centered chirality in the
resulting complexes. Because a catalytic reaction in-
volves multistep stoichiometric reactions, further reac-
tions of the metal-centered chiral complexes are of
special interest. From this viewpoint, we have recently
reported that the reactions of the planar-chiral Cp′Ru
complexes with an iodide ligand gave iodo complexes,
the metal-centered chirality of which was thermody-
namically controlled.5 We present herein the diastereo-
selective formation of ruthenium-isocyanide complexes
by the ligand exchange reaction of the planar-chiral
Cp′Ru complexes under kinetic control. We also exam-
ined the reaction with phenylacetylene to give vinyl-
idene complexes, which were isolated as acetylide
complexes by treatment with alumina with high dia-
stereoselectivity. Although we used a racemic mixture
for each diastereomer of the starting complexes, all
structures are given with planar chirality with SCp for
clarity in this article.
The synthesis and reaction of chiral organometallic
complexes have attracted much attention because they
provide useful information for the development of new
asymmetric catalysts and for furthering our under-
standing of the mechanism of catalytic asymmetric
reactions.1 Although organometallic complexes with
chiral ligands comprise the majority of such chemistry,
other types of chiral complexes have become the focus
of increasing interest in recent years. A half-sandwich
complex with a three-legged piano stool structure
generates metal-centered chirality when the ligands
differ from each other.2 Although a significant number
of metal-centered chiral complexes have been prepared
so far, the control of the stereochemistry at the metal
center remains a challenging task.3
We have demonstrated that planar-chiral cyclopen-
tadienyl-ruthenium (Cp′Ru) complexes with a tethered
(1) Comprehensive Asymmetric Catalysis I-III; Jacobsen, E. N.,
Pflatz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin, 1999.
(2) For recent reviews, see: (a) Brunner, H. Angew. Chem., Int. Ed.
1999, 38, 1195. (b) Brunner, H. Eur. J. Inorg. Chem. 2001, 905.
(c) Ganter, C. Chem. Soc. Rev. 2003, 32, 130.
(3) For recent references, see: (a) Drommi, D.; Faraone, F.; Francio,
G.; Belletti, D.; Graiff, C.; Tiripicchio, A. Organometallics 2002, 21,
761. (b) Murata, K.; Konishi, H.; Ito, M.; Ikariya, T. Organometallics
2002, 21, 253. (c) Ritleng, V.; Pfeffer, M.; Sirlin, C. Organometallics
2003, 22, 347. (d) Faller, J. W.; D’Alliessi, D. G. Organometallics 2003,
22, 2749. (e) Brunner, H.; Zwack, T.; Zabel, M.; Beck, W.; Bo¨hm, A.
Organometallics 2003, 22, 1741. (f) Pinto, P.; Marconi, G.; Heinemann,
F. W.; Zenneck, U. Organometallics 2004, 23, 374. (g) Davenport, A.
J.; Davies, D. L.; Fawcett, J.; Russell, D. R. Dalton Trans. 2004, 1481.
(h) Kataoka, Y.; Nakagawa, Y.; Shibahara, A.; Yamagata, T.; Mashima,
K.; Tani, K. Organometallics 2004, 23, 2095. (i) Doppiu, A.; Englert,
U.; Salzer, A. Chem. Commun. 2004, 2166. (j) Alezra, V.; Bernardinelli,
G.; Corminboeuf, C.; Frey, U.; Ku¨ndig, E. P.; Merbach, A. E.; Saudan,
C. M.; Viton, F.; Weber, J. J. Am. Chem. Soc. 2004, 126, 4843.
(k) Kataoka, Y.; Shimada, K.; Goi, T.; Yamagata, T.; Mashima, K.; Tani,
K. Inorg. Chim. Acta 2004, 357, 2965. (l) Brunner, H.; Ko¨llnberger,
A.; Mehmood, A.; Tsuno, T.; Zabel, M. Organometallics 2004, 23, 4006.
(m) Cayuela, E.; Jalo´n, F. A.; Manzano, B. R.; Espino, G.; Weissen-
steiner, W.; Mereiter, K. J. Am. Chem. Soc. 2004, 126, 7049.
Results
Treatment of the diastereomerically pure ruthenium
complex [(η5:η1-2,4-Me2-C5H2CO2CH2CH2PPh2)Ru(PPh3)-
(4) (a) Matsushima, Y.; Onitsuka, K.; Takahashi, S. Chem. Lett.
2000, 760. (b) Onitsuka, K.; Dodo, N.; Matsushima, Y.; Takahashi, S.
Chem. Commun. 2001, 521. (c) Onitsuka, K.; Ajioka, Y.; Matsushima,
Y.; Takahashi, S. Organometallics 2001, 20, 3274. (d) Matsushima,
Y.; Onitsuka, K.; Kondo, T.; Mitsudo, T.; Takahashi, S. J. Am. Chem.
Soc. 2001, 123, 10405. (e) Matsushima, Y.; Onitsuka, K.; Takahashi,
S. Organometallics 2004, 23, 2439. (f) Matsushima, Y.; Onitsuka, K.;
Takahashi, S. Organometallics 2004, 23, 3763.
(5) Matsushima, Y.; Onitsuka, K.; Takahashi, S. Dalton Trans. 2004,
547.
10.1021/om0500523 CCC: $30.25 © 2005 American Chemical Society
Publication on Web 04/23/2005

2748 Organometallics, Vol. 24, No. 11, 2005
Matsushima et al.
Table 1. Reactions of 1-I and/or 1-II with
Scheme 1
tert-Butyl Isocyanidea
entry
substrate
product
yield/%
de/%b,c
1
1a-I
2a
2a
2b
2b
2c
2d
2d
2d
2e
2f
85
83
90
86
87
93
90
88
88
89
85
85
81
44 (II)
46 (II)
80 (II)
80 (II)
>99 (I)
44 (II)
46 (II)
46 (II)
76 (II)
18 (I)
2
1a-I + 1a-II (75:25)
3
1b-I
4
1b-I + 1b-II (90:10)
5
1c-I
1d-I
6
7
1d-I + 1d-II (50:50)
8
1d-II
1e-I
1f-I
1g-I
1h-I
1i-I
9
10
11
12
13
2g
2h
2i
56 (II)
34 (II)
76 (I)
a Reaction conditions: CH2Cl2, reflux, 12 h (entries 1-5);
CH2Cl2, reflux, 36 h (entries 6-10); ClCH2CH2Cl, reflux, 12 h
(entries 11-13). b Determined by 31P NMR. c The symbol in pa-
rentheses indicates the configuration of the major products as
determined by NOE measurement and X-ray crystallography.
(NCMe)][PF6] (1a-I), the configuration of which is
S
CpSRu/RCpRRu,6 with 10 equiv of tert-butyl isocyanide
in refluxing dichloromethane for 12 h led to the ligand
exchange reaction to give isocyanide complex [(η5:η1-2,
4-Me2-C5H2CO2CH2CH2PPh2)Ru(PPh3)(CNBut)][PF6] (2a)
in 85% yield (Scheme 1). The 31P NMR spectrum of 2a
clearly showed that the product consisted of two dia-
stereomers, 2a-I (SCpSRu/RCpRRu) and 2a-II (SCpRRu
/
R
CpSRu), with 44% de,6 and the configuration of the
major product was determined by differential NOE
measurement. The NOE signals of two protons on the
Cp′ ring were observed by irradiation of the signal
assigned to the methyl group at the 4-position of the
Cp′ ring, whereas irradiation of the signal assigned to
the methyl group at the 2-position of the Cp′ ring
produced NOE signals not only of the Cp′ proton at the
3-position but also of the But protons on isocyanide.
These results clearly suggest that the isocyanide is
situated close to the methyl group at the 2-position of
the Cp′ ring in the major product. Thus, the major
isomer is 2a-II and the minor one is 2a-I. When a
mixture of the two diastereomers 1a-I and 1a-II
(75:25) was used as the starting material, complexes
2a-I and 2a-II in a 27:73 ratio (46% de) were produced
in 83% yield, suggesting that the stereochemistry of the
starting material does not influence the diastereoselec-
tivity of the product. This is similar to our previous
results in the reaction of complex 1 with Bu4NI,5 but is
in sharp contrast to the analogous reactions of ruthe-
nium complexes having chiral groups on the Cp′ ring
or on the phosphine ligand, which proceed with reten-
tion of configuration at the metal center.7
Figure 1. ORTEP drawing of complex 2c-I. Hydrogen
-
atoms and counteranion PF6 are omitted for clarity.
contrast, the reaction of But analogue 1c-I produced a
single diastereomer (2c-I), the configuration at the
metal of which is opposite of those of the major isomers
from complexes 2a and 2b (entry 5). The structure of
complex 2c-I was unequivocally determined by X-ray
crystallography (Figure 1).
As the reactivities of trimethylphosphine (1d-f) and
triphenylphosphite (1g-i) complexes toward tert-butyl
isocyanide were lower than those of triphenyphosphine
analogues 1a-c, slightly severe conditions were re-
quired for improving the yield of isocyanide complexes.
Thus, complexes 1d-f were reacted with tert-butyl
isocyanide for 36 h, and the reactions of complexes 1g-i
were performed in refluxing 1,2-dichloroethane. The
reactions of 1d-I and/or 1d-II gave a mixture of iso-
cyanide complexes 2d-I and 2d-II in good yields, and
the selectivity of 2d-I and 2d-II was also independent
of the stereochemistry of the substrate (entries 6-8).
Complex 2e-II was obtained as a major isomer from the
reaction of 1e-I (entry 9). Although the structure of the
major isomer produced in the reaction of 1f-I was
Then, we examined the reactions of several ruthe-
nium complexes, the representative results of which are
given in Table 1, along with the results described above.
The reaction of complex 1b-I, which has a phenyl group
at the 4-position of the Cp′ ring, produced isocyanide
complexes 2b-I and 2b-II with 80% de (entry 3), and
the reaction of a mixture of 1b-I and 1b-II in a 90:10
ratio gave essentially the same result (entry 4). By
(6) The assignment for the absolute configuration at the metal center
(R or S) in complexes with trimethylphosphine is opposite those of
triphenylphosphine and triphenylphosphite with the same structure
due to the difference in the sequence of the tethered phosphine and
the phosphorus ligand.
(7) (a) Morandini, F.; Consiglio, G.; Lucchini, V. Organometallics
1985, 4, 1202. (b) Cesarotti, E.; Walker, M. A. P. C.; Hursthouse, M.
B.; Vefghi, R.; Schofield, P. A.; White, C. J. Organomet. Chem. 1985,
286, 343.

Ruthenium-Isocyanide and -Acetylide Complexes
Organometallics, Vol. 24, No. 11, 2005 2749
Scheme 2
Figure 2. ORTEP drawing of complex 4a-I. Hydrogen
atoms and solvate are omitted for clarity.
Table 2. Reactions of 1-I and/or 1-II with
Phenylacetylenea
entry
substrate
product
yield/%
de/%b,c
1
1a-I
4a
4a
4b
4b
4c
4d
4d
4d
4e
4f
89
85
90
92
91
87
94
96
82
92
>99 (I)
>99 (I)
>99d
2
1a-I + 1a-II (75:25)
different from those of 1d-I and 1e-I, as observed in the
triphenyphosphine analogue, the diastereoselectivity of
2f-I was much lower than that of 2c-I (entry 10). A
similar tendency was observed for the diastereoselec-
tivity in the reactions of 1g-i (entries 11-13).
3
1b-I
4
1b-I + 1b-II (90:10)
>99d
5e
6
1c-I
1d-I
>99 (I)
74 (II)
70 (II)
74 (II)
70 (II)
40 (I)
7
1d-I + 1d-II (50:50)
8
1d-II
1e-I
1f-I
9
Recrystallization of a mixture of 2a-I and 2a-II in a
28:72 ratio from dichloromethane-diethyl ether led to
a change of the diastereomeric ratio to 83:17. It is
noteworthy that the diastereomeric ratio was not changed
by refluxing the mixture of 2a-I and 2a-II (83:17) in
dichloromethane for 12 h. Although similar treatments
were performed in the presence of isocyanide and
acetonitrile, no epimerization was detected. These re-
sults contrast the fact that epimerization between two
diastereomers was observed in analogous iodo com-
plexes.5
Next, we examined the diastereoselectivity in the
formation of the ruthenium-vinylidene complex, which
is known to be an important intermediate in some
catalytic reactions.8 Treatment of 1a-I with 10 equiv of
phenylacetylene in dichloromethane under reflux gave
vinylidene complex 3a in a diastereometically pure form
(Scheme 2).9 However, the isolation of vinylidene com-
plex 3a was unsuccessful. Thus, vinylidene complex 3a
was converted into acetylide complex 4a by treatment
with alumina.10 Complex 4a was formed as a single
diastereomer, the structure of which was determined
by X-ray analysis. As shown in Figure 2, complex 4a
has the configuration SCpSRu/RCpRRu (4a-I). The reaction
of a mixture of the two diastereomers 1a-I and 1a-II
10
a Reaction conditions: CH2Cl2, reflux, 48 h. b Determined by
31P NMR. c The symbol in parentheses indicates the configuration
of the major products as determined by NOE measurement and
X-ray crystallography. d The configuration of the major products
could not be determined. e Reaction conditions: CH2Cl2, room
temperature, 48 h.
(75:25) gave complex 3a as a single diastereomer, which
was also isolated after conversion into acetylide complex
4a-I in 85% yield, suggesting that the stereochemistry
of the starting material does not influence the diastereo-
selectivity of the product. This result is similar to that
observed in isocyanide complexes 2 (see above), but is
in sharp contrast to the known chemistry of analogous
ruthenium complexes with a chiral phosphine ligand,
which stereospecifically produce the vinylidene com-
plexes with retention of configuration at the ruthenium
atom.9
Table 2 gives the representative results of the reac-
tions of 1-I and/or 1-II with phenylacetylene followed
by treatment with alumina to give acetylide complexes
4-I and/or 4-II. We also examined the diastereoselec-
tivity of vinylidene complex 3 by measuring 31P NMR
spectra of the reaction mixture before treatment with
alumina and found the diastereoselectivity of 4 was
essentially the same as that of 3. It seems to be
reasonable that the transformation of 3 into 4 proceeds
with retention of configuration at the ruthenium atom,
because no bond cleavage around the ruthenium atom
is required in this step. Although the reaction of complex
1b produced a single diastereomer (4b), the stereochem-
istry of 4b could not be determined (entries 3 and 4).
Upon treatment of complex 1c-I, a single diastereomer
(8) For recent reviews, see: (a) Bruneau, C.; Dixneuf, P. H. Acc.
Chem. Res. 1999, 32, 311. (b) Katayama, H.; Ozawa, F. Coord. Chem.
Rev. 2004, 248, 1703.
(9) (a) Consiglio, G.; Morandini, F.; Ciani, G. F.; Sironi, A. Organo-
metallics 1986, 5, 1976. (b) Consiglio, G.; Morandini, F. Inorg. Chim.
Acta 1987, 127, 79. (c) Slugovc, C.; Simanko, W.; Mereiter, K.; Schmid,
R.; Kirchner, K.; Xiao, L.; Weissensteiner, W. Organometallics 1999,
18, 3865.
(10) Hodge, A. J.; Ingham, S. L.; Kakkar, A. K.; Khan, M. S.; Lewis,
J.; Long, N. J.; Parker, D. G.; Raithby, P. R. J. Organomet. Chem. 1995,
488, 205.

2750 Organometallics, Vol. 24, No. 11, 2005
Matsushima et al.
Scheme 3
Scheme 4
The results in Table 1 suggest that the diastereo-
selectivity of 2 depended on the substituent at the
4-position of the Cp′ ring and the phosphorus ligand.
The bulky substituent, But, on the Cp′ ring and the
bulky phosphorus ligands, such as PPh3 and P(OPh)3,
led to the increase in the selectivity of 2-I, whereas the
combination of the small substituent, Me and Ph, and
phosphorus ligand, PMe3, selectively produced 2-II.
These steric effects may be reasonably explained by
using intermediate 5, which has a two-legged piano stool
structure (Scheme 4). The approach of isocyanide to the
ruthenium atom of 5 from side A gives 2-I, whereas the
coordination from side B produces 2-II. As one of the
two phenyl rings on the tethered phosphine ligand
protrudes equatorially, the approach of isocyanide from
side A is affected by steric hindrance. Consequently, the
approach from side B is faster than that from A,
resulting in the selective formation of 2-II. This expla-
nation is applicable to the results obtained from the
combination of a small substituent and a small phos-
phorus ligand. Although the But group on the Cp′ ring
would provide an adverse effect on the attack from side
A, the selectivity of 2-I was higher than those in the
reactions of 1, having a Me or a Ph group on the Cp′
ring. In particular, 2c-I was obtained as a sole product
in the reaction of 1c-I, which had a bulky phosphine
ligand. This inverse selectivity is likely caused by the
structural change of the intermediate (5′) due to the
steric repulsion between the But group on the Cp′ ring
and the phosphorus ligand. Thus, the phosphorus ligand
is located apart from the But group and effectively blocks
the attack from side B. This explanation is consistent
with the fact that the selectivity of 2-I increases with
increasing bulkiness of the phosphorus ligand.
Figure 3. ORTEP drawing of complex 4c-I. Hydrogen
atoms are omitted for clarity.
(4c-I) was also obtained (entry 5), and the stereochem-
istry was confirmed by X-ray analysis, as shown in
Figure 3. Although complexes 1d-f were also reacted
with phenylacetylene to give analogous acetylide com-
plexes (4d-f) as mixtures of two diastereomers, the
configuration at the ruthenium atom of the major
product was opposite that of triphenylphosphine ana-
logues (entries 6-10). Similar reactions of complexes
1g-i did not produce any acetylide complexes at all, and
the starting materials were recovered quantitatively.
When the reaction was performed in refluxing
1,2-dichloroethane, the product was a complex mixture
from which no acetylide complex could be isolated.
A diastereomerically pure sample of 4d-II was ob-
tained by recrystallization of a mixture of 4d-I and
4d-II (13:87) from dichloromethane-hexane. When
complex 4d-II was refluxed in dichloromethane for a
long time, no epimerization took place, as observed for
2a-I and 2a-II.11
Discussion
Because no epimerization between the two diastere-
omers 2a-I and 2a-II was detected, isocyanide complex
2 was not in equilibrium depending on the thermody-
namic stability of the diastereomers. Thus, the dia-
stereoselectivity of isocyanide complex 2 is not under
thermodynamic control but under kinetic control. Al-
though it may seem unique that the diastereoselectivity
was not affected by the stereochemistry of the starting
material, there are two possible interpretations for this.
One is that the epimerization between 1-I and 1-II is
much faster than the ligand exchange reaction with
isocyanide, and the other is the formation of an inter-
mediate that has no metal-centered chirality. Although
slow epimerization between 1-I and 1-II was observed
for 1a and 1b, no epimerization was detected for 1d.4b
The results of the reactions using 1d-I and/or 1d-II
clearly suggest that the latter interpretation is plau-
sible. Thus, a coordinatively unsaturated complex (5)
is generated by the dissociation of acetonitrile, and tert-
butyl isocyanide coordinates to 5, giving 2 (Scheme 3).9c
The diastereoselectivity of acetylide complex 4 must
be determined in the step for forming vinylidene com-
plex 3, because the transformation of 3 into 4 proceeded
with maintenance of the diastereomeric ratio and no
epimerization took place in 4. Although we conducted
several experiments to determine whether the diastereo-
selectivity of 3 was under kinetic or thermodynamic
control, no conclusive results were obtained. The results
in Table 2 show the steric effect of the substituent on
the Cp′ ring and the phosphorus ligand on the diastereo-
selectivity of 4, similar to that for 2. However, if the
selectivity were to depend on the thermodynamic stabil-
ity of the resulting vinylidene complexes 3, a more
(11) Carmona, D.; Vega, C.; Lahoz, F. J.; Atencio, R.; Oro, L. A.;
Lamata, M. P.; Viguri, F.; Jose´, E. S. Organometallics 2000, 19, 2273.

Ruthenium-Isocyanide and -Acetylide Complexes
Organometallics, Vol. 24, No. 11, 2005 2751
Ruthenium complexes 1a-i were prepared by the method
previously reported.4b,12 All other chemicals available com-
mercially were used without further purification.
Scheme 5
Reaction of [(η5:η1-2-Me-4-R-C5H2CO2CH2CH2PPh2)Ru-
(PPh3)(NCMe)][PF6] (R ) Me, Ph, But) 1a-c with tert-
Butyl Isocyanide. To a solution of ruthenium complex 1
(0.10 mmol) in dichloromethane (5 mL) was added tert-butyl
isocyanide (80 mg, 1.0 mmol), and the reaction mixture was
refluxed for 12 h. After removal of the solvent under reduced
pressure, the residual oil was washed with diethyl ether
several times. The crude product was purified by silica gel
column chromatography using a mixture of dichloromethane-
acetone (v/v ) 5/1) as eluent to give red solid. Yield and
diastereoselectivity of the product 2 are given in Table 1.
[(η5:η1-2,4-Me2-C5H2CO2CH2CH2PPh2)Ru(PPh3)(CNBut)]-
[PF6] (2a-I and 2a-II). IR (cm-1
, KBr): 2143 (νCtN),
1722 (νCdO). FAB-MS: m/z 796 (M - PF6-). Anal. Calcd for
C45H46F6NO2P3Ru: C, 57.45; H, 4.93; N, 1.49. Found: C, 57.37;
H, 4.98; N, 1.69. Major product (2a-I): 1H NMR (400 MHz):
δ 7.88-7.33 (m, 17H, Ph), 6.95-6.90 (m, 6H, Ph), 6.63-6.58
(m, 2H, Ph), 5.85 (s, 1H, Cp′), 4.94 (ddd, 1H, J ) 23.7, 11.2,
7.1 Hz, OCH2), 4.49 (s, 1H, Cp′), 3.70-3.64 (m, 1H, OCH2),
3.11-3.02 (m, 1H, PCH2), 2.93-2.81 (m, 1H, PCH2), 2.52
(s, 3H, Cp′Me), 1.68 (s, 3H, Cp′Me), 1.45 (s, 9H, CMe3).
13C NMR (151 MHz): δ 165.6 (CdO), 141.6-129.1 (Ph), 117.8
(Cp′), 104.1 (Cp′), 94.3 (Cp′), 89.3 (Cp′), 83.6 (d, J ) 7 Hz, Cp′),
66.0 (CMe3), 59.7 (OCH2), 30.6 (CMe3), 25.3 (d, J ) 34 Hz,
PCH2), 13.3 (Cp′Me), 12.2 (Cp′Me); the signal assignable to the
isocyano-carbon could not be detected. 31P NMR (162 MHz):
δ 47.7 (d, J ) 27 Hz), 36.4 (d, J ) 27 Hz). Minor product
(2a-II): 1H NMR (400 MHz): δ 7.88-7.33 (m, 23H, Ph), 6.24-
6.19 (m, 2H, Ph), 5.17-5.07 (m, 1H, OCH2), 4.84 (s, 1H, Cp′),
4.78 (s, 1H, Cp′), 4.09-4.02 (m, 1H, OCH2), 2.93-2.81 (m, 1H,
PCH2), 2.72-2.63 (m, 1H, PCH2), 2.41 (s, 3H, Cp′Me), 1.35
(d, 3H, J ) 2.9 Hz, Cp′Me), 1.23 (s, 9H, CMe3). 31P NMR
(162 MHz): δ 46.1 (d, J ) 26 Hz), 38.0 (d, J ) 26 Hz).
sterically demanding substituent and phosphorus ligand
would produce 3-I because the steric repulsion between
the substituent on the Cp′ ring and the phosphorus
ligand is important.5 The results in Table 2 are also in
agreement with this explanation. Therefore, the factor
contributing to the stereochemistry of 4 is still unclear.
Although the stereochemistry of 4b could not be
determined, the diastereoselectivity of triphenylphos-
phine complexes 4a-c was very high compared to that
of trimethylphosphine derivatives 4d-e. This phenom-
enon is likely due to the steric factor of the phosphine
ligand, because the selectivity of 4-I in 4f is much higher
than those in 4d and 4e. It is well known that the
η2-alkyne complex is generated as an intermediate in
the formation of the vinylidene complex. As the coordi-
nation sphere of η2-alkyne intermediate 6 is fairly
crowded, the steric effect of the phosphine ligand would
be enhanced (Scheme 5).
[(η5:η1-2-Me-4-Ph-C5H2CO2CH2CH2PPh2)Ru(PPh3)-
(CNBut)][PF6] (2b-I and 2b-II). IR (cm-1, KBr): 2137
(νCtN), 1715 (νCdO). FAB-MS: m/z 858 (M - PF6-). Anal. Calcd
for C50H48F6NO2P3Ru: C, 59.88; H, 4.82; N, 1.40. Found: C,
60.05; H, 4.92; N, 1.40. Major product (2b-I): 1H NMR
(270 MHz): δ 7.76-7.22 (m, 20H, Ph), 7.01 (d, 2H, J )
7.1 Hz, Ph), 6.60-6.40 (m, 8H, Ph), 6.15 (s, 1H, Cp′), 5.18-
5.02 (m, 1H, OCH2), 5.10 (s, 1H, Cp′), 4.08-3.98 (m, 1H,
OCH2), 3.17-3.08 (m, 2H, PCH2), 2.65 (s, 3H, Cp′Me), 1.43
(s, 9H, CMe3). 13C NMR (151 MHz): δ 165.5 (CdO), 141.5-
127.3 (Ph), 113.2 (Cp′), 104.7 (Cp′), 92.6 (d, J ) 10 Hz, Cp′),
91.5 (Cp′), 78.0 (d, J ) 7 Hz, Cp′), 66.0 (CMe3), 59.7 (OCH2),
30.6 (CMe3), 23.2 (d, J ) 35 Hz, PCH2), 13.5 (Cp′Me); the signal
assignable to the isocyano-carbon could not be detected.
31P NMR (162 MHz): δ 42.9 (d, J ) 26 Hz), 35.1 (d, J )
Summary
We have described the diastereoselective formation
of ruthenium-isocyanide and -vinylidene complexes, the
latter of which were isolated as acetylide complexes. The
planar-chiral cyclopentadienyl-phosphine ligand showed
high ability to control the stereochemistry at the metal
center in the resulting ruthenium complexes, whereas
the metal-centered chirality of the starting complexes
had no influence on the diastereoselectivity. A signifi-
cant steric effect of the substituent on the Cp′ ring and
the phosphorus ligand was observed in both reactions.
Because the complexes prepared here have potential
applications in other reactions, the results should be
useful for developing the stereoselective transformation
of isocyanides and acetylenes. Further studies that focus
on the application to asymmetric catalysis are in
progress.
1
26 Hz). Minor product (2b-II): H NMR (270 MHz): δ 7.99
(d, 2H, J ) 7.4 Hz, Ph), 7.90 (br, 2H, Ph), 7.70-7.11 (m, 26H,
Ph), 5.44 (s, 1H, Cp′), 5.37 (s, 1H, Cp′), 5.21-5.14 (m, 1H,
OCH2), 4.11-4.07 (m, 1H, OCH2), 2.95-2.88 (m, 1H, PCH2),
2.77-2.73 (m, 1H, PCH2), 0.72 (s, 9H, CMe3). 31P NMR
(162 MHz): δ 46.9 (d, J ) 25 Hz), 38.8 (d, J ) 25 Hz).
[(η5:η1-2-Me-4-But-C5H2CO2CH2CH2PPh2)Ru(PPh3)-
(CNBut)][PF6] (2c-II). 1H NMR (400 MHz): δ 8.02-7.98
(m, 2H, Ph), 7.67-7.11 (m, 21H, Ph), 6.23 (t, 2H, J ) 8.5 Hz,
Ph), 5.19-5.09 (m, 1H, OCH2), 5.01-4.99 (m, 1H, Cp′), 4.51-
4.49 (m, 1H, Cp′), 3.90-3.83 (m, 1H, OCH2), 3.18-3.09
(m, 1H, PCH2), 2.68 (dt, 1H, J ) 15.4, 4.6 Hz, PCH2), 1.59
(s, 9H, CMe3), 1.59 (d, 3H, J ) 2.7 Hz, Cp′Me), 1.14 (s, 9H,
CMe3). 13C NMR (151 MHz): δ 166.8 (CdO), 147.8-129.0 (Ph),
114.1 (Cp′), 91.5 (Cp′), 87.5 (d, J ) 10 Hz, Cp′), 74.6 (d, J )
7 Hz, Cp′), 66.0 (Cp′), 60.4 (CMe3), 60.3 (OCH2), 33.3 (CMe3),
Experimental Section
All reactions were carried out under an argon atmosphere,
1
but the workup was performed in air. H, 13C, and 31P NMR
spectra were measured on JEOL JNM-EX270, -LA400, and
-LA600 spectrometers using acetone-d6 for isocyanide com-
plexes and CDCl3 for acetylide complexes as a solvent. Chemi-
cal shifts are given in ppm based on SiMe4 as an internal
standard for 1H and 13C NMR, and 85% H3PO4 as an external
standard for 31P NMR. IR and mass spectra were taken on a
Perkin-Elmer system 2000 FT-IR and JEOL JMS-600H in-
strument, respectively. Elemental analyses were performed by
the Material Analysis Center, ISIR, Osaka University.
(12) Dodo, N.; Matsushima, Y.; Uno, M.; Onitsuka, K.; Takahashi,
S. J. Chem. Soc., Dalton Trans. 2000, 35.

2752 Organometallics, Vol. 24, No. 11, 2005
Matsushima et al.
31.2 (CMe3), 20.4 (d, J ) 30 Hz, PCH2), 12.2 (Cp′Me); the signal
assignable to the isocyano carbon could not be detected.
31P NMR (162 MHz): δ 48.0 (d, J ) 25 Hz), 33.2 (d, J )
25 Hz). IR (cm-1, KBr): 2127 (νCtN), 1713 (νCdO). FAB-MS: m/z
838 (M - PF6-). Anal. Calcd for C48H52F6NO2P3Ru: C, 58.65;
H, 5.33; N, 1.42. Found: C, 58.75; H, 5.36; N, 1.66.
Reaction of [(η5:η1-2-Me-4-R-C5H2CO2CH2CH2PPh2)Ru-
(PMe3)(NCMe)][PF6] (R ) Me, Ph, But) (1d-f) with tert-
Butyl Isocyanide. This reaction was performed in a manner
similar to that for 1a-c with a longer reaction time (36 h).
Yield and diastereoselectivity of the products are given in
Table 1.
detected. 31P NMR (162 MHz): δ 41.7 (d, J ) 31 Hz), 8.3
(d, J ) 31 Hz). Minor product (2f-I): H NMR (400 MHz):
1
δ 7.91-7.86 (m, 2H, Ph), 7.70-7.68 (m, 1H, Ph), 7.63-7.47
(m, 5H, Ph), 7.19 (br, 2H, Ph), 5.38 (s, 1H, Cp′), 5.27 (s, 1H,
Cp′), 5.07-4.97 (m, 1H, OCH2), 4.05 (br, 1H, OCH2), 3.08-
2.81 (m, 2H, PCH2), 2.41 (s, 3H, Cp′Me), 1.66 (s, 9H, CMe3),
1.45 (s, 9H, CMe3), 1.21 (d, 9H, J ) 9.8 Hz, PMe3). 31P NMR
(162 MHz): δ 40.3 (d, J ) 30 Hz), 10.4 (d, J ) 30 Hz).
Reaction of [(η5:η1-2-Me-4-R-C5H2CO2CH2CH2PPh2)-
Ru{P(OPh)3}(NCMe)][PF6] (R ) Me, Ph, But) (1g-i) with
tert-Butyl Isocyanide. Ruthenium complexes 1g-i
(0.1 mmol) were treated with tert-butyl isocyanide (0.08 g,
1.0 mmol) in refluxing 1,2-dichloroethane (5 mL) for 12 h.
Purification similar to that for 1a-c gave the products in
yields with diastereoselectivity given in Table 1, respectively.
[(η5:η1-2,4-Me2-C5H2CO2CH2CH2PPh2)Ru(PMe3)(CNBut)]-
[PF6] (2d-I and 2d-II). IR (cm-1, KBr): 2126 (νCtN), 1705
(νCdO). FAB-MS: m/z 610 (M - PF6-). Anal. Calcd for
C30H40F6NO2P3Ru: C, 47.75; H, 5.34; N, 1.86. Found: C, 47.90;
H, 5.24; N, 1.88. Major product (2d-I): 1H NMR (600 MHz):
δ 7.78-7.63 (m, 4H, Ph), 7.46 (br, 4H, Ph), 7.13 (br, 2H, Ph),
5.22 (s, 1H, Cp′), 5.11 (s, 1H, Cp′), 5.06-5.00 (m, 1H, OCH2),
3.96-3.92 (m, 1H, OCH2), 2.94-2.80 (m, 2H, PCH2), 2.42
(s, 3H, Cp′Me), 2.31 (d, 3H, J ) 2.6 Hz, Cp′Me), 1.65 (s, 9H,
CMe3), 1.14 (d, 9H, J ) 9.9 Hz, PMe3). 13C NMR (151 MHz):
δ 164.9 (CdO), 140.7-129.8 (Ph), 115.5 (Cp′), 104.0 (Cp′), 93.3
(Cp′), 85.6 (d, J ) 9 Hz, Cp′), 82.3 (d, J ) 6 Hz, Cp′), 59.4
(CMe3), 59.3 (OCH2), 30.8 (CMe3), 23.0 (d, J ) 35 Hz, PCH2),
20.0 (d, J ) 34 Hz, PMe3), 13.7 (Cp′Me), 13.4 (Cp′Me); the
signal assignable to the isocyano carbon could not be detected.
31P NMR (162 MHz): δ 45.3 (d, J ) 32 Hz), 10.2 (d, J )
32 Hz). Minor product (2d-II): 1H NMR (600 MHz): δ 7.88-
7.85 (m, 2H, Ph), 7.78-7.63 (m, 6H, Ph), 7.37 (br, 2H, Ph),
5.18 (s, 1H, Cp′), 5.06-5.00 (m, 1H, OCH2), 4.95 (s, 1H, Cp′),
3.96-3.92 (m, 1H, OCH2), 3.21-3.15 (m, 1H, PCH2), 2.94-
2.80 (m, 1H, PCH2), 2.39 (d, 3H, J ) 3.9 Hz, Cp′Me), 2.34
(s, 3H, Cp′Me), 1.54 (s, 9H, CMe3), 1.12 (d, 9H, J ) 9.9 Hz,
PMe3). 31P NMR (162 MHz): δ 43.1 (d, J ) 31 Hz), 10.8
(d, J ) 31 Hz).
[(η5:η1-2-Me-4-Ph-C5H2CO2CH2CH2PPh2)Ru(PMe3)-
(CNBut)][PF6] (2e-I and 2e-II). IR (cm-1, KBr): 2128
(νCtN), 1715 (νCdO). FAB MS: m/z 672 (M - PF6-). Anal. Calcd
for C35H42F6NO2P3Ru: C, 51.47; H, 5.18; N, 1.72. Found: C,
51.47; H, 5.06; N, 1.64. Major product (2e-I): 1H NMR
(400 MHz): δ 7.92 (d, 2H, J ) 7.3 Hz, Ph), 7.77-7.73 (m, 5H,
Ph), 7.64 (t, 2H, J ) 7.3 Hz, Ph), 7.55 (t, 1H, J ) 7.3 Hz, Ph),
7.44-7.43 (m, 3H, Ph), 7.11-7.07 (m, 2H, Ph), 6.00 (s, 1H,
Cp′), 5.79 (s, 1H, Cp′), 5.15-5.05 (m, 1H, OCH2), 4.12-4.08
(m, 1H, OCH2), 3.00-2.95 (m, 2H, PCH2), 2.55 (s, 3H, Cp′Me),
1.67 (s, 9H, CMe3), 0.82 (d, 9H, J ) 10.3 Hz, PMe3). 13C NMR
(151 MHz): δ 165.0 (CdO), 140.4-127.2 (Ph), 115.9 (Cp′),
106.2 (Cp′), 89.4 (Cp′), 84.0 (d, J ) 6 Hz, Cp′), 80.8 (Cp′), 59.7
(CMe3), 59.6 (d, J ) 5 Hz, OCH2), 30.2 (CMe3), 22.8 (d, J )
35 Hz, PCH2), 18.8 (d, J ) 34 Hz, PMe3), 14.0 (Cp′Me); the
signal assignable to the isocyano carbon could not be detected.
31P NMR (162 MHz): δ 44.6 (d, J ) 32 Hz), 10.5 (d, J )
32 Hz). Minor product (2e-II): 31P NMR (162 MHz): δ 44.0
(d, J ) 30 Hz), 12.1 (d, J ) 30 Hz).
[(η5:η1-2,4-Me2-C5H2CO2CH2CH2PPh2)Ru{P(OPh)3}-
(CNBut)][PF6] (2g-I and 2g-II). IR (cm-1, KBr): 2161
(νCtN), 1722 (νCdO). FAB-MS: m/z 844 (M - PF6-). Anal. Calcd
for C45H46F6NO5P3Ru: C, 54.66; H, 4.69; N, 1.42. Found: C,
54.44; H, 4.66; N, 1.67. Major product (2g-I): 1H NMR
(600 MHz): δ 7.98-7.95 (m, 2H, Ph), 7.68-7.67 (m, 3H, Ph),
7.55-7.52 (m, 2H, Ph), 7.48-7.46 (m, 1H, Ph), 7.41-7.38
(m, 2H, Ph), 7.24-7.21 (m, 6H, Ph), 7.12 (t, 3H, J ) 7.5 Hz,
Ph), 6.76 (d, 6H, J ) 8.6 Hz, Ph), 5.19 (s, 1H, Cp′), 5.14-5.08
(m, 1H, OCH2), 4.14-4.09 (m, 1H, OCH2), 4.07 (s, 1H, Cp′),
3.09-3.02 (m, 2H, PCH2), 2.43 (d, 3H, J ) 3.8 Hz, Cp′Me),
2.23 (s, 3H, Cp′Me), 1.71 (s, 9H, CMe3). 13C NMR (151 MHz):
δ 164.6 (CdO), 152.6 (CtN), 140.1-121.2 (Ph), 116.5 (Cp′),
106.0 (Cp′), 94.2 (Cp′), 86.0 (d, J ) 7 Hz, Cp′), 83.6 (d, J )
14 Hz, Cp′), 60.2 (CMe3), 59.8 (d, J ) 5 Hz, OCH2), 30.9 (CMe3),
23.2 (d, J ) 35 Hz, PCH2), 13.4 (Cp′Me), 13.3 (Cp′Me). 31P NMR
(162 MHz): δ 133.2 (d, J ) 52 Hz), 42.9 (d, J ) 52 Hz). Minor
1
product (2g-II): H NMR (600 MHz): δ 2.41 (s, 3H, Cp′Me),
2.26 (d, 3H, J ) 3.4 Hz, Cp′Me), 1.64 (s, 9H, CMe3); the signals
assignable to the other protons could not be identified due to
overlap with those of the major product. 31P NMR (162 MHz):
δ 132.2 (d, J ) 55 Hz); the other signal could not be detected
due to overlap with that of the major product.
[(η5:η1-2-Me-4-Ph-C5H2CO2CH2CH2PPh2)Ru{P(OPh)3}-
(CNBut)][PF6] (2h-I and 2h-II). 13C NMR (151 MHz): δ 164.9
(CdO), 164.6 (CdO), 152.4 (d, J ) 15 Hz, CtN), 152.3 (d, J )
14 Hz, CtN), 139.9-120.8 (Ph), 116.7 (Cp′), 113.2 (d, J )
5 Hz, Cp′), 108.0 (Cp′), 91.8 (Cp′), 83.5 (d, J ) 13 Hz, Cp′),
82.7 (d, J ) 13 Hz, Cp′), 82.3 (d, J ) 7 Hz, Cp′), 78.7 (Cp′),
60.5 (CMe3), 60.0 (d, J ) 5 Hz, OCH2), 60.3 (d, J ) 5 Hz,
OCH2), 30.9 (CMe3), 30.4 (CMe3), 22.9 (d, J ) 35 Hz, PCH2),
20.2 (d, J ) 34 Hz, PCH2), 13.5 (Cp′Me), 13.3 (Cp′Me). IR
(cm-1, KBr): 2151 (νCtN), 1727 (νCdO). FAB-MS: m/z 906
(M - PF6-). Anal. Calcd for C50H48F6NO5P3Ru: C, 57.15; H,
4.60; N, 1.33. Found: C, 57.21; H, 4.82; N, 1.34. Major
product (2h-I): 1H NMR (400 MHz): δ 7.90-7.85 (m, 2H, Ph),
7.73-7.29 (m, 13H, Ph), 7.15 (t, 6H, J ) 7.3 Hz, OPh), 7.07
(t, 3H, J ) 7.3 Hz, OPh), 6.41 (d, 6H, J ) 8.5 Hz, OPh), 5.86
(d, 1H, J ) 1.7 Hz, Cp′), 5.18 (d, 1H, J ) 1.7 Hz, Cp′), 5.27-
5.15 (m, 1H, OCH2), 4.34-4.26 (m, 1H, OCH2), 3.15-3.03
(m, 2H, PCH2), 2.44 (s, 3H, Cp′Me), 1.75 (s, 9H, CMe3).
31P NMR (162 MHz): δ 128.3 (d, J ) 51 Hz), 42.1 (d, J )
51 Hz). Minor product (2h-II): 1H NMR (400 MHz): δ 7.84-
7.78 (m, 2H, Ph), 7.73-7.29 (m, 19H, Ph, OPh), 7.21 (t, 3H,
J ) 7.3 Hz, OPh), 6.85 (d, 6H, J ) 8.5 Hz, OPh), 5.81 (m, 1H,
Cp′), 5.27-5.15 (m, 1H, OCH2), 4.67 (s, 1H, Cp′), 4.18-4.10
(m, 1H, OCH2), 3.35-3.25 (m, 2H, PCH2), 2.56 (d, 3H, J )
8.5 Hz, Cp′Me), 1.16 (s, 9H, CMe3). 31P NMR (162 MHz):
δ 132.3 (d, J ) 53 Hz), 44.3 (d, J ) 53 Hz).
[(η5:η1-2-Me-4-But-C5H2CO2CH2CH2PPh2)Ru(PPh3)-
(CNBut)][PF6] (2f-I and 2f-II). IR (cm-1, KBr): 2112 (νCtN),
1715 (νCdO). FAB-MS: m/z 652 (M - PF6-). Anal. Calcd for
C33H46F6NO2P3Ru: C, 49.75; H, 5.82; N, 1.76. Found: C, 49.55;
H, 5.74; N, 1.74. Major product (2f-II): 1H NMR (400 MHz):
δ 8.00-7.95 (m, 2H, Ph), 7.63-7.47 (m, 6H, Ph), 7.37 (br, 2H,
Ph), 5.19 (s, 1H, Cp′), 5.17 (s, 1H, Cp′), 5.07-4.97 (m, 1H,
OCH2), 3.76-3.69 (m, 1H, OCH2), 3.08-2.81 (m, 2H, PCH2),
2.40 (s, 3H, Cp′Me), 1.51 (s, 9H, CMe3), 1.50 (s, 9H, CMe3),
1.14 (d, 9H, J ) 10.3 Hz, PMe3). 13C NMR (151 MHz): δ 166.5
(CdO), 140.9-129.2 (Ph), 111.7 (Cp′), 92.4 (Cp′), 89.9 (Cp′),
80.3 (d, J ) 7 Hz, Cp′), 77.1 (d, J ) 6 Hz, Cp′), 60.3 (CMe3),
59.9 (OCH2), 33.8 (CMe3), 32.1 (CMe3), 31.3 (CMe3), 22.4
(d, J ) 34 Hz, PCH2), 18.8 (d, J ) 32 Hz, PMe3), 13.2 (Cp′Me);
the signal assignable to the isocyano carbon could not be
[(η5:η1-2-Me-4-But-C5H2CO2CH2CH2PPh2)Ru{P(OPh)3}-
(CNBut)][PF6] (2i-I and 2i-II). IR (cm-1, KBr): 2144 (νCtN),
1732 (νCdO). FAB-MS: m/z 886 (M - PF6-). Anal. Calcd for
C48H52F6NO5P3Ru: C, 55.92; H, 5.08; N, 1.36. Found: C, 55.72;
H, 5.00; N, 1.16. Major product (2i-II): 1H NMR (400 MHz):
δ 8.02-7.99 (m, 2H, Ph), 7.69-7.48 (m, 8H, Ph), 7.25 (t, 6H,

Ruthenium-Isocyanide and -Acetylide Complexes
Organometallics, Vol. 24, No. 11, 2005 2753
J ) 8.6 Hz, OPh), 7.15 (t, 3H, J ) 7.5 Hz, OPh), 6.82 (d, 6H,
J ) 8.6 Hz, OPh), 5.37 (m, 1H, Cp′), 5.17-5.10 (m, 1H, OCH2),
4.20 (s, 1H, Cp′), 3.94-3.89 (m, 1H, OCH2), 3.34-3.29 (m, 1H,
PCH2), 3.19 (dt, 1H, J ) 15.4, 4.2 Hz, PCH2), 2.50 (d, 3H, J )
5.9 Hz, Cp′Me), 1.57 (s, 9H, CMe3), 1.37 (s, 9H, CMe3).
13C NMR (151 MHz): δ 166.0 (CdO), 152.7 (d, J ) 14 Hz, CN),
140.6-121.2 (Ph), 114.2 (Cp′), 92.6 (Cp′), 79.6 (d, J ) 4 Hz,
Cp′), 79.4 (d, J ) 7 Hz, Cp′), 60.7 (d, J ) 5 Hz, OCH2), 60.6
(CMe3), 32.9 (CMe3), 31.1 (CMe3), 30.08 (CMe3), 21.1 (d, J )
35 Hz, PCH2), 13.4 (Cp′Me). 31P NMR (162 MHz): δ 131.7
(d, J ) 55 Hz), 40.0 (d, J ) 55 Hz). Minor product (2i-I):
1H NMR (600 MHz): δ 6.75 (d, 6H, J ) 7.8 Hz, OPh), 2.25
(s, 3H, Cp′Me), 1.77 (s, 9H, CMe3), 1.43 (s, 9H, CMe3); the
signals assignable to the other protons could not be identified
due to overlap with those of the major product. 31P NMR
(162 MHz): δ 132.5 (d, J ) 50 Hz), 38.4 (d, J ) 50 Hz).
Reaction of Ruthenium Complexes 1a-f with Phenyl-
acetylene. To a dichloromethane solution (5 mL) of ruthenium
complex 1 (0.1 mmol) was added phenylacetylene (0.11 g,
1.0 mmol), and the reaction mixture was refluxed for 48 h.
The solvent was evaporated, and the residual oil was washed
with diethyl ether several times. The residue was dissolved
in dichloromethane and placed on an alumina column. The
benzene elution was collected, and the solvent was removed
under reduced pressure to give a yellow solid. Yield and
diastereoselectivity of the product 4 are given in Table 2. The
reaction of 1c was performed at room temperature for 4 days
because no vinylidene complex was formed in the reaction in
refluxing dichloromethane.
(d, J ) 10 Hz, Cp′), 58.8 (OCH2), 33.0 (CMe3), 30.3 (CMe3),
19.5 (d, J ) 26 Hz, PCH2), 12.3 (Cp′Me). 31P NMR (162 MHz):
δ 44.4 (d, J ) 29 Hz), 21.7 (d, J ) 29 Hz). IR (cm-1, KBr):
2081 (νCtC), 1713 (νCdO). FAB-MS: m/z 856 (M+). Anal. Calcd
for C51H48O2P2Ru: C, 71.56; H, 5.65. Found: C, 71.56; H, 5.65.
(η5:η1-2,4-Me2-C5H2CO2CH2CH2PPh2)Ru(PMe3)(Ct
CPh) (4d). IR (cm-1, KBr): 2076 (νCtC), 1697 (νCdO). FAB-
MS: m/z 628 (M+). Anal. Calcd for C33H36O2P2Ru: C, 63.15;
H, 5.78. Found: C, 63.14; H, 5.68. Major product (4d-II):
1H NMR (600 MHz): δ 7.65 (t, 2H, J ) 8.1 Hz, Ph), 7.52-7.48
(m, 3H, Ph), 7.31 (d, 2H, J ) 8.1 Hz, Ph), 7.26-7.15 (m, 6H,
Ph), 7.04 (t, 1H, J ) 7.3 Hz, Ph), 5.02-4.95 (m, 1H, OCH2),
4.77 (s, 1H, Cp′), 4.58 (s, 1H, Cp′), 3.79-3.74 (m, 1H, OCH2),
3.31-3.24 (m, 1H, PCH2), 2.34 (s, 3H, Cp′Me), 2.27-2.22
(m, 1H, PCH2), 2.22 (s, 3H, Cp′Me), 1.00 (d, 9H, J ) 9.2 Hz,
PMe3). 13C NMR (151 MHz): δ 164.7 (CdO), 142.2-127.5 (Ph),
123.4 (RuCtC), 114.4 (Cp′), 105.6 (RuCtC), 94.8 (Cp′), 89.2
(Cp′), 84.5 (d, J ) 10 Hz, Cp′), 79.5 (d, J ) 9 Hz, Cp′), 58.3
(d, J ) 4 Hz, OCH2), 22.1 (d, J ) 34 Hz, PCH2), 20.6 (d, J )
30 Hz, PMe3), 14.2 (Cp′Me), 13.6 (Cp′Me). 31P NMR
(162 MHz): 45.1 (d, J ) 39 Hz), 9.7 (d, J ) 39 Hz). Minor
product (4d-I): 1H NMR (600 MHz): δ 7.91-7.88 (m, 2H, Ph),
7.74-7.73 (m, 1H, Ph), 7.41-6.95 (m, 12H, Ph), 5.07 (ddd, 1H,
J ) 20.1, 10.7, 7.1 Hz, OCH2), 4.61 (s, 1H, Cp′), 4.53 (s, 1H,
Cp′), 3.87-3.82 (m, 1H, OCH2), 2.76-2.64 (m, 2H, PCH2), 2.35
(d, 3H, J ) 3.0 Hz, Cp′Me), 2.30 (d, 3H, J ) 1.6 Hz, Cp′Me),
0.98 (d, 9H, J ) 9.1 Hz, PMe3). 31P NMR (162 MHz): δ 38.2
(d, J ) 36 Hz), 9.5 (d, J ) 36 Hz).
(η5:η1-2-Me-4-Ph-C5H2CO2CH2CH2PPh2)Ru(PMe3)(Ct
CPh) (4e). IR (cm-1, KBr): 2084 (νCtC), 1704 (νCdO). FAB-
MS: m/z 690 (M+). Anal. Calcd for C38H38O2P2Ru: C, 66.17;
H, 5.55. Found: C, 66.44; H, 5.35. Major product (4e-II):
1H NMR (600 MHz): δ 7.66-6.69 (m, 20H, Ph), 5.37 (s, 1H,
Cp′), 5.17 (s, 1H, Cp′), 5.10-5.03 (m, 1H, OCH2), 3.95-3.90
(m, 1H, OCH2), 3.34-3.27 (m, 1H, PCH2), 2.50 (s, 3H, Cp′Me),
2.27 (dt, 1H, J ) 14.6, 4.9 Hz, PCH2), 0.71 (d, 9H, J ) 9.6 Hz,
PMe3). 13C NMR (151 MHz): 164.7 (CdO), 142.0-125.0 (Ph),
123.5 (RutCC), 114.7 (Cp′), 105.7 (RuC≡C), 97.2 (Cp′), 86.2
(Cp′), 80.8 (d, J ) 7 Hz, Cp′), 79.7 (d, J ) 11 Hz, Cp′), 58.5
(d, J ) 3 Hz, OCH2), 21.7 (d, J ) 35 Hz, PCH2), 19.5 (d, J )
31 Hz, PMe3), 13.9 (Cp′Me). 31P NMR (162 MHz): 43.6 (d, J )
(η5:η1-2,4-Me2-C5H2CO2CH2CH2PPh2)Ru(PPh3)(Ct
1
CPh) (4a-I). H NMR (400 MHz): δ 8.02-8.00 (m, 2H, Ph),
7.39-6.79 (m, 26H, Ph), 6.38 (t, 2H, J ) 8.3 Hz, Ph), 5.06 (ddd,
1H, J ) 19.5, 11.2, 8.3 Hz, OCH2), 4.52 (d, 1H, J ) 2.2 Hz,
Cp′), 3.99 (d, 1H, J ) 2.2 Hz, Cp′), 3.89-3.84 (m, 1H, OCH2),
2.67-2.58 (m, 1H, PCH2), 2.35-2.34 (s, 3H, Cp′Me), 2.14
(dt, 1H, J ) 14.9, 5.1 Hz, PCH2), 1.39 (s, 3H, Cp′Me). 13C NMR
(151 MHz): δ 166.3 (CdO), 142.6-127.4 (Ph), 127.1 (Cp′),
123.0 (Cp′), 110.8 (d, J ) 4 Hz, Cp′), 109.9 (d, J ) 20 Hz, RuCt
C), 87.0 (d, J ) 11 Hz, RuCtC), 84.7 (Cp′), 81.3 (d, J ) 9 Hz,
Cp′), 58.1 (d, J ) 4 Hz, OCH2), 18.5 (d, J ) 25 Hz, PCH2), 14.2
(Cp′Me), 11.8 (Cp′Me). 31P NMR (162 MHz): δ 47.5 (d, J )
31 Hz), 35.3 (d, J ) 31 Hz). IR (cm-1, KBr): 2076 (νCtC), 1704
(νCdO). FAB-MS: m/z 814 (M+). Anal. Calcd for C48H42O2P2-
Ru: C, 70.84; H, 5.20. Found: C, 70.62; H, 5.27.
1
38 Hz), 9.5 (d, J ) 38 Hz). Minor product (4e-I): H NMR
(600 MHz): δ 7.66-6.69 (m, 20H, Ph), 5.19 (s, 1H, Cp′), 5.09
(s, 1H, Cp′), 5.10-5.03 (m, 1H, OCH2), 4.05-4.00 (m, 1H,
OCH2), 2.79-2.69 (m, 2H, PCH2), 2.42 (d, 3H, J ) 2.5 Hz,
Cp′Me), 1.03 (d, 9H, J ) 9.1 Hz, PMe3). 31P NMR (162 MHz):
δ 39.1 (d, J ) 36 Hz), 10.6 (d, J ) 36 Hz).
(η5:η1-2-Me-4-Ph-C5H2CO2CH2CH2PPh2)Ru(PPh3)(Ct
CPh) (4b). 1H NMR (400 MHz): δ 7.80-7.76 (m, 2H, Ph),
7.66-7.64 (m, 2H, Ph), 7.48-6.77 (m, 27H, Ph), 6.33 (t, 2H,
J ) 8.5 Hz, Ph), 6.26 (d, 2H, J ) 7.3 Hz, Ph), 5.16-5.06
(m, 1H, OCH2), 5.09 (s, 1H, Cp′), 4.50 (s, 1H, Cp′), 3.96
(dt, 1H, J ) 10.3, 5.1 Hz, OCH2), 2.74-2.66 (m, 1H, CH2P),
2.20 (dt, 1H, J ) 14.6, 5.1 Hz, PCH2), 1.50 (s, 3H, Cp′Me).
13C NMR (100 MHz): δ 166.2 (CdO), 142.3-127.0 (Ph), 122.7
(Cp′), 113.1 (d, J ) 5 Hz, Cp′), 110.8 (RuCtC or Cp′), 110.1-
(RuCtC or Cp′), 86.2 (Cp′), 84.9 (d, J ) 13 Hz, RuCtC), 78.3
(d, J ) 8 Hz, Cp′), 58.3 (d, J ) 4 Hz, OCH2), 20.0 (d, J )
26 Hz, PCH2), 12.1 (Cp′Me). 31P NMR (162 MHz): δ 47.8
(d, J ) 31 Hz), 36.2 (d, J ) 31 Hz). IR (cm-1, KBr): 2080
(νCtC), 1708 (νCdO). FAB-MS: m/z 876 (M+). Anal. Calcd for
C53H44O2P2Ru: C, 72.59; H, 5.17. Found: C, 72.39; H, 4.88.
(η5:η1-2-Me-4-But-C5H2CO2CH2CH2PPh2)Ru(PPh3)(Ct
(η5:η1-2-Me-4-But-C5H2CO2CH2CH2PPh2)Ru(PMe3)(Ct
CPh) (4f). IR (cm-1, KBr): 2080 (νCtC), 1714 (νCdO). FAB-MS:
m/z 670 (M+). Anal. Calcd for C36H42O2P2Ru: C, 64.56; H, 6.32.
Found: C, 65.02; H, 6.26. Major product (4f-I): 1H NMR
(400 MHz): δ 8.02-7.97 (m, 2H, Ph), 7.50-6.92 (m, 13H, Ph),
5.04-4.94 (m, 1H, OCH2), 4.87 (s, 1H, Cp′), 4.53 (s, 1H, Cp′),
3.64-3.57 (m, 1H, OCH2), 2.82-2.74 (m, 1H, PCH2), 2.53
(dt, 1H, J ) 14.1, 4.4 Hz, PCH2), 2.37 (s, 3H, Cp′Me), 1.54
(s, 9H, CMe3), 0.95 (d, 9H, J ) 9.1 Hz, PMe3). 13C NMR
(151 MHz): δ 167.7 (CdO), 143.0-127.3 (Ph), 123.4 (RuCt
C), 115.3 (Cp′), 110.7 (RuCtC), 103.9 (Cp′), 87.2 (Cp′), 78.2
(d, J ) 10 Hz, Cp′), 73.9 (d, J ) 8 Hz, Cp′), 58.5 (d, J ) 3 Hz,
OCH2), 32.5 (CMe3), 30.7 (CMe3), 22.8 (d, J ) 31 Hz, PCH2),
19.0 (d, J ) 31 Hz, PMe3), 13.7 (Cp′Me). 31P NMR (162 MHz):
δ 35.9 (d, J ) 35 Hz), 9.0 (d, J ) 35 Hz). Minor product
1
CPh) (4c-I). H NMR (400 MHz): δ 8.08 (t, 3H, J ) 8.4 Hz,
Ph), 7.38-7.25 (m, 16H, Ph), 7.04 (t, 2H, J ) 7.5 Hz, Ph), 6.99
(t, 2H, J ) 7.5 Hz, Ph), 6.91 (t, 1H, J ) 7.1 Hz, Ph), 6.81
(d, 2H, J ) 8.4 Hz, Ph), 6.73 (t, 2H, J ) 7.5 Hz, Ph), 6.49
(t, 2H, J ) 8.4 Hz, Ph), 5.07 (ddd, 1H, J ) 19.0, 11.2, 7.9 Hz,
OCH2), 4.77 (s, 1H, Cp′), 3.72 (s, 1H, Cp′), 3.68-3.64 (m, 1H,
OCH2), 3.02-2.96 (m, 1H, PCH2), 2.14 (dt, 1H, J ) 14.5,
4.8 Hz, PCH2), 1.63 (s, 3H, Cp′Me), 1.59 (s, 9H, CMe3).
13C NMR (151 MHz): δ 167.8 (CdO), 142.8-127.4 (Ph), 127.2
(d, J ) 10 Hz, Cp′), 122.8 (Cp′), 114.3 (d, J ) 11 Hz, RuCtC),
105.8 (Cp′), 86.9 (d, J ) 11 Hz, RuCtC), 86.4 (Cp′), 71.7
1
(4f-II): H NMR (400 MHz): δ 7.85-7.79 (m, 2H, Ph), 7.50-
6.92 (m, 13H, Ph), 5.04-4.94 (m, 1H, OCH2), 4.87 (s, 1H, Cp′),
4.59 (s, 1H, Cp′), 3.79-3.73 (m, 1H, OCH2), 3.45-3.37 (m, 1H,
PCH2), 2.39 (s, 3H, Cp′Me), 2.20 (dt, 1H, J ) 14.4, 4.6 Hz,
PCH2), 1.37 (s, 9H, CMe3), 1.04 (d, 9H, J ) 9.0 Hz, PMe3).
31P NMR (162 MHz): δ 45.41 (d, J ) 36 Hz), 7.6 (d, J )
36 Hz).
X-ray Diffraction Analyses of Complexes 2c-I, 4a-I,
and 4c-I. Crystals suitable for X-ray diffraction were mounted

2754 Organometallics, Vol. 24, No. 11, 2005
Matsushima et al.
Table 3. Summary of Crystallographic Data for Complexes 2c-I, 4a-I, and 4c-I
2c-I
4a-I‚0.5CHCl3
4c-I‚CH2Cl2
empirical formula
fw
cryst dimens/mm
cryst syst
lattice params
a/Å
C48H52F6NO2P3Ru
982.93
C48.5H42.5Cl1.5O2P2Ru
873,57
C52H50Cl2O2P2Ru
982.93
0.30 × 0.20 × 0.05
0.50 × 0.25 × 0.05
0.25 × 0.20 × 0.15
monoclinic
triclinic
monoclinic
13.739(6)
18.886(6)
17.871(5)
12.584(6)
19.703(9)
9.045(7)
98.03(6)
104.57(3)
72.12(4)
2060(2)
P1h (# 2)
2
9.875(2)
21.578(2)
21.305(2)
b/Å
c/Å
R/deg
â/deg
93.53(3)
101.92(1)
γ/deg
V/Å3
4628(2)
P21/n (# 14)
4
1.411
2024
5.05
4441(1)
P21/c (# 14)
4
1.407
1944
5.86
space group
Z value
Dcalcd/g cm-3
F(000)
1.408
898
µ(Mo KR)/cm-1
no. reflns measd
total
5.94
11 450
9954
9100
unique
11 106 (Rint ) 0.160)
5661 (I > 2.0σ(I))
602
9518 (Rint ) 0.094)
7843 (I > 2.0σ(I))
554
8844 (Rint ) 0.160)
5016 (I > 2.0σ(I))
582
no. observations
no. params
residuals: R1; wR2
GOF
0.054; 0.114
1.098
0.86, -1.02
0.047; 0.082
1.186
0.92, -1.51
0.065; 0.130
1.177
1.25, -1.05
peak, hole/e Å-3
on a glass fiber with epoxy resin. All measurements were
performed on a Rigaku AFC7R or AFC5R automated four-
circle diffractometer using graphite-monochromated Mo KR
radiation (λ ) 0.71069 Å). A summary of crystallographic data
is given in Table 3. Additional information on the collection of
the data and the refinement of the structures is available as
Supporting Information.
Ministry of Education, Science, Sports and Culture. We
thank the members of the Material Analysis Center,
ISIR, Osaka University, for spectral measurements,
X-ray diffraction, and microanalyses.
Supporting Information Available: Details of crystal-
lographic work (CIF file). This material is available free of
charge via the Internet at http://pubs.acs.org.
Acknowledgment. This work was supported in part
by a Grant-in-Aid for Scientific Research from the
OM0500523