Preparation of a series of chalcogenolate-bridged diruthenium complexes and their catalytic activities toward propargylic substitution reactions

Article abstract of DOI:10.1021/om034137k

A series of chalcogenolate(Se,Te)-bridged diruthenium complexes (neutral and cationic) as well as their allenylidene complexes have been newly prepared, and their catalytic activities toward the propargylic substitution reactions have been compared with those using the corresponding thiolate(S)-bridged complexes. Results of both catalytic and stoichiometric reactions using these complexes together with their redox properties show that the ease of the charge transfer from one Ru atom (working as an electron pool) to the other in the complexes (synergistic effect) may be one of the important factors in promoting a key ligand exchange step for these catalytic reactions. The finding presented here may provide a new possibility of polynuclear transition metal complexes for organic transformations.

Full text of DOI:10.1021/om034137k

2
6
Organometallics 2004, 23, 26-30
P r ep a r a tion of a Ser ies of Ch a lcogen ola te-Br id ged
Dir u th en iu m Com p lexes a n d Th eir Ca ta lytic Activities
tow a r d P r op a r gylic Su bstitu tion Rea ction s
,
†
†
†
Yoshiaki Nishibayashi,* Hiroaki Imajima, Gen Onodera,
‡
,†
Masanobu Hidai, and Sakae Uemura*
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering,
Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, J apan, and Department of
Materials Science and Technology, Faculty of Industrial Science and Technology,
Tokyo University of Science, Noda, Chiba 278-8510, J apan
Received August 28, 2003
A series of chalcogenolate(Se,Te)-bridged diruthenium complexes (neutral and cationic)
as well as their allenylidene complexes have been newly prepared, and their catalytic
activities toward the propargylic substitution reactions have been compared with those using
the corresponding thiolate(S)-bridged complexes. Results of both catalytic and stoichiometric
reactions using these complexes together with their redox properties show that the ease of
the charge transfer from one Ru atom (working as an electron pool) to the other in the
complexes (synergistic effect) may be one of the important factors in promoting a key ligand
exchange step for these catalytic reactions. The finding presented here may provide a new
possibility of polynuclear transition metal complexes for organic transformations.
In tr od u ction
Sch em e 1
We have recently disclosed the ruthenium-catalyzed
efficient propargylic substitution reactions of propargylic
alcohols with various heteroatom- and carbon-centered
nucleophiles to afford the corresponding propargylated
1
products in high yields with a complete regioselectivity.
The reactions are catalyzed by thiolate-bridged diru-
thenium complexes such as [Cp*RuCl(µ2-SR)]2 (Cp* )
5
n
i
η -C5Me5; R ) Me (1a ), Pr, Pr) and [Cp*RuCl(µ2-SMe)2-
RuCp*(OH2)]OTf (OTf ) OSO2CF3) (1b) but not by
2
various monoruthenium complexes which have been
known to work as reagents for stoichiometric propar-
3
gylic subtitution reactions. Results of some stoichio-
metric and catalytic reactions indicate that the prop-
argylic substitution reactions proceed via allenylidene
intermediates as shown in Scheme 1, where only one of
the two Ru atoms works as a reactive site throughout
the reaction.4 Here, the reason only the diruthenium
-6
*
To whom correspondence should be addressed. E-mail: ynishiba@
scl.kyoto-u.ac.jp (Y.N.); uemura@scl.kyoto-u.ac.jp (S.U.).
†
Kyoto University.
Tokyo University of Science.
complexes are effective for these catalytic reactions
seems to be that one Ru moiety, which is not involved
in allenylidene formation, works as an electron pool or
a mobile ligand to another Ru site (Scheme 2), by taking
into account the theoretical report of synergistic effects
‡
(1) (a) Nishibayashi, Y.; Wakiji, I.; Hidai, M. J . Am. Chem. Soc. 2000,
1
22, 11019. (b) Nishibayashi, Y.; Wakiji, I.; Ishii, Y.; Uemura, S.; Hidai,
M. J . Am. Chem. Soc. 2001, 123, 3393. (c) Nishibayashi, Y.; Onodera,
G.; Inada, Y.; Hidai, M.; Uemura, S. Organometallics 2003, 22, 873.
(
d) Inada, Y.; Nishibayashi, Y.; Hidai, M.; Uemura, S. J . Am. Chem.
Soc. 2002, 124, 15172.
2) The thiolate-bridged diruthenium complexes have been found
(
(5) For recent examples, see: (a) Trost, B. M.; Flygare, J . A. J . Am.
Chem. Soc. 1992, 114, 5476. (b) Maddock, S. M.; Finn, M. G. Angew.
Chem., Int. Ed. 2001, 40, 2138. (c) Yeh, K.-L.; Liu, B.; Lo, H.-L.; Huang,
H.-L.; Liu, R.-S. J . Am. Chem. Soc. 2002, 124, 6510. (d) Datta, S.;
Chang, C.-L.; Yeh, K.-L.; Liu, R.-S. J . Am. Chem. Soc. 2003, 125, 9294.
(6) (a) Nishibayashi, Y.; Inada, Y.; Hidai, M.; Uemura, S. J . Am.
Chem. Soc. 2002, 124, 7900. (b) Nishibayashi, Y.; Yoshikawa, M.;
Inada, Y.; Hidai, M.; Uemura, S. J . Am. Chem. Soc. 2002, 124, 11846.
(c) Nishibayashi, Y.; Inada, Y.; Hidai, M.; Uemura, S. J . Am. Chem.
Soc. 2003, 125, 6060. (d) Nishibayashi, Y.; Yoshikawa, M.; Inada, Y.;
Milton, M. D.; Hidai, M.; Uemura, S. Angew. Chem., Int. Ed. 2003,
42, 2681.
to provide unique bimetallic reaction sites for activation and trans-
formation of various terminal alkynes; see: Nishibayashi, Y.; Yama-
nashi, M.; Wakiji, I.; Hidai, M. Angew. Chem., Int. Ed. 2000, 39, 2909
and references therein.
(3) (a) Cadierno, V.; Conejero, S.; Gamasa, M. P.; Gimeno, J .
Organometallics 2001, 20, 3175. (b) Cadierno, V.; Conejero, S.; Gamasa,
M. P.; Gimeno, J . Organometallics 2002, 21, 3716.
(4) For recent reviews, see: (a) Werner, H. Chem. Commun. 1997,
9
1
03. (b) Touchard, D.; Dixneuf, P. H. Coord. Chem. Rev. 1998, 178-
80, 409. (c) Bruce, M. I. Chem. Rev. 1998, 98, 2797. (d) Cadierno, V.;
Gamasa, M. P.; Gimeno, J . Eur. J . Inorg. Chem. 2001, 571.
1
0.1021/om034137k CCC: $27.50 © 2004 American Chemical Society
Publication on Web 11/27/2003

Chalcogenolate-Bridged Diruthenium Complexes
Organometallics, Vol. 23, No. 1, 2004 27
Sch em e 2
Sch em e 3
Ch a r t 1
of two equal Rh metals in the dirhodium-catalyzed
7
reaction between a diazo compound and an alkane.
and 3a are summarized in Chart 1. Although the
diamagnetic nature of 3a suggests the existence of a
bonding interaction between the two Ru(III) atoms, we
cannot exclude the possibility that the diamagnetism
of complex 3a might be due to some exchange interac-
tion via the orbitals of the bridging Te by considering a
longer Ru-Ru bond.
Next, catalytic activities of 1-3 toward the propar-
gylic substitution reactions were investigated for com-
parison. Treatment of 1-phenyl-2-propyn-1-ol (4a ) with
acetone in the presence of 1a or 2a (5 mol %) and
NH4BF4 (10 mol %) at reflux temperature for 3 h
afforded 4-phenyl-5-hexyn-2-one (5a ) in 88% or 95%
isolated yield, respectively (Table 1, runs 1 and 2).
Surprisingly, no propargylic alkylation occurred in the
presence of 3a under the same reaction conditions
(Table 1, run 3). When the reaction of 4a with acetone
was carried out in the presence of a cationic complex
such as 1b or 2b (2.5 mol %), 5a was obtained in 93%
or 95% GLC yield, respectively (Table 2, runs 1 and 2).
In sharp contrast, again no catalytic reaction proceeded
at all in the presence of 3b (Table 2, run 3).
To obtain some experimental evidence for this syn-
ergistic effect in our case, we have prepared a series of
chalcogenolate(Se,Te)-bridged diruthenium complexes
and compared their catalytic activities with those of
previously prepared thiolate(S)-bridged complexes in
propargylic substitution reactions. We describe here the
results and discuss the relation between Ru-Ru bond
lengths in the complexes as well as their redox poten-
tials and catalytic activities, to clarify the role of the
two Ru moieties.
Resu lts a n d Discu ssion
When an equimolar mixture of the tetranuclear
ruthenium(II) complex [Cp*Ru(µ3-Cl)]4 and dimethyl
diselenide was stirred in tetrahydrofuran (THF) at room
temperature for 20 h, the methaneselenolate-bridged
diruthenium complex [Cp*RuCl(µ2-SeMe)]2 (2a ) was
obtained in 54% isolated yield after recrystallization
(Scheme 3). Treatment of 2a with an equimolar amount
of AgOTf gave the corresponding cationic diruthenium
complex [Cp*RuCl(µ2-SeMe)2RuCp*(OH2)]OTf (2b) in
8
9% isolated yield as a single isomer. Similarly, the
methanetellurolate-bridged diruthenium complexes
Cp*RuCl(µ2-TeMe)]2 (3a ) and [Cp*RuCl(µ2-TeMe)2-
A similar phenomenon, a difference of catalytic activ-
ity, was also observed in propargylic substitution reac-
tions of 4a with various other nucleophiles such as
alcohol, amine, amide, and aromatic compounds. Typical
results are shown in Tables 1 and 2. Thus, the catalytic
use of 1 or 2 resulted in the formation of the corre-
sponding propargylated products in moderate to high
yields with complete regioselectivity, while the corre-
sponding propargylated products were not obtained by
use of 3.
[
RuCp*(OH2)]OTf (3b) were prepared using dimethyl
ditelluride in 83% and 72% isolated yields, respectively.
The molecular structures of all these complexes,
including the already prepared S analogues (Scheme 3),
were unambiguously determined by X-ray analysis, and
their ORTEP drawings are shown in the Supporting
Information. The Ru-Ru bond distance (3.04 Å) of 3a
is longer than those observed for the thiolate- and
selenolate-bridged complexes (1a , 2.84 Å; 2a , 2.92 Å),
and it is slightly longer than a typical Ru-Ru single
Reactions of cationic selenolate- and tellurolate-
bridged diruthenium complexes 2b and 3b with 1 equiv
of 1,1-bis(4′-methylphenyl)-2-propyn-1-ol (4b) in 1,2-
dichloroethane at room temperature for 1 h afforded the
allenylidene complexes 2c and 3c in 94% and 91%
isolated yields, respectively, as in the case of the
8
bond (2.71-3.02 Å). Selected bond lengths of 1a , 2a ,
(
7) Nakamura, E.; Yoshikai, N.; Yamanaka, M. J . Am. Chem. Soc.
002, 124, 7181.
8) Gao, Y.; J ennings, M. C.; Puddephatt, R. J .; J enkins, H. A.
Organometallics 2001, 20, 3500 and references therein.
2
1
a
corresponding thiolate complex 1c (Scheme 4). The
(
structures of allenylidene complexes are supported by

2
8
Organometallics, Vol. 23, No. 1, 2004
Nishibayashi et al.
Ta ble 1. P r op a r gylic Su bstitu tion Rea ction s of
Sch em e 4
P r op a r gylic Alcoh ol (4a ) w ith Nu cleop h iles Usin g
a Neu tr a l Ru Com p lex a s Ca ta lysta
previously been clarified by an X-ray study.1a Treatment
of 1c or 2c with 3 equiv of 1,1-diphenyl-2-propyn-1-ol
(4c) in EtOH at 60 °C for 6 h gave 5b in 38% or 49%
yield together with 5c in 70% yield, respectively.
However, in the reaction of 3c with 4c, only a quite low
yield of 5b as well as 5c was obtained. This fact clearly
shows that, in the tellurolate case, either the step of a
nucleophilic attack on Cγ (B f C in Scheme 1) in the
allenylidene moiety of 3c does not proceed smoothly or
the ligand exchange with another propargylic alcohol
(D f A in Scheme 1) does not occur readily.
a
All the reactions of 4a (0.60 mmol) with nucleophile were
carried out in the presence of catalyst (5 mol %) and NH4BF4 (10
mol %). Isolated yield. Acetone was used as solvent. d Ethanol
b
c
e
was used as solvent. Aniline (5 equiv) was used as nucleophile.
ClCH2CH2Cl was used as solvent. 2-Pyrrolidinone (5 equiv) was
used as nucleophile. 2-Methylfuran (10 equiv) was used as
nucleophile.
f
g
h
To obtain more information on the reaction mecha-
nism, the redox properties of 1b, 2b, and 3b were
9
Ta ble 2. P r op a r gylic Su bstitu tion Rea ction s of
P r op a r gylic Alcoh ol (4a ) w ith Nu cleop h iles Usin g
examined by cyclic voltammetry. The cyclic voltammo-
grams of 1b and 2b revealed two reversible waves at
E1/2 ) +0.58, +1.15 V and E1/2 ) +0.53, +1.11 V,
a
a Ca tion ic Ru Com p lex a s Ca ta lyst
III
IV
respectively, assignable to the redox couples [Ru /Ru ]
IV
IV
and [Ru /Ru ]. In contrast, the cyclic voltammogram
of 3b exhibited one irreversible wave at Ep ) +1.91 V.
This finding shows that the oxidation (namely, an
electron transfer) of 1b and 2b proceeds more smoothly
than that of 3b. The charge transfer from one Ru atom
to the other in the S and Se cases facilitates the ligand
exchange between alkynes on D and propargylic alcohol
(
step a in Scheme 2) because of the higher oxidation
IV
state of Ru reducing the back-donation ability from
the Ru to the coordinated alkyne moiety of D. The
difficulty of the charge transfer in the tellurolate case
corresponds to a quite low catalytic activity of 3a and
3
b.
Con clu sion
A series of chalcogenolate(Se,Te)-bridged diruthenium
complexes (neutral and cationic) as well as their alle-
nylidene complexes were newly prepared, and their
catalytic activities toward the propargylic substitution
reactions were compared with those of the correspond-
a
All the reactions of 4a (0.60 mmol) with nucleophile were
b
carried out in the presence of catalyst (5 mol %). Isolated yield.
c
e
d
Catalyst (2.5 mol %) was used. Acetone was used as solvent.
/[nBu
N]BF (0.002 mmol/ml), with a scan rate of 0.1
2 4 4
GLC yield. f Ethanol was used as solvent. g Aniline (5 equiv) was
(9) In CH
2
Cl
V s- and a saturated calomel electrode (SCE) reference electrode.
10) For recent reviews, see: (a) Bera, J . K.; Dunbar, K. R. Angew.
1
h
i
used as nucleophile. ClCH2CH2Cl was used as solvent. 2-
Pyrrolidinone (5 equiv) was used as nucleophile. 2-Methylfuran
10 equiv) was used as nucleophile.
(
j
Chem., Int. Ed. 2002, 41, 4453. (b) Tanase, T. Bull. Chem. Soc. J pn.
2002, 75, 1407.
(
(11) For recent examples, see: (a) Tejel, C.; Ciriano, M. A.; Villar-
roya, B. E.; L o´ pez, J . A.; Lahoz, F. J .; Oro, L. A. Angew. Chem., Int.
Ed. 2003, 42, 530. (b) Murahashi, T.; Uemura, T.; Kurosawa, H. J .
Am. Chem. Soc. 2003, 125, 8436.
the spectral data of 2c and 3c by comparison with the
previous data of 1c. The molecular structure of 1c has

Chalcogenolate-Bridged Diruthenium Complexes
Organometallics, Vol. 23, No. 1, 2004 29
ing thiolate-bridged ones already prepared. As a result,
it was revealed that S- and Se-bridged complexes were
quite effective as catalysts for many propargylic sub-
stitution reactions, while Te-bridged complexes did not
show any catalytic activity. By comparison of these
results with the structure of these complexes deter-
mined by X-ray studies as well as their redox potentials,
it can be proposed that the charge transfer from one
Ru atom to the other may be one of the important
factors for the above catalytic reactions, one Ru moiety
working as an electron pool or a mobile ligand to another
Ru moiety (synergistic effect).
C
5
Me
SSe ‚CH
[Cp *Ru Cl(µ
5
), 2.49 (s, 6H, SeMe). Anal. Calcd for C23
Cl : C, 30.41; H, 4.25. Found: C, 30.67; H, 4.14.
-TeMe) Ru Cp *(OH )]OTf (3b): yield 72%;
black crystals. H NMR: δ 1.83 (s, 30H, C Me ), 2.52 (s, 6H,
TeMe). Anal. Calcd for C23 Ru STe : C, 28.76; H,
.99. Found: C, 28.57; H, 3.84.
Ru th en iu m -Ca ta lyzed P r op a r gylic Su bstitu tion Rea c-
3 4 2
H38ClF O Ru -
2
2
2
2
1
2
2
5
5
H
38ClF
3
O
4
2
2
3
tion s of P r op a r gylic Alcoh ols w ith Nu cleop h iles. A
typical experimental procedure for the reaction of 1-phenyl-
2
-propyn-1-ol (4a ) with acetone catalyzed by [Cp*RuCl(µ
SMe)] (1a ) is described below. In a 50 mL flask were placed
a (0.03 mmol) and NH BF (0.06 mmol) under N . Anhydrous
2
-
2
1
4
4
2
acetone (36 mL) was added, and then the mixture was
magnetically stirred at room temperature. After the addition
of 4a (0.60 mmol), the reaction flask was kept at reflux
temperature for 4 h. The reaction mixture was treated with
brine (150 mL) and extracted with diethyl ether (20 mL × 3).
Exp er im en ta l Section
1
Gen er a l Meth od . H NMR (400, 300, and 270 MHz) and
1
3
C NMR (100, 75, and 67.8 MHz) spectra were recorded using
CDCl as solvent. Quantitative GLC analyses were performed
The ether layer was dried over anhydrous MgSO . For isola-
4
tion, the extract was concentrated under reduced pressure by
an aspirator, and then the residue was purified by TLC (SiO2)
with EtOAc-hexane (1/9) as an eluent to give 5a as a yellow
solid (91 mg, 0.53 mmol, 88% yield).
3
on a Shimadzu GC-14A instrument equipped with a flame
ionization detector using a 25 m × 0.25 mm CBP10 fused silica
capillary column. GC-MS analyses were carried out on a
Shimadzu GC-MS QP-5000 spectrometer. Elemental analyses
were performed at the Microanalytical Center of Kyoto Uni-
versity. Mass spectra were measured on a J EOL J MS600H
mass spectrometer. All reactions were carried out under a dry
nitrogen atmosphere. Solvents were dried by the usual meth-
ods and distilled before use.
-P h en yl-5-h exyn -2-on e (5a ).1b 1H NMR: δ 2.13 (s, 3H),
4
2
.26 (s, 1H), 2.80 (dd, 1H, J ) 16 and 5.2 Hz), 3.00 (dd, 1H, J
13
)
16 and 8.4 Hz), 4.20 (br, 1H), 7.22-7.39 (m, 5H). C NMR:
δ 30.4, 32.4, 51.5, 71.0, 84.8, 127.1, 127.2, 128.6, 140.1, 205.4.
-1
IR (KBr, cm ): 1720 (CdO), 2118 (CtC), 3291 (tCH). Anal.
Calcd for C12
Spectroscopic data of other products are as follows.
1-E t h oxy-2-p r op yn yl)b en zen e:1a pale yellow oil. 1H
NMR: δ 1.26 (t, 3H, J ) 7.0 Hz), 2.63 (d, 1H, J ) 2.0 Hz),
H12O: C, 83.69; H, 7.02. Found: C, 83.41; H, 7.00.
P r ep a r a tion of th e Meth a n ech a lcogen ola te-Br id ged
Dir u th en iu m Com p lex [Cp *Ru Cl(µ
Te). A typical experimental procedure for the preparation of
Cp*RuCl(µ -SMe)] (1a ) is described below. To a suspension
of [Cp*RuCl] (498 mg, 0.46 mmol) in THF (20 mL) was added
2 2
-YMe)] (Y ) S, Se,
(
[
2
2
3
8
2
1
.55 (qd, 1H, J ) 7.0 and 8.8 Hz), 3.75 (qd, 1H, J ) 7.0 and
.8 Hz), 5.16 (d, 1H, J ) 2.0 Hz), 7.33-7.40 (m, 3H), 7.52 (d,
H, J ) 7.3 Hz). 13C NMR: δ 15.1, 63.9, 71.1, 75.3, 81.8, 127.3,
4
dimethyl disulfide (86.7 mg, 0.92 mmol), and the mixture was
stirred at room temperature for 24 h. The solvent was then
removed under vacuum. The residue was recrystallized from
-1
28.4, 128.5, 138.3. IR (neat, cm ): 2114 (CtC), 3293 (tCH).
Anal. Calcd for C11
H, 7.47.
H
12O: C, 82.46; H, 7.55. Found: C, 82.56;
CH
mmol, 71%). H NMR: δ 1.62 (s, 30H, C
SMe). Anal. Calcd for C22 Ru C, 41.44; H, 5.69.
Found: C, 41.32; H, 5.69. The same complex has also been
2 2
Cl -n-hexane to give black crystals of 1a (410 mg, 0.64
1
5
5
Me ), 2.51 (s, 6H,
1
P h en yl(1-p h en yl-2-p r op yn yl)a m in e: pale yellow oil. H
NMR: δ 2.43 (d, 1H, J ) 2 Hz), 4.01 (br, 1H), 5.26 (s, 1H),
H
36Cl
2
2 2
S :
1
a
6.69 (d, 2H, J ) 8 Hz), 6.77 (d, 1H, J ) 7 Hz), 7.16-7.21 (m,
2 2 3
prepared by treatment of [Cp*RuCl ] with MeSSiMe .
H), 7.30-7.38 (m, 3H), 7.58 (d, 2H, J ) 7 Hz). 1 C NMR: δ
3
2
4
1
Spectroscopic data and isolated yields of other complexes
9.7, 73.1, 82.9, 113.9, 118.7, 127.1, 128.1, 128.7, 129.1, 138.9,
are as follows.
-
1
46.2. IR (KBr, cm ): 2114 (CtC), 3279 (tCH), 3372 (NH).
13N: C, 86.92; H, 6.32; N, 6.76. Found:
C, 86.70.; H, 6.68; N, 7.10.
-(1-P h en yl-2-p r op yn yl)-2-p yr r olid in on e: yellow oil. H
1
[
Cp *Ru Cl(µ
2
-SeMe)]
2
(2a ): yield 54%; black crystals. H
Anal. Calcd for C15
H
NMR: δ 1.63 (s, 30H, C
5
5
Me ), 2.44 (s, 6H, SeMe). Anal. Calcd
for C22
.75.
Cp *Ru Cl(µ
NMR: δ 1.70 (s, 30H, C
for C22 Ru Te : C, 31.88; H, 4.38. Found: C, 31.74; H,
.34.
P r ep a r a t ion of Ca t ion ic Met h a n ech a lcogen ola t e-
Br id ged Dir u t h en iu m Com p lexes [Cp *R u Cl(µ -YMe)
Ru Cp *(OH )]OTf (Y ) S, Se, Te). A typical experimental
procedure for the preparation of [Cp*RuCl(µ -SMe) RuCp*-
)]OTf (1b) is described below. In a 50 mL flask was
placed 1a (965 mg, 1.51 mmol) under N . Anhydrous tetrahy-
H
36Cl
2
Ru
2
Se
2
: C, 36.12; H, 4.96. Found: C, 35.93; H,
1
1
4
1
NMR: δ 1.86-2.03 (m, 2H), 2.40-2.46 (m, 2H), 2.55 (d, 1H, J
[
2
-TeMe)]
2
(3a ): yield 83%; black crystals. H
)
2.2 Hz), 2.97-3.03 (m, 1H), 3.49-3.55 (m, 1H), 6.31 (d, 1H,
5
Me
5
), 2.20 (s, 6H, TeMe). Anal. Calcd
13
J ) 2.2 Hz), 7.28-7.38 (m, 3H), 7.46 (d, 2H, J ) 6.2 Hz).
C
H
36Cl
2
2
2
NMR: δ 20.4, 21.7, 30.9, 41.4, 76.1, 126.7, 126.8, 127.4, 127.7,
4
1
27.8, 127.9, 172.2. HRMS: calcd for C13
H13NO [M] 199.0997,
found 199.0998.
2
2
-
2
-Meth yl-5-(1-p h en yl-2-p r op yn yl)fu r a n :6b pale yellow oil.
2
1
H NMR: δ 2.23 (s, 3H), 2.41 (d, 1H, J ) 3.0 Hz), 5.00 (s, 1H),
2
2
1
3
1
d
5.88 (s, 1H), 6.06 (d, 1H, J ) 3.0 Hz), 7.25-7.43 (m, 5H).
NMR: δ 13.6, 37.0, 71.8, 82.3, 106.2, 107.4, 127.3, 127.7, 128.6,
C
(OH
2
2
1
38.5, 151.3, 152.0. Anal. Calcd for C14H12O: C, 85.68; H, 6.16.
drofuran (THF) (20 mL) was added, and then the mixture was
magnetically stirred at room temperature. After the addition
of AgOTf (398 mg, 1.55 mmol), the reaction flask was kept at
room temperature for 20 h. Then, the solvent was removed
under reduced pressure, and the residue was recrystallized
Found: C, 85.41; H, 5.88.
5b:1a pale yellow oil. H NMR: δ 1.26 (t, 3H, J ) 7.2 Hz),
2.31 (s, 6H), 2.83 (s, 1H), 3.52 (q, 2H, J ) 7.2 Hz), 7.10 (d, 4H,
J ) 7.6 Hz), 7.42 (d, 4H, J ) 7.6 Hz). 13C NMR: δ 15.3, 21.0,
1
-1
from CH
SMe) RuCp*(OH
NMR: δ 1.63 (s, 30H, C
2
Cl
2
-n-hexane to give black crystals of [Cp*RuCl(µ
2
-
H
60.2, 76.8, 79.6, 83.9, 126.4, 128.8, 137.2, 140.7. IR (neat, cm ):
2110 (CtC), 3287 (tCH). Anal. Calcd for C19H20O: C, 86.32;
H, 7.63. Found: C, 85.95; H, 7.51.
1
2
2
)]OTf (1b; 1.02 g, 1.32 mmol, 87%).
Me ), 2.51 (s, 6H, SMe), 3.30 (brs, 2H,
). C NMR: δ 1.1, 10.5, 96.5. Anal. Calcd for C23
3
S : C, 35.91; H, 4.98. Found: C, 35.78; H, 4.11.
5
5
1
3
5c:1a pale yellow oil. H NMR: δ 1.27 (t, 3H, J ) 7.2 Hz),
2.86 (d, 1H, J ) 2.0 Hz), 3.54 (q, 2H, J ) 7.2 Hz), 7.22-7.33
(m, 6H), 7.56 (d, 4H, J ) 8.0 Hz). 13C NMR: δ 15.3, 60.4, 77.2,
1
OH
2
3 4
H38ClF O -
Ru
2
Spectroscopic data and isolated yields of other complexes
are as follows.
-
1
79.9, 83.5, 126.5, 127.6, 128.1, 143.4. IR (neat, cm ): 2110
[
Cp *R u Cl(µ
2
-SeMe)
2
R u Cp *(OH
2
)]OTf‚CH
2
Cl
2
(2b ‚
(CtC), 3285 (tCH). Anal. Calcd for C17H16O: C, 86.41; H, 6.82.
Found: C, 85.97; H, 6.67.
1
CH
2
Cl ): yield 89%; black crystals. H NMR: δ 1.69 (s, 30H,
2

3
0
Organometallics, Vol. 23, No. 1, 2004
Nishibayashi et al.
cm-1): 1933 (CdCdC). Anal. Calcd for C40
Ru -
2
P r ep a r a tion of Allen ylid en e Com p lexes [Cp *Ru Cl(µ
2
-
H
50ClF
3
O
3
YMe)
experimental procedure for the preparation of [Cp*RuCl(µ
SMe) RuCp*(CdCdCTol
0 mL flask was placed 1b (342 mg, 0.44 mmol) under N
Anhydrous EtOH (10 mL) was added, and then the mixture
was magnetically stirred at room temperature. After addition
of 1,1-di-p-tolyl-2-propyn-1-ol (4b) (105 mg, 0.44 mmol), the
reaction flask was kept at room temperature for 1 h. A
precipitated purple solid was filtered off, washed with n-
2
Ru Cp *(CdCdCTol
2
)]OTf (Y ) S, Se, Te). A typical
SSe ‚CH Cl : C, 42.88; H, 4.56. Found: C, 42.83; H, 4.56.
2
2
2
1
2
-
3c: yield 91%; black crystals. H NMR: δ 1.78 (s, 15H), 1.94
(s, 15H), 2.34 (s, 6H), 2.36 (s, 6H), 7.21 (d, 4H, J ) 8.4 Hz),
7.58 (d, 4H, J ) 8.4 Hz). 13C NMR: δ 12.4, 12.7, 95.1, 102.3,
2
2
)]OTf (1c) is described below. In a
2
2
.
-
1
129.3, 131.2, 140.7, 143.7, 164.5, 189.9, 298.5. IR (KBr, cm ):
1925 (CdCdC). Anal. Calcd for C40 Ru STe C,
41.39; H, 4.34. Found: C, 41.52; H, 4.43.
H
50ClF
3
O
3
2
2
:
Ack n ow led gm en t. This work was supported by a
Grant-in-Aid for Scientific Research for Young Scientists
hexane, and recrystallized from CH
crystals of 1c (401 mg, 0.41 mmol, 93%). H NMR: δ 1.68 (s,
2 2
Cl -n-hexane to give black
1
(
A) (No. 15685006) from the Ministry of Education,
1
7
2
5H), 1.87 (s, 15H), 2.36 (s, 6H), 2.68 (s, 6H), 7.22 (d, 4H, J )
.6 Hz), 7.54 (d, 4H, J ) 7.6 Hz). 13C NMR: δ 10.4, 10.7, 19.6,
2.0, 98.8, 104.5, 129.9, 132.1, 140.4, 144.5, 162.2, 182.6, 296.6.
Culture, Sports, Science and Technology of J apan. We
also thank Dr. Izuru Takei of the Tokyo University of
Science for assistance with cyclic voltammetry analysis.
-1
IR (KBr, cm ): 1952 (CdCdC). Anal. Calcd for C40
3 3
H50ClF O -
Ru : C, 49.55; H, 5.20. Found: C, 48.98; H, 5.31.
Spectroscopic data and isolated yield of other complexes are
2
S
3
Su p p or tin g In for m a tion Ava ila ble: Text giving experi-
mental procedures and tables and figures giving crystal-
lographic data of 1a , 1b, 2a , 2b, 3a , and 3b; crystallographic
data are also available as CIF files. This material is available
free of charge via the Internet at http://pubs.acs.org.
as follows.
1
2
c: yield 94%; black crystals. H NMR: δ 1.70 (s, 15H), 1.88
(
7
1
s, 15H), 2.35 (s, 6H), 2.57 (s, 6H), 7.21 (d, 4H, J ) 8.0 Hz),
.52 (d, 4H, J ) 8.0 Hz). 13C NMR: δ 11.0, 11.3, 21.9, 96.6,
02.8, 129.4, 131.4, 140.2, 143.8, 162.0, 185.4, 298.1. IR (KBr,
OM034137K