Reactions of ruthenium benzylidenes with H2O to give benzaldehyde and (aqua)ruthenium complex

Article abstract of DOI:10.1016/j.jorganchem.2004.08.017

The second generation of Grubbs type catalyst, (PCy₃)(H₂IMes)Cl₂Ru = CHPh (1) undergoes the Cl replacement with CH₃CN to give cationic ruthenium carbene complexes, [(RCN)₃(H₂IMes) Ru = CHPh](OTf)₂ (2, R = CH₃ (a), Ph (b)) in the presence of AgOTf. The reaction of 2a with H₂O in the presence of CH₃CN gives (aqua)ruthenium complex, [Ru(H₂IMes)(NCCH₃)₄(H₂O)] (OTf)₂ (3) and benzaldehyde. Benzaldehyde is also observed in the reaction of 1 with H₂O. Plausible reaction pathways are suggested for the degradation of ruthenium benzylidenes to give benzaldehyde on the basis of the isotope labeling experiments.

Full text of DOI:10.1016/j.jorganchem.2004.08.017

Journal of Organometallic Chemistry 689 (2004) 3535–3540
www.elsevier.com/locate/jorganchem
Reactions of ruthenium benzylidenes with H2O to give
benzaldehyde and (aqua)ruthenium complex
a
a
b
a,
a,
*
Mieock Kim , Min-Sik Eum , Moon Young Jin , Ki-Won Jun *, Chul Wee Lee
,
b
Kyoung A Kuen , Chong Hyeak Kim , Chong Shik Chin
c
d
a
Chemical Technology Division, Korea Research Institute of Chemical Technology, P.O. Box 107 Yuseong, Daejon, Seoul 305-600, Korea
Advanced Materials Division, Korea Research Institute of Chemical Technology, P.O. Box 107 Yuseong, Daejon, Seoul 305-600, Korea
Chemical Analysis Laboratory, Korea Research Institute of Chemical Technology, P.O. Box 107 Yuseong, Daejon, Seoul 305-600, Korea
b
c
d
Department of Chemistry, Sogang University, Seoul 121-742, Korea
Received 21 February 2004; accepted 12 August 2004
Available online 15 September 2004
Abstract
The second generation of Grubbs type catalyst, (PCy3)(H2IMes)Cl2Ru@CHPh (1) undergoes the Cl replacement with CH3CN to
give cationic ruthenium carbene complexes, [(RCN)3(H2IMes)Ru@CHPh](OTf)2 (2, R = CH3 (a), Ph (b)) in the presence of AgOTf.
The reaction of 2a with H2O in the presence of CH3CN gives (aqua)ruthenium complex, [Ru(H2IMes)(NCCH3) (H2O)](OTf)2 (3)
4
and benzaldehyde. Benzaldehyde is also observed in the reaction of 1 with H2O. Plausible reaction pathways are suggested for the
degradation of ruthenium benzylidenes to give benzaldehyde on the basis of the isotope labeling experiments.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Ruthenium benzylidene; Aquaruthenium complex; Ruthenium; Degradation
1. Introduction
tions of ruthenium benzylidenes with primary alcohol
and water have been recently reported [3a,3b], the mech-
anism is still not unambiguously elucidated. Particu-
larly, the behavior of the benzylidene moiety in the
complex during the reaction is not understood yet.
Herein, we wish to report the degradation of the second
generation of Grubbs type ruthenium benzylidene
(PCy3)(H2IMes)Cl2Ru@CHPh (1) [6] and cationic ruthe-
nium benzylidenes [(RCN)3(H2IMes)Ru@CHPh](OTf)2
(2, R = CH3 (a), Ph (b)) by reacting withH2O to give benz-
aldehyde, and to suggest their deactivation pathways
based on isotope labeling experiments.
Transition metal carbene complexes are useful cata-
lysts and important intermediates in organic reactions
such as olefin metathesis, cyclopropanation, furan syn-
thesis, and C–C coupling reactions [1]. Especially, ruthe-
nium alkylidenes have been of special interest as olefin
metathesis catalyst over the past decade, since they pos-
sess significant advantages in terms of stability and ease
of storage and handling [1b,2].
In spite of this interest, the studies on the deactivation
of ruthenium alkylidenes by water, alcohol, and others
have been rarely reported while hydrolysis and nucleo-
philic substitution are well known in Fischer carbene
complexes [3–5]. Furthermore, although the degrada-
2. Results and discussion
*
Since considerable efforts have been recently focused
on modification of the ligand environment of the second
Corresponding authors. Tel.: +82428607671; fax: +82428607388.
E-mail address: kwjun@krict.re.kr (K.-W. Jun).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.08.017

3536
M. Kim et al. / Journal of Organometallic Chemistry 689 (2004) 3535–3540
˚
generation of Grubbs type catalyst due to the needs for
new catalyst with stability and activity [6,7]. We also
have been encouraged to try the replacement of Cl lig-
and of 1 with neutral ligand by the previous reports
on cationic ruthenium catalysts which are highly active
in olefin metathesis [8].
New cationic ruthenium carbenes [(RCN)3(H2IMes)-
Ru@CHPh](OTf)2 (2, R = CH3 (a), Ph (b)) are obtained
from reactions of (PCy3)(H2IMes)Cl2Ru@CHPh (1)
with RCN in the presence of AgOTf.
and O(H2O)–Hꢀ ꢀ ꢀO(OTf2) is 3.08(1) A, and bond angle
of O(H2O)–Hꢀ ꢀ ꢀO(OTf1) is 171(8)ꢁ and O(H2O)–
Hꢀ ꢀ ꢀO(OTf2) is 152(5)ꢁ. Two CH3CN ligands located
parallel to the aromatic rings of N-heterocyclic carbene
of 2a have bigger angles of C–Ru–N and smaller angles of
Ru–N–C than those of the other two CH3CN ligands of
2a probably due to steric interactions (Fig. 1).
In order to get some information on the decomposi-
tion pathways of ruthenium carbenes 1 and 2 with
H2O, labeling experiments were carried out. In this
work, deutrated benzaldehyde (DCOC6D5) is observed
in both reactions of (PCy3)(H2IMes)Cl2Ru@CDC6D5
(1-d6) [3b] and [(CH3CN)3(H2IMes)Ru@CDC6D5]-
(OTf)2 (2a-d6) with H2O while both 1 and 2a react with
D2O to yield undeutrated benzaldehyde (HCOPh).
These results strongly suggest that the proton of H
COPh is oriented from benzylidene proton (Ru@CH
Ph) of 1 and 2a. It is also found that the source of the
oxygen required for formation of benzaldehyde is H2O
by formation of 18O-labeled benzaldehyde from the
reaction of 1 and 2a with H218O.
2+
N
N
N
N
Cl
L
2AgOTf, 3L
2OTf
Ru
Ru
-2AgCl, PCy3
Cl
L
Ph
Ph
PCy3
L
1
2
L= CH3CN (a), PhCN (b)
ð1Þ
The most characteristic spectroscopic feature of 2 is
1
the resonance of carbene proton Ru@CHPh in the H
These results clearly demonstrate that benzaldehyde
is formed from benzylidene group and H2O. A specula-
tive mechanism is shown in Scheme 1. In the proposed
mechanism, first, nucleophilic attack of H2O on the
a-carbon of carbene ligand of 2a would occur to give
intermediate A, which would undergo b-hydrogen
abstraction to lead to an (aqua)ruthenium complex 3
and benzaldehyde. Nucleophilic attacks on the carbene
carbon of methylidene [10a,10b] alkylidene [10a], benzy-
lidene [10c] and dialrylcarbene [10d] have been rarely re-
ported while they are well known for Fisher carbenes
[4,11]. The formation of Ru–H bond, though cannot be
supported by any direct evidence, can be speculated in a
NMR spectra at d 17.34 (for 2a) and 17.81 (for 2b),
which are considerably shifted to lower field compared
with 1. And the absence of phosphine ligand in 2 is con-
firmed by no signal in 31P NMR spectra of 2, and the
free phosphine in the reaction solution. This is in agree-
ment with the previous report that phosphine of 1 can be
replaced with N-donor ligand [9].
It is observed that ruthenium benzylidenes 1 and 2a
are decomposed to give unknown metal mixtures and
the only organic product, benzaldehyde in the presence
of H2O. To obtain well defined decomposition metal
product, the reaction of 2a with H2O is carried out in
the presence of excess CH3CN, which resulted in the
formation of cationic (aqua)ruthenium complex [Ru-
(H2IMes)(NCCH3)4(H2O)](OTf)2 (3) (75%) and benzal-
dehyde (93%) in high yields (Eq. (2)). Unlike 2a,
however, well defined decomposition metal product
has not been obtained from the reaction of 1 with
H2O even in the presence of excess CH3CN or PCy3.
C3
C4
C21
C14
C16
C17
N2
C18
C11
C10
C6
N5 C15
C9
C20
C1
C29
C19
C22
C23
C28
C7
2+
C8
N30
C13
C12
Ru
N
N
N27
N24
C31
C32
CH3CN
H2O
N33
C34
O
H
NCCH3
NCCH3
H3CCN
2a
C25
Ru
+
-H2
C35
H3CCN
C26
O36
OH2
3
Fig. 1. ORTEP drawing of [Ru(H2IMes)(NCCH3)4 (H2O)](OTf)2 (3)
˚
with 50% thermal ellipsoids probability. Selected bond distances (A)
ð2Þ
The molecular structure of 3 is determined by X-ray
and angles (ꢁ): Ru–C1 = 2.015(5); Ru–N24 = 2.035(4); Ru–
N
27 = 2.024(5);
Ru–N30 = 2.041(4);
Ru–N33 = 2.018(5);
Ru–
O36 = 2.199(4); C1–Ru–O36 = 178.79(19); C1–Ru–N24 = 97.41(19);
C1–Ru–N27 = 92.4(2); C1–Ru–N30 = 97.82(19); C1–Ru–N33 = 92.9(2);
crystallography which shows the hydrogen bonding
interaction between proton of H2O ligand and oxygen
of triflate anion (see Fig. 1 and Supporting Informa-
tion). From X-ray crystallographic data it was observed
N24–Ru–N30 = 164.72(18);
N27–Ru–N33 = 174.69(18);
27 = 88.10(17); N24–Ru–N33 = 91.85(17); N22–Ru–N30 = 92.57(17);
30–Ru–N33 = 86.08(17); Ru–N24–C25 = 165.4(4); Ru–N27–C28
N24–Ru–
N
N
=
˚
that the distance of O(H2O)–Hꢀ ꢀ ꢀO(OTf1) is 2.70(1) A
175.1(4); Ru–N30–C31 = 162.4(4); Ru–N33–C34 = 172.8(5).

M. Kim et al. / Journal of Organometallic Chemistry 689 (2004) 3535–3540
3537
2+
H2O
H2IMes
2+
H2IMes
2+
+
H2IMes
H2O
L
O
L
L
D
L
L
HH
Ru
L
L
L
Ru
Ru
C6D5
O
-H2
C6D5
L
D
L
L
OH2
D
C6D5
2a-d6
3
A
L = CH3CN
H2IMes =
N
N
Scheme 1.
similar way of the formation of metal to H bond sug-
gested in the reaction of Fischer carbene with RSH [5a].
During the investigation on degradations of 1 and 2a
by H2O, it is found that the cationic ruthenium carbene
2a is more stable than 1 toward H2O. The benzylidene
signal of 2a is observed with the significant size even
after 2 days while that of 1 disappears within 36 h in
the mixed solution of DCE-d4 (1.5 mL)/H2O (1.0 mL)
in the air at room temperature. Kharasch addition [12]
products and ruthenium hydride [3a,3b,12] are not ob-
served during these experiments in CHCl3 and dichloro-
ethane, respectively (Fig. 2).
In the preliminary experiments for the ring opening
metathesis polymerization (ROMP) of norbornene, 2a
shows good catalytic activity (60 ꢁC, 10 min, [Mono-
mer]/[catalyst] = 300, yield = 94%) and the resulting pol-
ynorbornenes have significantly high cis contents of 76%
determined by 1H NMR spectroscopy (Fig. 3) while
complex 1 produce polynorbornenes with predominant
trans contents [6a].
reaction pathways for the degradation of 1 and 2a by
H2O to give benzaldehyde by labeling experiments. Fur-
ther studies to apply 2 to various olefin metathesis reac-
tions and to understand their mechanism are underway
in our laboratory.
3. Experimental
3.1. General information
A standard vacuum system and Schlenk type glass-
ware were used in most of experimental procedures in
handling ruthenium compounds.
(PCy3)(H2IMes)Cl2Ru@CHPh (1) was purchased
from Strem and D2O, H218O, and styrene-d8 were pur-
chased from Aldrich. (PCy3)(H2IMes)Cl2Ru@CDC6D5
(1-d6) was prepared from the reaction of 1 and sty-
rene-d8 by the literature method [3b].
NMR spectra were recorded on either a Varian Gemi-
ni 200, 300 or 500 spectrometer (1H, 300 or 500 MHz;
13C, 126 MHz; 31P, 81.0 MHz). IR spectra were obtained
on a Nicolet 205 spectrophotometer. Elemental analyses
In summary, we demonstrated new cationic ruthe-
nium benzylidenes 2 obtained by Cl abstraction of the
second generation Grubbs catalyst 1 and suggested the
Fig. 2. 1H NMR spectra of compounds of 1 and 2a in the solution of DCE–d4 (1.5 mL)/H2O (1.0 mL) and an internal standard (anthracene) at room
temperature in air.

3538
M. Kim et al. / Journal of Organometallic Chemistry 689 (2004) 3535–3540
Fig. 3. 1H NMR spectrum of polynorbornene by 2a at 500 MHz in CDCl3.
were carried out by a Carlo Erba EA 1108 CHNS-O
analyzer. Gas chromatography/mass spectra were meas-
ured with Hewlett–Packard HP 5890A VG-trio 2000.
FAB-Mass measurements were carried out with JMS-
DX303Mass Spectrometer.
(s, 3H, CH3CN). 13C NMR (126 MHz, CDCl3): d
325.6 (s, Ru@CHPh), 202.4 (s, carbene carbon of
H2IMes), 134.1 (para C H of Ru@CHPh), 130.2 (ortho
C H of Ru@CHPh), 129.9 (s, CH of H2IMes), 128.3
(s, meta CH of Ru@CHPh), 52.1 (s, CH2 carbons of
H2IMes), 20.9 (s, para CH3 of H2IMes), 17.9 (ortho
CH3 of H2IMes), 4.1 (NCCH3), 2.9 (NCCH3), 202.4,
151.2, 140.1, 136.9, 127.4, 121.5, 118.9. HETCOR (1H
(500 MHz) ! 13C (126 MHz)): d 17.34 ! 325.6; 7.61 !
134.1; 7.45 ! 130.2; 7.35 ! 128.3; 6.87 ! 129.9; 3.98 !
52.1; 2.34 ! 4.1; 2.23 ! 20.9; 2.19 ! 17.9; 2.11 ! 2.9.
IR (KBr, cmꢁ1): 2295 (s, mC„N), 1269, 1160 and 1031
(s, due to uncoordinated OTfꢁ). Anal. Calc. for Ru1S2-
F6O6N5C36H41: C, 47.05; H, 4.50; N, 7.62. Found: C,
47.15; H, 4.55; N, 7.57%. MS (FAB) m/z Calc. for
[M+– OTf – CH3CN]: 729.
3.2. Synthesis
3.2.1. Synthesis of [(RCN)3(H2IMes)Ru@CHPh]-
(OTf)2 (2, R = CH3 (a), Ph (b))
These compounds were prepared by the same method
as described below for 2a. The reaction mixture of 1 (0.1
g, 0.12 mmol) and AgOTf (0.06 g, 0.24 mmol) in CHCl3
(10 mL) was stirred in the presence of CH3CN (0.02 mL,
0.36 mmol) at 25 ꢁC for 30 min before the white solid
(AgCl) was removed by filtration. Addition of n-pentane
(20 mL) resulted in precipitation of greenish beige
microcrystals that were collected by filtration, washed
with n-pentane (3 · 10 mL) and dried under vacuum.
The yield was 0.1 g or 96% based on [Ru(@CH-
Ph)(IMes) (CH3CN)3](OTf)2 (2a).
[Ru(@CHPh)(IMes)(CH3CN)3](OTf)2 (2a). 1H
NMR (500 MHz, CDCl3): d 17.34 (s, 1H, Ru@CHPh),
7.61 (t, J(H–H) = 7.0 Hz, 1H, para CH of Ru@CHPh),
7.45 (d, J(H–H) = 7.0 Hz, 2H, ortho CH of Ru@CHPh),
7.35 (t, J(H–H) = 7.0 Hz, 2H, meta CH of Ru@CHPh),
6.87 (s, 4H, CH of H2IMes), 3.98 (s, 4H, CH2 of
H2IMes), 2.34 (s, 6H, CH3CN), 2.23 (s, 6H, para CH3
of H2IMes), 2.19 (s, 12H, ortho CH3 of H2IMes), 2.11
[Ru(@CHPh)(IMes)(PhCN)3](OTf)2 (2b) (89%
1
yield). H NMR (500 MHz, CDCl3): d 17.81 (s, 1H,
Ru@CHPh), 6.82 (s, 4H, CH of H2IMes), 4.10 (s, 4H,
CH2 of H2IMes), 2.30 (s, 12H, ortho CH3 of H2IMes),
2.09 (s, 6H, para CH3 of H2IMes). 13C NMR (126
MHz, CDCl3): d 328.4 (s, Ru@CHPh), 200.0 (carbene
carbon of H2Imes), 134.1, 133.1, 130.2, 129.8, 129.6
(CH carbons), 52.5 (s, CH2 carbons of IMes), 20.7 (s,
para CH3 of IMes), 18.3 (ortho C H3 of IMes), 151.9,
140.5, 137.0, 128.7, 127.6, 125.1, 124.0, 121.4, 118.9,
110.8, 109.8. HETCOR (1H (500 MHz) ! 13C (126
MHz)): d 17.81 ! 328.4; 6.82 ! 129.8; 7.45 ! 130.2;
7.35 ! 128.3; 6.87 ! 129.9; 4.10 ! 52.5; 2.30 ! 20.7;

M. Kim et al. / Journal of Organometallic Chemistry 689 (2004) 3535–3540
3539
2.09 ! 18.3. IR (KBr, cmꢁ1): 2258 (s, mC„N), 1269, 1155
and 1030 (s, due to uncoordinated OTfꢁ). Anal. Calc.
for RuS2C51H47 F6N5O6:C, 55.43; H, 4.29; N, 6.34.
Found: C, 55.82; H, 4.53; N, 6.36%.
men under ambient conditions. The epoxy-coated
crystal was mounted on an Bruker P4 four-circle X-
ray diffractometer and the intensity data were collected
in the h–2h scan mode using graphite monochromated
˚
Mo Ka radiation (k = 0.71073 A). The unit cell param-
3.2.2. Synthesis of [(CH3CN)3(H2IMes)Ru@CDC6D5]-
(OTf)2 (2a-d6)
eters and an orientation matrix for the compound were
determined from the least-squares fit of 41 accurately
centered reflections with h range of 3.33–12.48ꢁ. Three
standard reflections were monitored every 97 reflections;
no remarkable decays were observed through data col-
lection. Lorentz and polarization corrections were ap-
plied to the intensity data, and a semi-empirical
absorption correction based on the psi-scans was
applied [13a].
This compound was prepared by the same method as
described above for 2a using (PCy3)(H2IMes)
Cl2Ru@CDC6D5 (1-d6). The yield was 0.1 g or 95%
1
based on 2a-d6. H NMR spectrum of 2a-d6 shows all
the signals for 2a except the disappearance of the singlet
signal at d 17.34 due to Ru@CHPh and the signals at d
7.61, 7.45, and 7.35 due to Ru@CHPh.
All calculations in the structural solution and refine-
ment were performed using the Bruker SHELXTL crystal-
lographic software package [13b]. Space groups were
assigned on the basis of the systematic absences and
intensity statistics, and were confirmed by successful
refinements. The structure was solved by the direct
method [13c] and successively refined by the full-matrix
least-squares method followed by difference Fourier
maps. All the non-hydrogen atoms were refined aniso-
tropically; all the hydrogen atoms were put into calcu-
lated positions with the isotropic thermal parameters.
Final difference of electron density maps contained no
3.3. Reactions of 1, 1-d6, 2a and 2a-d6 with H2O, D2O,
and H218O
These reactions were carried out by the same manner
as described below for 2a and H2O. A reaction mixture
of 2a (0.10 g, 0.11 mmol) and H2O (15 mL) in CHCl3 (10
mL) was stirred for 4 days at 25 ꢁC in the presence of
CH3CN (0.006 mL, 0.12 mmol). Addition of n-pentane
(20 mL) to the CHCl3 solution resulted in precipitation
of beige microcrystals that were collected by filtration,
washed with n-pentane (3 · 10 mL) and dried under vac-
uum (0.09 g, and 75%). The filtrate was distilled at 25 ꢁC
under vacuum to less than 1.0 mL, and the residue was
eluted with n-pentane on a column packed with silica gel
to obtain benzaldehyde (ca. 93% yield), which was de-
Table 1
Details of crystallographic data collection for 3
1
tected by H NMR and GC/MS.
Chemical formula
Formula weight
Temperature (K)
Crystal dimension (mm)
Crystal system
C31H41F6N6O7RuS2
888.89
286(2)
[Ru(H2IMes)(NCCH3)4(H2O)](OTf)2 (3). 1H
NMR (500 MHz, CDCl3): d 6.98 (s, 4H, CH of
H2IMes), 5.26 (s, 2H, OH2), 3.91 (s, 4H, CH2 of
H2IMes), 2.28–2.22 (30H, CH3 of H2IMes and
NCCH3). 13C NMR (126 MHz, CDCl3): d 206.35 (car-
bene carbon of H2IMes), 129.6 (CH carbons of
H2IMes), 52.7 (CH2 carbons of H2IMes), 21.1 and
17.7 (CH3 carbons of H2IMes), 4.5 (NCCH3), 138.9,
138.1, 124.7. IR (KBr, cmꢁ1): 2296 and 2286 (s, mC„N),
1266, 1155 and 1031 (s, OTfꢁ). Anal. Calc. for
RuS2C31H40 F6N6O7: C, 41.94; H, 4.54; N, 9.47. Found:
C, 42.03; H, 4.58; N, 9.34%.
0.50 · 0.38 · 0.12
Monoclinic
P21/n
Space group
˚
a (A)
˚
14.222(7)
14.995(4)
18.824(3)
90
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90.105(18)
90
3
˚
V (A )
4015(2)
4
1.471
Z
q(calc) (g cmꢁ1
)
[Ru(H2IMes)(NCCH3)4(D2O)](OTf)2 (3-d2). 1H
NMR spectra of 3-d2 show all the signals for 3 except
the disappearance of one singlet at 5.26 due to Ru–OH2.
DCOC6D5 (benzaldehyde-d6). MS m/z = 112 [M+].
HC18OC6H5 (benzaldehyde-18O). MS m/z = 108 [M+].
l (mmꢁ1
F(000)
)
5.72
1820
Radiation
Wavelength
h Range (ꢁ)
hkl range
Mo Ka
0.71073
1.79 to 26.51
ꢁ1 6 h 6 17
ꢁ1 6 k 6 18
ꢁ23 6 l 6 23
9184
No. of reflections
No. of independent reflections
4. X-ray structure determination
7520
8170
No. of obs. (|Fo| > 2rFo) data
No. of parameters
R1
Crystals of 3 were grown by slow evaporation from
CHCl3 solution. A pale yellow plate crystal of the title
compound was coated with epoxy glue in order to pre-
vent spontaneous liberation of ligands from the speci-
482
0.0602
wR2
GOF
0.1624
1.023

3540
M. Kim et al. / Journal of Organometallic Chemistry 689 (2004) 3535–3540
[5] (a) C.F. Bernasconi, M. Ali, J. Am. Chem. Soc. 121 (1999)
11384;
significant features. Further details of the crystallo-
graphic and experimental data of 3 are given in Table 1.
(b) C.P. Casey, W.P. Brunsvold, Inorg. Chem. 16 (1977)
391.
[6] (a) C.W. Bielawski, R.H. Grubbs, Angew. Chem. Int. Ed. 39
(2000) 2903;
Acknowledgements
(b) T. Weskamp, F.J. Kohl, W. Hieringer, D. Gleich, W.A.
Herrmann, Angew. Chem. Int. Ed. 38 (1999) 2416;
(c) J. Huang, H.-J. Schanz, E.D. Stevens, S.P. Nolan, Organo-
metallics 18 (1999) 5375;
The authors thank The Program for Development of
Next Generation Technology (PDNGT) and Ministry of
Commerce, Industry, & Energy (MOICE) for their
financial support of this study.
(d) M. Scholl, S. Ding, C.W. Lee, R.H. Grubbs, Org. Lett. 1
(1999) 953.
[7] (a) K. Grela, S. Harutyunyan, A. Michrowska, Angew. Chem.
Int. Ed. 41 (2002) 4038;
(b) H. Wakamatsu, S. Blechert, Angew. Chem. Int. Ed. 41 (2002)
2403;
Appendix A. Supplementary material
(c) H. Wakamatsu, S. Blechert, Angew. Chem. Int. Ed. 41 (2002)
794;
Supplementary data associated with this article can
be found, in the online version at doi:10.1016/
j.jorganchem.2004.08.017.
(d) K. Denk, J. Fridgen, W.A. Herrmann, Adv. Synth. Catal. 344
(2002) 666;
(e) T.-L. Choi, R.H. Grubbs, Angew. Chem. Int. Ed. 42 (2003)
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