Synthesis of siloxy-modified second generation Hoveyda-Grubbs catalysts and their catalytic activity

Article abstract of DOI:10.1016/j.jorganchem.2009.08.007

Efficient syntheses of the first ruthenium alkylidene complexes bearing siloxide ligands are described. Second generation Hoveyda-Grubbs catalyst is shown to undergo efficient functionalization with a number of potassium silanolates to give disiloxy deriv

Full text of DOI:10.1016/j.jorganchem.2009.08.007

Journal of Organometallic Chemistry 694 (2009) 3918–3922
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis of siloxy-modified second generation Hoveyda–Grubbs catalysts and
their catalytic activity
Szymon Rogalski, Cezary Pietraszuk, Bogdan Marciniec *
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Pozna n´ , Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 30 May 2009
Received in revised form 5 August 2009
Accepted 5 August 2009
Available online 9 August 2009
Efficient syntheses of the first ruthenium alkylidene complexes bearing siloxide ligands are described.
Second generation Hoveyda–Grubbs catalyst is shown to undergo efficient functionalization with a num-
ber of potassium silanolates to give disiloxy derivatives. The complexes obtained are found catalytically
active in selected metathesis transformations.
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Siloxide complexes
Ruthenium alkylidene complexes
Olefin metathesis
1
. Introduction
Transition metal compounds bearing siloxy ligand(s) are of
Continuing our interest in synthesis, reactivity and catalytic
activity of TM–OSi complexes we started the study of ruthenium
complexes. There is scarce information in literature on ruthenium
siloxide complexes [1]. Caulton synthesized siloxide complexes of
great interest, particularly as models of metal complexes immobi-
lized on silica and silicate surfaces and are known to catalyse a
variety of organic reactions [1–3]. More than 100 transition metal
complexes bearing terminal or bridging siloxy ligand have been
synthesized and structurally and/or spectroscopically character-
ized for last 25 years [1]. However, information on the application
of late TM siloxide complexes in catalysis is scarce [1]. Siloxide
complexes, predominantly of early transition metals (Ti, W, Mo)
are known to be effectively utilized in molecular catalysis, particu-
larly in polymerization [4], metathesis [5], epoxidation of alkenes
the type [RuH(OSiR
3
)(CO)(PR
3
)
2
] (where PR
[16], [Cp Ru(PR
3
= Pi-Pr
)(OSiR
3
; OSiR = OSiPh ,
2
Ph; OSiR
3
= O-
SiPh
3
,
OSiMe
2
Ph, OSiMe
3
)
3
3
)] and
*
[Cp Ru(PR
3
3
)(CO)(OSiR )] (where = Pi-Pr
2
Ph, PCy
3
3
*
OSiMe
chloride derivative with potassium silanolate. Siloxy derivative
[Ru (H)( -OSiEt )(CO)10] was obtained with poor yield via a reac-
tion of Ru (CO)12 with Et SiOH in the presence of [Cp Fe (CO)
[18]. Siloxysilyl substituted triruthenium clusters have been ob-
tained by interaction of HSi(OSiMe and HSiMe(OSiMe with
Ru (CO)12 [19]. Finally hydrolysis of [{(t-Bu PCH SiMe N}Ru(O-
SO CF )] led to planar 14e trans-[Ru(t-Bu PCH SiMe O) ] [20]. Cat-
2 3
Ph, OSiMe ) [17] by treatment of the respective ruthenium
3
l
3
3
3
2
2
4
]
3
)
3
3 2
)
[
6] and dehydrogenative coupling of silanes [7]. In our group, a
3
2
2
2 2
)
number of siloxy complexes of rhodium [8] and iridium [9] have
been synthesized and characterized. Moreover, we demonstrated
the catalytic activity of these complexes in a number of transfor-
mations such as silylative coupling of vinylsilanes with olefins
2
3
2
2
2
2
alytic activity of the synthesized complexes has not been
examined.
Ruthenium alkylidene complexes of the type proposed by Grub-
bs, containing two anionic ligands in their structure are very
attractive, in particular, in the context of their significant role in
catalysis of olefin metathesis.
Herein we report the first examples of ruthenium alkylidene
complexes bearing siloxide ligands, based on the second genera-
tion Hoveyda–Grubbs catalyst, and demonstrate their catalytic
activity in selected metathesis transformations. The choice of
the second generation Hoveyda–Grubbs catalyst as a starting
material was made on the basis of reports concerning successful
exchange of chloride ligands in this complex [see for example
Ref. [22]].
[
9a,10], curing of polysiloxanes via hydrosilylation [11], hydrofor-
mylation [12] and silylcarbonylation [13] of vinylsilanes as well
as hydrogenation and transfer hydrogenation [14]. Recently, we
have demonstrated efficient immobilization of rhodium complexes
by direct reaction of its siloxy derivative with silica [15]. We expect
that it is a general and convenient method of immobilization of
late transition metal complexes.
*
Corresponding author. Tel.: +48 61 8291 366; fax: +48 61 8291 508.
E-mail addresses: bogdan.marciniec@amu.edu.pl, marcinb@main.amu.edu.pl (B.
Marciniec).
0
022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.08.007

S. Rogalski et al. / Journal of Organometallic Chemistry 694 (2009) 3918–3922
3919
2
. Results and discussion
temperature. All attempts to isolate the monosubstituted deriva-
tive failed. Similar observations were made earlier by Buchmeiser
when studying exchange of chlorine ligands with the trifluoroace-
tate ones [22].
2.1. Synthesis
Stirring the benzene solution of the second generation of Hov-
eyda–Grubbs catalyst (1) [21] with two equivalents of potassium
2
.2. Reactivity
dimethyl(tert-butyl)silanolate at 60 °C led to gradual change of col-
1
our from green to brown. Monitoring of the reaction by H NMR
Treatment of benzene solution of siloxy derivative (2) with HCl/
spectroscopy indicated disappearance of the signal at d = 16.7
and formation of a new signal at d = 15.2 ppm. After 3 h of the reac-
tion course nearly quantitative conversion (98%) of 1 and forma-
tion of new alkylidene complex with 95% of NMR yield was
observed. Evaporation of the solvent followed by extraction of
the product with pentane gave new alkylidene complex whose
2
Et O results in an immediate change in colour from brown to
1
green. Analysis of the reaction mixture by H NMR spectroscopy
revealed the quantitative formation of the second generation Hov-
eyda–Grubbs catalyst (1) (Eq. (3)). Similar reactivity of tert-butoxy
derivative of the first generation catalyst was reported by Grubbs
[
6 6
23]. Titration of C D solution of 2 with etheral solution of HCl
1
13
1
H and C NMR spectra corresponded to those of the siloxide com-
plex of ruthenium (2).
in an NMR tube monitored by H NMR revealed gradual disappear-
ance of the signal at 15.2 ppm and appearance of the signal at
1
6.7 ppm which can be assigned to Hoveyda–Grubbs complex (1)
(
Eq. (2)). Complete exchange of siloxide ligands with the chloride
N
N
N
N
Mes
Cl
Mes
Mes
SiO
Mes
ones was observed after addition of stoichiometric amount of
HCl. The reaction was accompanied by the formation of corre-
sponding disiloxane.
R
3
Ru
O
+
2 KOSiR3
Ru
O
+
2 KCl
Cl
benzene
OSiR
3
o
2
5 C, 24h
o
or 60 C, 3h
1
2 - 6
(OMe)] (5), SiPh
Mes
N
N Mes
SiR
3
= SiMe
2
(t-Bu) (2), SiMe
3
(3), Si(i-Pr)
3
(4), SiMe
2
[4-C
6
H
4
3
(6)
t-BuMe SiO
HCl/Et O
2
2
+
ð1Þ
By using the same procedure a series of new siloxy derivatives
Ru
OSiMe t-Bu
2
Oi-Pr
of the second generation Hoveyda–Grubbs catalyst were synthe-
sized (Eq. (1)). New siloxy complexes were obtained with the
ð2Þ
Mes
N
N Mes
NMR yield exceeding 90% for SiMe
2
(t-Bu), Si(i-Pr)3, SiMe
2
[4-
Cl
t-BuMe SiOSiMe t-Bu
2 2
C H
6 4
(OMe)], SiPh and 75% for SiR = SiMe
3
3
3
. However, during the
+
C D , rt
Ru
6
6
isolation procedure, the relatively good solubility of siloxy com-
plexes in pentane led to reduced isolated yields.
Cl
Oi-Pr
The yields of the complexes formed in the reactions performed
in the optimized conditions are given in Table 1. Milder reaction
conditions (25 °C) do not lead to higher yields and requires the
use of excess amounts of potassium silanolate, whose separation
from the complex formed is difficult.
All efforts to synthesise siloxy derivative of the first or second
generation Grubbs catalyst failed. Treatment of the catalysts
with sodium or potassium silanolates monitored by 1H NMR re-
sulted in gradual disappearance of the signal of hydrogen at car-
bene carbon (d = 20.6 and 19.6 ppm, respectively). No appearance
of new signals in the carbene region of the spectrum was
observed.
Precise monitoring of the reaction course revealed the forma-
tion of minor amounts (up to 20%) of monosiloxy complex, which
seems to be in equilibrium with the starting complex (1) and dis-
iloxy derivative. Despite variations in the reaction conditions and
stoichiometry no exclusive or predominant formation of monosil-
oxy derivatives was observed. The highest content of monosiloxy
complex (the 2:2:1 molar ratio of 1, mono- and disiloxy derivative)
yield = 100%
Siloxy substituted complexes (2–6), unlike the Hoveyda–Grub-
bs catalyst (1), are sensitive to water. However, the solids 2–6
can be stored for weeks in a glove-box without detectable
decomposition.
2
.3. Catalytic activity
In order to evaluate the catalytic activity of the siloxy
complexes (2–6) synthesized, preliminary catalytic tests were
performed. The results obtained indicated a similar catalytic
activity of 2–6 in RCM of diethyl diallyl malonate (Eq. (3))
(Table 2).
EtOOC COOEt
EtOOC COOEt
[Ru=C]
ð3Þ
Moreover, we performed comparative investigation of rela-
tive activity of representative siloxy complex (2), second gener-
ation Hoveyda–Grubbs catalyst (1) and Grubbs first generation
3
was detected when 1 was treated with KOSiPh in benzene at room
2 3 2
catalyst [RuCl (PCy ) (@CHPh)] (7) in selected model reactions,
that is RCM of diethyl diallyl malonate (Eq. (3)) (Fig. 1), CM
of Z-1,4-diacetoxybutene with allylbenzene (Eq. (4)) (Fig. 2)
and ROMP of 1,5-cyclooctadiene (Eq. (5)) (Fig. 3). These results
revealed significant decrease in the catalytic activity of disiloxy
complex (2) in relation to that of the parent Hoveyda–Grubbs
catalyst (1). In cross-metathesis and ROMP, disiloxy derivatives
were found to exhibit higher activity than the first generation
Grubbs catalyst. Disappointingly, in RCM of diethyl diallyl mal-
onate, disiloxy complex (2) was the least reactive of all the
complexes tested.
Table 1
Synthesis of ruthenium siloxide alkylidene complexes.
SiR
3
[Ru]:[KOSiR
3
]
Temperature Complex Isolated
(°C)/time (h)
yield (%)
SiMe
SiMe
SiMe
2
3
3
(t-Bu)
1:2
1:4
1:2
1:2
60/3
25/24
60/3
60/3
60/3
60/3
2
3
3
4
5
6
80
55
60
78
75
76
Si(i-Pr)
SiMe [4-C
SiPh
3
2
6
H
4
(OMe)] 1:2
1:2
3

3
920
S. Rogalski et al. / Journal of Organometallic Chemistry 694 (2009) 3918–3922
Table 2
100
RCM of diethyl diallyl malonate in the presence of 1 and ruthenium alkylidene
siloxides 2–6.
1
2
7
Catalyst
Time (h)
Yield (%)
80
1
2
3
5
6
0.5
2
2
2
2
100
60
54
58
55
60
40
20
0
Reactions conditions: CH
2
Cl
2
, reflux, 1 mol% of catalyst.
100
80
60
40
20
0
0.0
0.2
0.4
0.6
0.8
1.0
Time [h]
Fig. 3. ROMP of 1,5-cyclooctadiene in the presence of 1, 2 and 7.
These results have shown strongly deactivating effect of siloxy
ligands on the catalytic activity of Hoveyda–Grubbs type catalyst
in the reactions tested.
1
2
7
The exchange of anionic ligands in the Grubbs type com-
plexes was found to significantly modify the catalytic activity
of the complexes. Replacement of chlorine ligands with alkoxyl
ones, including fluorinated derivatives, in complex 7 brings the
disappearance of catalytic activity [22]. On the other hand,
Buchmeiser and Nuyken demonstrated that the catalytic activ-
ity of Hoveyda–Grubbs catalyst (1) is enhanced or preserved
by substitution of chlorine with electron-withdrawing ligands
0.0
0.1
0.2
0.3
0.4
0.5
Time [h]
Fig. 1. RCM of diethyl diallyl malonate in the presence of 1, 2 and 7. Reaction
conditions: 1 mol% of catalyst, 0.1 M, CH Cl , 30 °C.
2
2
[
21].
Our results indicate that substitution of chloride ligands in com-
plex 1 with the - and -donor siloxy groups brings about a dis-
100
r
p
tinct decrease in the catalytic activity in all reactions tested.
However, when ruthenium siloxide (2) was used as catalyst in
the cross-metathesis of triethoxyvinylsilane with styrene (Eq. (6))
its lower catalytic activity was found advantageous. In the pres-
ence of siloxy complex 2, the reaction led to exclusive and nearly
quantitative formation of silylstyrene while the use of 1 resulted
in formation of significant amount of the stilbene, the product of
competitive homo-metathesis of styrene (Table 3).
80
60
40
20
0
1
2
7
(EtO) Si
3
+
ð6Þ
(
EtO) Si
[Ru=CHR]
3
+
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Time [h]
Fig. 2. CM of Z-1,4-diacetoxybutene with allylbenzene in the presence of 1, 2 and 7.
Ph
+
AcO
OAc
Table 3
2
CM of styrene with vinyltriethoxysilane in the presence of Hoveyda–Grubbs catalyst
1) and selected siloxy derivatives (2–4).
(
ð4Þ
ð5Þ
2
.5 mol% [Ru]
Catalyst Conversion of silane
(%)
Yield of silylstyrene
(%)
Yield of stilbene
(%)
Ph
OAc
E / Z = 3.5 / 1
o
0
.2 M, CH Cl , 25 C
2 2
1
2
3
4
100
100
100
100
85a
96
99
98
15a
0
0
0
.1 mol % [Ru]
0
o
0
.5 M, CH Cl , 30 C
2 2
Reaction conditions: CH Cl , reflux, Ar, cat. 5%, 24 h.
2
2
n
a
2
2
h; [H C@CHSi]:[styrene] 1:1.

S. Rogalski et al. / Journal of Organometallic Chemistry 694 (2009) 3918–3922
3921
26.2, 21.1, 20.8, 18.8, ꢁ1.0; FD-MS [M]+ (not observed);
m.p. = 102–104 °C (decomposition).
3
. Conclusions
Second generation Hoveyda–Grubbs catalyst undergoes ex-
change of both chloride ligands with the siloxy ones to form sil-
oxy-substituted ruthenium alkylidene complexes, which exhibit
catalytic activity in selected olefin transformations. In view of the
new method of immobilization of transition metal complexes on
silica via interaction of metal siloxy derivative with hydroxy group
on silica, the complexes synthesized can be good candidates for di-
rect immobilization on silica.
4.3.3. [(H IMes)(OSiMe ) Ru{@CHC H (O-i-Pr)-2}] (3)
2
3 2
6 4
1
H NMR (C D , d, ppm): 14.99 (s, 1H, Ru@CHAr), 7.15–6.80 (m,
6
6
3H, aromatic CH), 7.0 (s, 4H, mesityl aromatic CH), 6.39 (d,
J = 8.1 Hz, 1H, aromatic CH), 4.39 (septet, J = 6.2 Hz, 1H,
(CH ) CHO), 3.41 (s, 4H, N(CH ) N), 2.55 (s, 12H, mesityl o-CH ),
3
2
2 2
3
2.27 (s, 6H, mesityl p-CH ), 1.35 (d, J = 6.2 Hz, 6H, (CH ) CHO,),
3
3 2
1
3
0.14 (s, 18H, OSi(CH ) ); C NMR (C D , d, ppm): 255.9, 219.1,
3
3
6 6
1
1
51.2, 144.8, 138.3, 138.1, 129.7, 129.6, 129.5, 125.1, 122.6,
21.4, 112.6, 73.5, 51.4, 26.0, 20.7, ꢁ1.2; FD-MS [M] , m/z (% inten-
+
4
. Experimental
sity): 728.3 (12), 729.3 (7), 730.3 (9), 731.2 (38), 732.2 (50), 733.2
(
59), 734.2 (100), 735.2 (40), 736.2 (56), 737.2 (26), 738.2 (7);
4.1. General methods and chemicals
m.p. = 182–184 °C.
All manipulations were carried out under dry argon using stan-
dard Schlenk techniques. 1H and C NMR spectra were recorded
13
4.3.4. [(H IMes){OSi(i-Pr) } Ru{@CHC H (O-i-Pr)-2}] (4)
2
3
2
6 4
1
6 6
H NMR (C D , d, ppm): 15.22 (s, 1H, Ru@CHAr), 7.09–6.76 (m,
on a Varian Gemini 300 at 300 and 75 MHz, respectively. Mass
spectra (FD-MS) were recorded on a Waters Micromass GTC Pre-
mier apparatus equipped with FD (Field Desorption) ion source
and time of flight analyzer (TOF).
All the chemicals were purchased from Aldrich. Reagent grade
pentane, THF and benzene were distilled from sodium/benzophe-
none under argon. HPLC grade dichloromethane and reagents for
3
H, aromatic CH), 7.0 (s, 4H, mesityl aromatic CH), 6.43 (d,
J = 8.0 Hz, 1H, aromatic CH), 4.48 (septet, J = 6.2 Hz, 1H,
CH CHO), 3.41 (s, 4H, N(CH N), 2.51 (s, 12H, mesityl o-CH ),
.28 (s, 6H, mesityl p-CH ), 1.33 (d, J = 6.2 Hz, 6H, (CH CHO),
.14 (d, J = 7.0 Hz, 36H, OSi{CH(CH ), 1.0 (septet, J = 7.0 Hz,
, d, ppm): 256.0, 219.8,
(
3
)
2
2
)
2
3
2
1
6
1
1
3
3 2
)
3 2 3
) }
1
3
H, OSi{CH(CH
3
2
) }
3
);
6 6
C NMR (C D
51.3, 144.8, 138.3, 129.7, 129.6, 127.3, 125.1, 122.8, 121.5,
catalytic tests were dried prior to use over CaH
argon.
2
and distilled under
+
13.2, 73.8, 51.4, 21.2, 19.7, 16.2, 14.1; FD-MS [M] , (not observed);
m.p. = 108–110 °C (decomposition).
4
.2. Synthesis of KOSiMe
2
t-Bu
4
.3.5. [(H
2
IMes){OSiMe
H NMR (C , d, ppm): 15.13 (s, 1H, Ru@CHAr), 7.62–7.40 (m,
H, C OMe), 7.15–6.87 (m, 4H C OMe and 3H, aromatic CH),
.03 (s, 4H, mesityl aromatic CH), 6.32 (d, J = 8.2 Hz, 1H, aromatic
CHO), 3.40 (s, 4H,
), 2.56 (s, 12H, mesityl o-CH ), 2.28
), 1.36 (d, J = 6.4 Hz, 6H, (CH CHO), 0.40 (s,
, d, ppm): 256.3, 219.5, 161.8,
2 6 4 2 6 4
(C H OMe-4)} Ru{@CHC H (O-i-Pr}] (5)
1
6 6
D
An oven dried 20 mL Schlenk flask closed with a septum and
4
7
6
H
4
6 4
H
equipped with a magnetic stirring bar was charged under argon
with 0.5 g (12.5 mmol) of KH and 10 mL of dry THF. The suspension
of potassium hydride was stirred at room temperature and 0.8 mL
CH), 4.18 (septet, J = 6.4 Hz, 1H, (CH
N(CH N), 3.31 (s, 6H, OCH
s, 6H, mesityl p-CH
3 2
)
2
)
2
3
3
(
5 mmol) of tertbutyldimethylsilanol was added dropwise to the
(
3
13
3 2
)
mixture. Stirring was continued for 24 h at room temp. After this
time the THF solution was filtered from the excess of potassium
hydride and evaporated to dryness giving potassium silanolate
with 98% yield.
1
1
1
3 2 6 6
2H, Si(CH ) Ar); C NMR (C D
51.3, 144.8, 138.3, 136.6, 129.6, 129.5, 129.3, 128.0, 126.8,
25.1, 122.9, 121.5, 112.9, 73.7, 51.4, 49.8, 21.8, 21.1, 19.3, ꢁ0.9;
+
FD-MS [M] , (not observed); m.p. = 95–98 °C (decomposition).
4
4
.3. Synthesis of siloxide complexes
4
.3.6. [(H
2
IMes)(OSiPh
H NMR (C , d, ppm): 15.57 (s, 1H, Ru@CHAr), 7.68–7.15 (m,
0H, OSiPh ), 7.13–6.90 (m, 3H, aromatic CH), 7.0 (s, 4H, mesityl
3 2 6 4
) Ru{@CHC H (O-i-Pr)-2}] (6)
1
6 6
D
2 2 2 6 4
.3.1. [(H IMes)(OSiMe t-Bu) Ru(@CH–C H (O-i-Pr)-2)] (2)
3
3
An oven dried 10 mL Schlenk flask equipped with a magnetic
aromatic CH), 5.90 (d, 1H, J = 8.2 Hz, aromatic CH), 3.85 (septet,
H, J = 6.2 Hz, (CH CHO), 3.35 (s, 4H, N(CH N), 2.41 (s, 12H,
mesityl o-CH ), 2.33 (s, 6H, mesityl p-CH ), 1.10 (d, J = 6.2 Hz, 6H,
, d, ppm): 259.7, 217.7, 151.6, 144.5,
41.9, 138.4, 136.4, 135.6, 130.0, 129.7, 129.5, 127.9, 126.9,
25.6, 122.4, 121.0, 113.3, 73.9, 51.5, 21.6, 21.2, 19.2; FD-MS
ꢁ5
stirring bar was charged under argon with 0.05 g (8.0 ꢀ 10 mol)
1
3
)
2
2 2
)
of Hoveyda–Grubbs second generation catalyst, 0.027 g
3
13
3
ꢁ4
(
1.6 ꢀ 10 mol) of KOSiMe
2
t-Bu and 3 mL of dry benzene. The
(
3 2 6 6
CH ) CHO); C NMR (C D
reaction mixture was stirred and heated in an oil bath at 60 °C
for 3 h. The colour change from green to brown and formation of
precipitate were observed. After a given reaction time the solvent
was evaporated to dryness and the siloxide complex was extracted
with 10 mL of dry pentane and filtered from the potassium salt un-
der argon. The solvent was evaporated to dryness giving the ruthe-
nium alkylidene siloxide complex with 80% yield. The other siloxy
complexes were synthesized by using similar procedure.
1
1
+
[
M] , m/z (% intensity): 1100.3 (13), 1101.3 (8), 1102.3 (10),
1
1
1
103.3 (28), 1104.4 (48), 1105.3 (63), 1106.3 (100), 1107.3 (72),
108.3 (65), 1109.3 (39), 1110.3 (21), 1111.3 (7); m.p. = 98–
00 °C (decomposition).
4.4. Catalytic tests
4
.3.2. Spectroscopic data
4.4.1. RCM
An oven dried 3 mL Schlenk flask with a side neck closed with a
septum, equipped with a condenser and a magnetic stirring bar
was charged under argon with 2.5 mL of CH Cl , 50 L of diethyl
L of dodecane (internal
standard). The mixture was stirred vigorously at 30 °C and 0.0017 g
(2.08 ꢀ 10 mol) of ruthenium siloxide alkylidene complex was
added under argon. A gentle flow of argon was applied. The reac-
tion was monitored by gas chromatography.
1
6 6
H NMR (C D , d, ppm): 15.16 (s, 1H, Ru@CHAr), 7.15–6.80 (m,
3
H, aromatic CH), 7.0 (s, 4H, mesityl aromatic CH), 6.37 (d,
J = 8.3 Hz, 1H, aromatic CH), 4.43 (septet, J = 6.2 Hz, 1H,
CH CHO), 3.39 (s, 4H, N(CH N), 2.52 (s, 12H, mesityl o-CH ),
.26 (s, 6H, mesityl p-CH ), 1.34 (d, J = 6.2 Hz, 6H, (CH CHO,),
.04 (s, 18H, OSi(CH C(CH ), 0.11 (s, 12H, OSi(CH C(CH );
, d, ppm): 256.2, 219.3, 151.4, 144.9, 138.4, 138.1,
29.6, 129.5, 129.4, 125.2, 122.8, 121.6, 112.7, 73.7, 51.5, 27.7,
2
2
l
ꢁ4
(
3
)
2
2
)
2
3
diallyl malonate (2.08 ꢀ 10 mol) and 20
l
2
1
3
3 2
)
ꢁ6
3
)
2
3
)
3
3
)
2
3
)
3
1
3
6 6
C NMR (C D
1

3
922
S. Rogalski et al. / Journal of Organometallic Chemistry 694 (2009) 3918–3922
4
.4.2. Cross-metathesis
An oven dried 3 mL Schlenk flask with a side neck closed with a
[3] (a) F.J. Feher, J. Am. Chem. Soc. 108 (1986) 3850–3852;
b) T. Wolczanski, Polyhedron 14 (1995) 3335–3362.
(
[
[
4] F.J. Feher, R.L. Blanski, J. Am. Chem. Soc. 114 (1992) 5886–5887.
5] F.J. Feher, T.L. Tajima, J. Am. Chem. Soc. 116 (1994) 2145–2146.
septum, equipped with a condenser and a magnetic stirring bar
was charged under argon with 0.5 mL of CH Cl , 13 L of allylben-
of Z-1,4-diacetoxy-2-butene
L of decane (internal standard). The
mixture was stirred vigorously at 25 °C and 0.002 g
2
2
l
[6] A. Choplin, B. Coutant, C. Dubuisson, P. Leyrit, C. McGill, F. Quignard, R. Teissier,
in: H.U. Blaser, A. Baiker, R. Prins (Eds.), Heterogeneous Catalysis and Fine
Chemicals IV, Stud. Surf. Sci. Catal, Elsevier, Amsterdam, 1997, p. 353.
ꢁ5
zene (9.75 ꢀ 10 mol), 31
lL
ꢁ
4
(
1.95 ꢀ 10 mol) and 50
l
[
7] L.D. Ornelos, A. Choplin, J.M. Basset, L.Y. Hsu, S. Shore, Nouv. J. Chim. 9 (1985)
155–157.
ꢁ
6
[8] (a) B. Marciniec, P. Krzyzanowski, J. Organomet. Chem. 493 (1995) 261–266;
(
2.44 ꢀ 10 mol) of ruthenium siloxide alkylidene complex was
(
(
b) P. Krzyzanowski, M. Kubicki, B. Marciniec, Polyhedron 15 (1996) 1–4;
c) B. Marciniec, P. Krzyzanowski, M. Kubicki, Polyhedron 15 (1996) 4233–
added under argon. A gentle flow of argon was applied. The reac-
tion was monitored by gas chromatography.
4239;
(
(
d) B. Marciniec, P. Błazejewska-Chadyniak, M. Kubicki, Can. J. Chem. 81
2003) 1292–1298.
4
.4.3. ROMP
[9] (a) B. Marciniec, I. Kownacki, M. Kubicki, Organometallics 21 (2002) 3263–
270;
b) I. Kownacki, M. Kubicki, B. Marciniec, Inorg. Chim. Acta 334 (2002) 301–
07.
3
(
3
An oven dried 3 mL Schlenk flask with a side neck closed with a
septum, equipped with a condenser and a magnetic stirring bar
was charged under argon with 3 mL of CH Cl 150
L of decane or
dodecane (internal standard). The reaction mixture was stirred
2
2
,
lL
[10] (a) B. Marciniec, E. Walczuk-Gusciora, P. Blazejewska-Chadyniak, J. Mol. Catal.
A: Chem. 160 (2000) 165–171;
ꢁ
3
(
1.22 ꢀ 10 mol) of 1,5-cyclooctadiene and 50
l
(
(
(
b) B. Marciniec, E. Walczuk-Gusciora, C. Pietraszuk, Organometallics 20
2001) 3423–3428;
c) B. Marciniec, M. Lewandowski, E. Bijpost, E. Malecka, M. Kubicki, E.
ꢁ6
and heated in an oil bath at 30 °C. Then 0.001 g (1.22 ꢀ 10 mol)
of ruthenium siloxide alkylidene complex was added under argon.
A gentle flow of argon was applied. The reaction was monitored by
gas chromatography.
Walczuk-Gusciora, Organometallics 18 (1999) 3968–3975.
11] (a) I. Kownacki, B. Marciniec, A. Macina, S. Rubinsztajn, D. Lamb, Appl. Catal.
A: Gen. 317 (2007) 53–57;
[
[
(
b) B. Marciniec, I. Kownacki, M. Kubicki, P. Krzyzanowski, E. Walczuk, P.
Błazejewska-Chadyniak, in: C.G. Screttas, B.R. Steele (Eds.), Perspectives in
Organometallic Chemistry, Royal Society of Chemistry, Cambridge, UK, 2003,
p. 253.
Acknowledgements
12] E. Mieczynska, A.M. Trzeciak, J.J. Ziołkowski, I. Kownacki, B. Marciniec, J. Mol.
Catal. A: Chem. 237 (2005) 246–253.
13] I. Kownacki, K. Szubert, M. Kubicki, Organometallics 24 (2005) 6179–6183.
14] I. Kownacki, M. Kubicki, K. Szubert, B. Marciniec, J. Organomet. Chem. 693
(2008) 321–328.
15] B. Marciniec, K. Szubert, M.J. Potrzebowski, I. Kownacki, K. Ł e˛ szczak, Angew.
Chem., Int. Ed. 47 (2008) 541–544.
16] J.T. Poulton, M.P. Sigalas, K. Folting, W.E. Streib, O. Eisenstein, K.G. Caulton,
Inorg. Chem. 33 (1994) 1476–1485.
Financial support from the Ministry of Science and Higher Edu-
cation (Poland), (Project No. 204 162 32/4248) is gratefully
acknowledged. S.R. wishes to acknowledge the grant from the
Operational Programme of Human Resources, Action 8.2., co-fi-
nanced by EU European Social Fund and Polish State. Materia Inc.
is kindly acknowledged for generous donation of ruthenium alkyl-
idene complexes.
[
[
[
[
[17] T.J. Johnson, K. Folting, W.E. Streib, J.D. Martin, J.C. Huffman, S.A. Jackson, O.
Eisenstein, K.G. Caulton, Inorg. Chem. 34 (1995) 488–499.
[
18] J. Puga, T.P. Fehlner, B.C. Gates, D. Braga, F. Grepioni, Inorg. Chem. 29 (1990)
2376–2381.
References
[
19] P. Braunstein, J.R. Galsworthy, W. Massa, J. Chem. Soc., Dalton Trans. (1997)
4
677–4681.
[
1] (a) B. Marciniec, H. Maciejewski, Coord. Chem. Rev. 223 (2001) 301–335. and
references therein;
[
[
20] A. Walstrom, M. Pink, K.G. Caulton, Inorg. Chem. 45 (2006) 5617–5620.
21] (a) S.B. Garber, J.S. Kingsburry, B.L. Gray, A.H. Hoveyda, J. Am. Chem. Soc. 122
(
b) B. Marciniec, in: A. Trzeciak, P. Sobota (Eds.), Education in Advanced
(
(
2000) 8168–8179;
Chemistry, vol. 9, Wydawnictwo Uniwersytetu Wrocławskiego, Pozna n´ -
b) A.H. Hoveyda, D.G. Gillingham, J.J. Van Veldhuizen, O. Kataoka, S.B. Garber,
Wrocław, 2005, pp. 194–214;
J.S. Kingsbury, J.P.A. Harrity, Org. Biomol. Chem. 2 (2004) 8–23.
(
c) B. Marciniec, M.J. Potrzebowski, I. Kownacki, K. Szubert, in: J.M. Basset, R.
[
[
22] J.O. Krause, O. Nuyken, K. Wurst, M.R. Buchmeiser, Eur. J. Chem. 10 (2004)
Psaro, D. Roberto, R. Ugo (Eds.), Modern Surface Organometallic Chemistry,
Wiley-VCH, Weinheim, 2009 (Chapter 7).
7
77–784.
23] M.S. Sanford, L.M. Henling, M.W. Day, R.H. Grubbs, Angew. Chem., Int. Ed. 39
2000) 3451–3453.
[
2] (a) F.R. Hartley, Supported Metal Complexes, Reidel, Boston, 1985;
(
(
b) Y. Iwasawa, Tailored Metal Catalysts, Reidel, Boston, 1986.