18-electron ruthenium phosphine sulfonate catalysts for olefin metathesis

Article abstract of DOI:10.1021/om500212x

The first instances of ruthenium alkylidene complexes based on chelating phosphine sulfonates are presented. Although these complexes are formally 18-electron complexes bearing cis phosphines and cis one-electron donors (sulfonates and chlorides), they are surprisingly active for ring-closing metathesis, cross-metathesis, and ring-opening metathesis polymerization, thus highlighting the unique potential of the sulfonate ligand in the design of a ruthenium metathesis catalyst.

Full text of DOI:10.1021/om500212x

Article
pubs.acs.org/Organometallics
1
8-Electron Ruthenium Phosphine Sulfonate Catalysts for Olefin
Metathesis
Oumar Bashir, Laurence Piche, and Jerome P. Claverie*
Queb
́
ec Center for Functional Materials, NanoQAM, Department of Chemistry, University of Quebec in Montreal, Succ Centre Ville
CP8888, Montreal, Quebec H3C3P8, Canada
*
S Supporting Information
ABSTRACT: The first instances of ruthenium alkylidene
complexes based on chelating phosphine sulfonates are
presented. Although these complexes are formally 18-electron
complexes bearing cis phosphines and cis one-electron donors
(
sulfonates and chlorides), they are surprisingly active for ring-
closing metathesis, cross-metathesis, and ring-opening meta-
thesis polymerization, thus highlighting the unique potential of
the sulfonate ligand in the design of a ruthenium metathesis
catalyst.
͡
INTRODUCTION
Chart 1. Structure of the PSO
Alkylidenes (1−5)
3
Ligands (0) and Ru
■
The discovery that well-defined ruthenium alkylidene com-
plexes are active catalysts for the metathesis reaction has
attracted considerable attention.
1
−5
The structure of these
catalysts conforms to the generic formula RuX (CHR)L L ,
2
1
2
−
whereby X are halides or pseudo-halides and L and L are 2 e
1
2
σ-donating ligands. Interestingly, catalysts bearing L-X chelating
ligands have been scrutinized only very recently. Most of them
6
−16
are based on chelating N-heterocyclic carbenes (NHCs)
and are found to promote Z-selectivity. Ruthenium alkylidenes
17
coordinated by bidendentate amino-benzyloxy ligands were
found to be unstable, and only the tridentate amino
bis(benzyloxy) complex could be isolated to yield a thermally
unstable alkylidene. Alkylidenes of Ru chelated by salicylaldi-
minates ligands are stable but demonstrate only moderate
1
8
activity. Surprisingly, catalysts based on chelating phosphines
are scarce in the literature. Fogg et al. reacted RuCl (PPh3)3
2
with the sodium salt of (diphenylphosphino)-1,1′-binaphthyl-2-
1
9
ol, but σ → π isomerization of the aryloxide moiety prevented
20,21
the formation of the expected alkylidene.
Ru alkylidenes
bearing a bidentate phosphine phenolate ligand PR R (C H -o-
1
2
6
4
t
O−), with R and R = Bu, adamantyl, and neopentyl, were
1
2
22,23
potential of sulfonate ligands when incorporated into meta-
thesis catalysts.
recently prepared by Torker et al.
These complexes
displayed an interesting Z-selectivity for the ring-opening
metathesis copolymerization of cyclooctene and norbornene.
We present here the first example of metathesis catalysts
͡
Chelating PSO ligands have been extensively scrutinized for
3
the preparation of palladium- and nickel-based polymerization
catalysts and were shown to promote main-chain incorporation
of a wide range of fundamental polar olefins (such as acrylates,
acrylonitrile, vinyl acetate, halogenated monomers) as well as
͡
based on chelating ortho phosphine sulfonate (PSO ) ligands
3
(Chart 1). We found that 1−3 are surprisingly active metathesis
catalysts despite the fact that they are 18-electron species, the
sulfonate and chloride are cis to each other, and they are based
on phosphines that are less donating than NHCs. The present
work is therefore the first illustration of the remarkable
Received: February 28, 2014
©
XXXX American Chemical Society
A
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Article
2
4
27
ethylene. When combined with Ru, these versatile ligands are
dmso, or acetone) in the presence of the corresponding L. In
25
͡ ͡
this study, neither Ru(PSO ) nor Ru(PSO ) L (L = water,
3 2 3 2 2
found to be useful for the transfer hydrogenation of ketones,
in the regioselective allylation of various substrates, for the
2
6
dmso, or acetone) was found to react with phenyl diazo-
methane to form the corresponding bischelated Ru alkylidene:
unreacted complex and stilbene were the only isolated
products. Single phosphine exchange was also found to occur
readily starting from 7, to yield 2a, 2b, and 2c, which were
separated from 8 by column chromatography (Scheme 2). In a
similar fashion to 1a and 1b, complexes 2a, 2b, and 2c resisted
27
insertion polymerization of ethylene, and for the alkylation of
2
8
͡
amines. The PSO ligands present several unique properties.
3
First, it is a highly asymmetrical ligand, containing a strongly
donating neutral phosphine (with basicity tunable by changing
the nature of the substituents) and very electron-poor anionic
sulfonate donor. As the activity of a Ru-based metathesis
catalyst increases with the basicity of one of the L ligands, and
29
͡
further substitution by a second PSO ligand.
3
3
0,31
͡
the PSO ligands
3
increases with the acidity of the X ligand,
should be ideal to form highly active metathesis catalysts.
Scheme 2. Preparation of Complexes 2
Interestingly, being a very poor donor, the SO can dissociate
3
completely from the metal atom, resulting in the formation of
3
2,33
an ion-pair (for L = NHC, M = Pd, Ni).
Second, the
1
sulfonate ligand can theoretically bind the metal in a κ O
2
fashion as a two-electron donor or in a κ O,O′ fashion as a
four-electron donor, but to our knowledge, prior to this work,
2
phosphine sulfonates having κ O,O′ SO groups have not been
3
isolated, except for one intermolecular complex where two of
34
the oxygen atoms of SO are bound to two distinct Pd atoms.
3
1
2
For Pd complexes, isomerization between both κ O and κ O,O′
forms has been shown to be at the origin of a Berry
pseudorotation process, which is pivotal to explain the unusual
͡
The formation of PSO alkylidenes was also probed via the
3
Meyer−Schuster rearrangement of 1,1-diphenyl-2-propyn-1-
35−38
ol.
͡
the alkyne, and the corresponding PSO phosphine, in a one-
3
Thus, 3a was formed upon reaction of RuCl (PPh ) ,
2 3 3
24
capacity for Pd-based catalysts to polymerize polar olefins.
pot reaction (Scheme 3). Only compound 3a could be isolated,
in agreement with the larger steric bulk of phosphines ob and
oc, despite their greater basicity.
RESULTS AND DISCUSSION
■
Compounds 1a, 1b, and 1c were readily prepared by ligand
exchange from Grubbs catalyst generation o, Ru(CHPh)-
͡
Cl (PPh ) , with the corresponding PSO ligand (Scheme 1).
Scheme 3. Preparation of 3a
2
3 2
3
Scheme 1. Formation of Complex 1 and Reactivity with
a
͡
Excess PSO Ligand
3
All compounds were fully analyzed by nuclear magnetic
resonance (NMR), mass spectrometry (MS), elemental
analysis, and, for 1a, 1b, and 3a, single-crystal X-ray diffraction
(
Figure 1). These compounds exhibit uncharacteristic features,
in comparison to other Ru alkylidenes. First, the two P atoms
are cis to each other (angle P1−Ru−P2 = 100° ± 5°, Table 1).
Second, all the complexes adopt a distorted octahedral
geometry, whereby two oxygens of the sulfonate are
coordinated to Ru, one (O1) trans to P2 and the other one
a
Yield 1a = 73%, 1b = 48%, 1c = 32%. The grayed structure was not
prepared by this route.
(
O2) trans to the alkylidene, although O2 is offset from the
Yields were found to decrease with the steric bulk of the
phosphine (oa < ob < oc). Only a single phosphine and
chloride substitution occurred, even when the reaction was
performed for prolonged time in the presence of excess
phosphine. Baffled by the lack of reactivity of 1a and 1b toward
ligand substitution, several other strategies were attempted to
force the formation of a bischelated Ru alkylidene, such as
adding K CO as HCl trap, starting from a deprotonated
octahedral coordination site (O2−Ru−C < 180°, and Ru−O2
longer than Ru−O1, Table 1) as expected for a small-size four-
member O −Ru−O −S chelate. Coordination of both O and
1
2
1
O is evidenced by the equal bond lengths for S−O1 and S−O2
2
and longer bond length for SO3 (Table 1). Thus, these Ru
alkylidenes are formally 18-electron octahedral complexes
2
39
bearing a unique κ O,O′ sulfonate ligand. Third, the Ru
C bond length is longer than in active Ru alkylidenes. A
literature survey over 31 Ru catalytically active alkylidenes (see
Table S1) indicates that the bond length of RuCHPh is
between 1.818 and 1.854 Å. Longer RuCHPh bonds,
between 1.859 and 1.879 Å, are found for 18-electron
complexes that are catalytically inactive (see Table S2). The
2
3
phosphine sulfonate (Na, K, and Ag salts), but none succeeded.
27
͡
Ru(PSO ) (R = Ph) has been reported by us in the past.
3
2
This complex, which is polymeric in nature (probably via the
intervention of bridging SO ), was found at that time to readily
3
−
͡
break up into monomeric 18 e Ru(PSO ) L (L = water,
3
2 2
B
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Figure 1. Labeled view of 1a, 1b, and 3a with 50% probability ellipsoids (hydrogen atoms and solvent molecules omitted).
a
Table 1. Selected Bond Lengths and Bond Angles for
Complexes 1a, 1b, and 3a
Scheme 4. Preparation of 4a and 5a
1
a
1b
3a
́
Bond Lengths (Å)
1.869
Ru−C
Ru−P1
Ru−P2
Ru−Cl
Ru−O1
Ru−O2
S−O1
1.873
2.413
2.308
2.369
2.221
2.362
1.489
1.477
1.434
1.884
2.371
2.305
2.370
2.232
2.403
1.485
1.481
1.435
2.338
2.295
2.380
2.226
2.407
1.490
S−O2
S−O3
1.486
1.433
Bond Angles (deg)
P1−Ru−P2
C−Ru−P1
O1−Ru−P2
O2−Ru−C
97.44
86.91
103.69
94.01
100.28
93.42
172.43
155.55
167.90
163.81
167.61
157.10
a
Conditions: (a) THF reflux, 12 h; (b) −40 °C, 90 min in CH Cl −
2
2
4
0
basic Al O ; (c) dimethylcarbonate, 70 °C, CH Cl reflux overnight.
fact that d(RuC) is longer in 18-electron complexes may be
explained by the presence of a destabilizing trans ligand sharing
the same metal orbitals as the alkylidene (akin to a trans
influence). However, complexes 1−3, which are formally 18-
electron, as also shown by unusually long RuC bond lengths,
are catalytically active (see below). For the sake of completion,
it should be mentioned that during the course of this study an
2
3
2
2
1
8-electron alkylidene complex bearing an unusual nitrato
8,11
ligand has been reported.
Before embarking upon a survey of the catalytic activity of
complexes 1−3, it should be noted that the preparation of
bischelated Ru alkylidenes was found to be possible using the
Meyer−Schuster route (Scheme 4), leading to the formation of
a stable allenylidene, 4a, which was rearranged into an
Figure 2. Labeled view of 4a with 50% probability ellipsoids
hydrogen atoms omitted) with selected bond lengths and angles.
(
41
indenylidene, 5a, upon acidic treatment. Complex 4a was
also characterized by X-ray diffraction (Figure 2), indicating the
temperatures ranging from 22 to 60 °C, the activation energy
2
1
2
͡
presence of two inequivalent PSO ligands, one bis-coordinated
for the κ O,O′ → κ O → κ O,O′ process was found to be 16.1
3
and strongly bound to Ru, as shown by short Ru−P4 and Ru−
O4 distances, and one tricoordinated, but less strongly bound,
as shown by longer Ru−P1, Ru−O1, and Ru−O2 distances. By
kcal/mol, which is of the same magnitude as the calculated
activation barriers for the η → η → η isomerization in allyl
complexes. In complex 5a, this isomerization process is also
3
1
3
42
3
1
P NMR, the signal of the two cis P appeared as two distinct
rapid, as shown by the presence of a single sharp resonance by
3
1
broad resonances that coalesce into a single resonance at 55 °C
in C D Cl , indicating the presence of a fluxional process
P NMR, which splits into two resonances at −50 °C in
CD Cl (activation energy: 10.6 kcal/mol).
2
4
2
2
2
2
1
͡
whereby the κ O,O′ sulfonate isomerizes into a κ O sulfonate,
The PSO3 Ru alkylidene complexes 1−5 have several
2
leading to the coordination of the other sulfonate in a κ O,O′
common features: the sulfonate ligands (or at least one of
them) are in a κ O,O′ binding mode, and therefore the
3
1
2
fashion. Using band-shape analysis of the P NMR data at
C
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complexes are 18 electron, a fact that is further confirmed by
the unusually long alkylidene bond lengths. Furthermore, both
phosphines are cis to each other. Last, the phosphine forming
the strongest Ru−P bond is the nonchelating one (shorter Ru−
Scheme 6. RCM and ROMP Experiments Performed to
Assess the Activity of Catalysts 1−3 and 9
P2 bond than Ru−P1), i.e., PPh in 1−3. The combinations of
3
these structural features would entice us to believe that 1−3 are
inactive in metathesis. First, Ru 18-electron carbenes are known
to promote cyclopropanation instead of metathesis, as the
intermediary metallacyclobutane is prone to reductive elimi-
4
3
nation. Second, complexes bearing cis X ligands are often
44
found to be inactive (although an exception was recently
reported), but they slowly interconvert to active trans X
4
5−47
catalysts.
It is now well established that the active species in metathesis
is the 14 e− RuLX (CHR), which is generated by
2
dissociation of the phosphine. In complexes bearing trans L
and trans X ligands, this dissociation step is rapid because the
trans influence of the strongly σ-donating L ligand (a phosphine
or a NHC) weakens the Ru−P bond. In our case, unlike
conventional Ru metathesis catalysts, we noticed that the Ru−
P bond trans to the sulfonate is short, and one could question
2
whether dissociation of PPh would in fact occur. PPh3
3
substitution by the more basic PCy , which most likely occurs
3
−
via dissociation of PPh first (as the complex is 18 e ), was
3
found to occur smoothly on 1 (Scheme 5), yielding complexes
9.
a
Scheme 5. Phosphine Substitution
a
Room temperature, 30 min.
The activity of catalysts 1−3 and 9a were assessed in ring-
closing metathesis (RCM) of diethyl diallyl malonate (10,
Scheme 6, Figure 3), diallyldiphenyl silane, 11, and linalool, 12,
ring-opening metathesis polymerization (ROMP) of norbor-
nene, 13, and cyclooctene, 14, and cross-metathesis (CM) of
octene, 15, which are all standard activity beacons for
metathesis catalysts (Table 2). These catalysts are all active,
with 1b exhibiting the greatest activity (Figure 3) of all of them,
͡
Figure 3. Comparison of the RCM kinetics of 10 with various
probably due to the greater σ-donating character of the PSO3
phosphine bearing two cyclohexyl groups. Surprisingly, catalyst
catalysts. Conditions: 10 = 0.02 M; 1 mol % of catalyst, CDCl , reflux
3
1
(
H NMR measurements).
9
a is more active than 1a, which is unexpected, as PCy , being
3
more donating than PPh , should be a worse leaving group.
This may be ascribed to a steric effect resulting from the faster
3
illustrate the interesting potential of the sulfonate ligand in
the design of novel metathesis catalysts.
dissociation of PCy in order to reduce steric encumbrance
3
around the metal center. Interestingly, catalyst 1b exhibits an
activity that is superior to Grubbs first-generation catalyst (G1)
and that approaches Grubbs second-generation catalyst (G2),
as shown in ring-closing of 10 (entries 4 and 5, 380 turnovers
in 45 min) or in cross-metathesis of 1-octene (entry 21, 55
turnovers in 2.7 h). Compound 5a was found to be inactive
despite several attemps to make it react, even at high
temperature (for example, ROMP of 13, [13]:[5] = 250:1, T
CONCLUSION
In summary, chelating phosphine sulfonates and more generally
chelating sufonated ligands have been exploited with great
success for Pd and Ni catalytic chemistry, because of their
remarkable electronic asymmetry as well as their geometric
flexibility. Their installation on ruthenium alkylidenes has been
presented for the first time here, yielding olefin metathesis
catalysts with an activity that surpasses the activity of
comparable nonchelating phosphine catalysts. It clearly ensues
■
48
24
=
80 °C in toluene, and RCM of 10, [10]:[5] = 100:1, T = 60
°
C in CDCl ). These preliminary activity results clearly
3
D
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Organometallics
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performed at the X-ray crystallography laboratory of the University
of Delaware, Department of Chemistry and Biochemistry.
Table 2. Survey of the Catalytic Activity of Catalysts 1−3 and
9
with Different Substrates S (Scheme 6)
(
PPh )[P(-6-SO -C H )(Ph) ]Cl-RuCH-Ph (1a). Inside a drybox,
3
3
6
4
2
entry
cat
S
[S]/[cat]
t (h)
yield (%)
100 mg (0.127 mmol, 1.0 equiv) of (PPh ) Cl RuCHPh and 87 mg
3 2 2
a
(0.254 mmol, 2.2 equiv) of oa were weighed in a vial to which 5 mL of
CH Cl was added. The solution was first stirred at room temperature
1
1b
1b
1b
1b
1b
1a
1a
1a
9a
G1
G1
G2
G2
2b
2b
3a
1b
1b
1b
1b
1b
1b
1a
1b
1b
1b
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
11
11
11
12
13
13
14
14
15
15
100
100
500
500
2000
100
100
100
100
100
500
100
500
100
100
100
100
100
20
0.75
3
90
95
47
77
19
14
35
45
59
91
23
99
99
52
85
15
18
41
61
35
90
70
33
55
55
62
a
2
2
2
a
for 30 min and then filtered on Celite, and the solvent was evaporated.
Methanol was added to wash the crude, the supernatant was removed,
and the crude was dried in vacuo to give the desired product as a
brown solid (76.8 mg, 0.093 mmol, 73%). The product could also be
further purified by passing the residue through a column of silica gel
(CH Cl /diethyl ether = 87:13 v/v). The progress of the compound
3
0.75
3
a
4
b
5
0.45
5.75
23
a
6
a
7
2
2
a
8
72
over the column was monitored visually (purple band). Air-stable
a
1
9
0.75
0.75
0.75
0.75
0.75
23
crystals were obtained by slow diffusion of diethyl ether in CH Cl . H
2
2
3
3
a
NMR (300 MHz, CDCl ): δ 15.64 (dd, J = 15.4, J = 12.7 Hz,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
3 HP HP
3
3
a
a
a
a
a
a
a
a
a
a
c
1H, RuCH), 7.83 (dd, J = 11.5, J = 8.0 Hz, 5H), 7.58 (dd,
J =
HP HH HP
HP
HH
3
3
3
= 14.2, J = 6.9 Hz, 3H), 7.49−7.23 (m, 8H), 7.17 (dd, J
3
3
16.7, J = 7.6 Hz, 6H), 7.10−6.97 (m, 3H), 6.89 (dt, J = 9.9,
HH
HH
3
13
JHH = 4.9 Hz, 5H), 6.83−6.75 (m, 2H), 5.84−5.54 (m, 2H).
C
NMR (CDCl ): δ 321.26 (s), 149.96 (s), 145.28 (d), 134.92 (s),
3
72
1
33.08 (m), 132.18 (s), 131.42 (m), 129.84 (d), 128.90 (s), 128.37
21
31
2
(
m), 126 (dd). P NMR (CDCl ): δ 53.50 (d, J = 34.8 Hz), 20.42
d, J = 34.8 Hz). Anal. Calcd for RuC H P SO Cl·0.82CH Cl (1
3 PP
2
2
(
PP
43 35
2
3
2
2
20
molecule of CH Cl was found in the solid-state structure of 1a): C,
2 2
20
58.40; H, 4.18. Found: C, 58.41; H, 4.06. Anal. Calcd for
100
1500
17000
100
1000
100
20
RuC H P SO Cl·0.85CH Cl : C, 58.36; H, 4.10. Found: C, 58.41;
4
3
35
2
3
2
2
+
+
H, 4.06. HRMS [ESI ] RuC H P SO Cl: calcd 795.0903 [M + H] ,
found 795.0348 [M + H] .
0.15
0.3
22
43 35
2
3
+
d
e
(PPh )[P(-6-SO -C H )(Cy) ]Cl-RuCH-Ph (1b). Inside a drybox,
3
3
6
4
2
f
100 mg (0.127 mmol, 1.0 equiv) of (PPh ) Cl RuCHPh, 100 mg
0.279 mmol 2.2 equiv) of ob, and K CO (35 mg, 0.279 mmol, 2.2
2 3
3
2
2
1
(
g
g
2.7
23
equiv) were weighed in a vial, and 5 mL of CH Cl was added. The
2
2
100
suspension was stirred at room temperature for 60 min. The solution
was filtered on basic alumina oxide, and the solvent evaporated. Fresh
diethyl ether was added to wash the green solid before drying in vacuo
(50.9 mg, 0.06 mmol, 48%). The product could be purified by silica gel
chromatography (CH Cl /diethyl ether = 87:13 v/v). Crystals were
a
b
[
S] = 0.02 mol/L, reflux, CDCl . [S] = 0.02 mol/L, toluene, 80 °C.
3
c
−3
d
[
S] = 4 × 10 mol/L, room temperature, CDCl (Z:E = 30:70). S =
.3 mol/L, room temperature, toluene (Z:E = 28:72). [S] = 0.5 mol/
3
e
1
f
L, room temperature, CDCl (Z:E = 40:60). [S] = 1 mol/L, room
temperature, CDCl (Z:E = 50:50). Neat, T = 60 °C (Z:E = 30:70).
2
2
3
g
1
obtained by slow diffusion of diethyl ether in CH Cl . H NMR (300
MHz, CDCl ): δ 20.29 (d, J = 2.6 Hz, 1H), 7.87 (dd, J = 7.6 Hz,
JHH = 3.6 Hz, 1H), 7.65 (t, J = = 6.3 Hz, 3H), 7.59 (dd, J
3
2 2
3
3
3
HP
HH
3
3
3
=
HH
HP
3
1
1
1.0 Hz, J = 7.7 Hz, 2H), 7.49−7.43 (m, 3H), 7.41−7.33 (m,
HH
that sulfonate anionic donors are of interest for the design of
highly active metathesis catalysts (sulfonated NHCs are
currently under scrutiny in our group). Furthermore, these
catalysts are active, despite both X ligands being in a cis position
3 3
0H), 7.32−7.28 (m, 3H), 7.17 (s, 1H), 7.00 (dd, J = 15.1 Hz, J
HP
HH
= 7.4 Hz, 3H), 3.53−3.28 (m, 2H), 1.97−1.20 (m, 16H), 1.21−1.08
(m, 4H). 13C NMR (75 MHz, CDCl ): δ 443.88 (s), 134.75 (s),
3
133.34 (s), 132.56−131.57 (m), 130.33 (s), 128.42 (t, J = 13.7 Hz),
−
31
2
3
2
0.93 (s), 26.31 (s). P NMR (122 MHz, CDCl ): δ 30.69 (d, J
=
and the formal electron count of the catalyst being 18 e . Such
3
PP
2
68.7 Hz), 11.83 (d, JPP = 268.7 Hz). Anal. Calcd for
surprising features are bound to lead to novel mechanistic and
structural studies, which should guide the design of more active
metathesis catalysts departing from the conventional 16 e−
RuX (CHR)L L pattern.
RuC H P SO Cl·0.3CH Cl ·0.1Et O: C, 59.97; H, 5.60. Found: C,
4
3
47
2
3
2
2
2
+
59.95; H, 5.61. HRMS [ESI ] RuC
Cl] , found 807.1223 [M − Cl] .
H P SO Cl: calcd 807.1764 [M
43
47 2 3
+
+
−
t
2
1 2
(
PPh )[P(-6-SO -C H )(Ph)( Bu)]Cl-RuCH-Ph (1c). Inside a
3
3
6
4
drybox, 130 mg (0.164 mmol, 1.0 equiv) of (PPh ) Cl RuCHPh,
3
2
2
EXPERIMENTAL SECTION
General Procedures. All manipulations were done under an inert
atmosphere using standard Schlenck and cannula techniques. Dry,
oxygen-free solvents were obtained using a solvent purification system.
■
56 mg (0.180 mmol, 1.1 equiv) of ligand oc, and K
2
CO
3
(35 mg, 0.279
mmol, 2.2 equiv) were weighed in a vial, and 5 mL of CH Cl was
2 2
added. The suspension was stirred at room temperature for 30 min.
The solution was filtered on basic alumina oxide, and the solvent
evaporated. The resulting brown solid was found to be partially soluble
in diethyl ether and in pentane, which rendered further purification
difficult. The spectroscopic data obtained here are for the crude
RuCl , 1,1-diphenyl-2-propyn-1-ol, and trifluoromethanesulfonic acid
3
were bought from Sigma-Aldrich and used without further purification.
4
9
50
51
52
[
RuCl (PPh ) ], [RuCl (DMSO)], phosphines oa, ob, and
2 3 3 2
29 53
1
3
oc, (PCy ) Cl RuCHPh, and Cl Ru(CH-o-OMeC H )PPh
product. H NMR (300 MHz, CD Cl ): δ 15.73 (t, J = 16.3 Hz,
3
2
2
2
6
4
3
2 2 HP
5
4
1
13
31
(
7) were synthesized according to published procedures. H, C,
1H), 7.8−6.4 (m, 30H), 1.3−1.1 (m, 9H), P NMR (122 MHz,
2 2
31
and P NMR spectra were recorded on a 600 or 300 MHz
CD Cl ): δ 53.67 (d, J = 41.5 Hz), 20.11 (d, J = 41.5 Hz).
2 2 PP PP
spectrometer at ambient temperature. NMR spectra were reported
[P(-6-SO -C H )(Cy) ]Cl-Ru(CH-O-Me-C H ) (2b). Inside a
3
6
4
2
6
4
31
1
13
relative to external 85% H PO ( P) or internal TMS ( H, C). Mass
glovebox, Cl Ru(CH-o-OMeC H )PPh (7) (40 mg, 0.073 mmol,
3
4
2
6
4
3
spectrometry analyses were performed using a time-of-flight LC/MS
liquid chromatography coupled to an MS spectrometer. Data were
collected in positive reflection mode. Analyte solutions were prepared
in CH Cl at concentrations of 1 mg/mL. Elemental analysis was
1.0 equiv) and ob (61.5 mg, 0.173 mmol, 2.4 equiv) were added in a
Schlenk flask containing 4 mL of CHCl . The flask was equipped with
3
a condenser, and the mixture was heated at 60 °C for 24 h. The
solvent was evaporated, and the crude was passed through a silica gel
column using CH Cl /CH OH = 10:1 v/v as eluent to yield a green
2
2
performed by the Service d’Analyses Elementaires, Departement de
Chimie, Universite de Montreal. Crystallographic analysis was
2
2
3
1
́
́
solid (17.3 mg, 0.029 mmol, yield = 40%). H NMR (300 MHz,
E
dx.doi.org/10.1021/om500212x | Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
acetone): δ 18.08 (d, J = 6.4 Hz, 1H), 7.82 (t, 3JHH = 7.2 Hz, 1H),
3
7.05 (dd, J = 13.9, 3J = 7.2 Hz, 4H), 6.95 (d, J = 7.5 Hz, 2H),
3
3
HP
HP HH HH
3
3
3
3
13
7
.72 (d, J = 11.9 Hz, 1H), 7.66−7.58 (m, 1H), 7.38 (d, J = 8.2
6.81 (dt, J = 18.4, J = 9.8 Hz, 11H). C NMR (75 MHz,
HP HH
HP
HH
3
Hz, 2H), 7.35−7.27 (m, 2H), 7.16 (t, J = 7.5 Hz, 1H), 4.27 (s,
CDCl ): δ 137.39−136.85 (m), 134.65 (s), 133.91 (s), 133.65 (s),
HH
3
31
3
H), 1.83−0.46 (m, 22H). P NMR (122 MHz, acetone): δ 54.77 (s).
133.49−133.37 (m), 130.87 (s), 130.33 (s), 130.02 (s), 128.64 (d, J =
Anal. Calcd for RuC H PSO Cl·0.2CH Cl : C, 50.17; H, 5.48.
9.2 Hz), 128.00−127.58 (m), 127.17 (s), 118.98−118.52 (m), 62.10
26
34
4
2
2
+
31
Found: C, 50.19; H, 4.42. HRMS [ESI ] RuC H PSO Cl: calcd
(s), 29.10 (s). P NMR (122 MHz, CDCl ): δ 35.54 (s). Anal. Calcd
2
6
34
4
3
+
+
5
75.0905 [M − Cl] , found 575.0958 [M − Cl] .
for RuC H P S O ·Et O: C, 62.41; H, 4.35. Found: C, 61.74; H,
5
1
38
2
2
6
2
t
[
P(-6-SO -C H )(Ph)( Bu)]Cl-Ru(CH-O-Me-C H ) (2c). Inside a
3
6
4
6
4
4.56. Anal. Calcd for RuC H P S O ·0.35CH Cl ·1.05Et O: C,
51 38 2 2 6 2 2 2
+
glovebox, Cl Ru(CH-o-OMeC H )PPh (40 mg, 0.073 mmol, 1.0
2 6 4 3
61.69; H, 4.59. Found: C, 61.74; H, 4.56. HRMS [ESI ]
equiv) and oc (56 mg, 0.173 mmol, 2.4 equiv) were added to a
+
RuC H P S O : calcd 975.0706 [M + H] , found 975.0782 [M +
51
38
2
2
6
Schlenk flask containing 4 mL of CHCl . The flask was equipped with
+
3
H] .
PCy )[P(-6-SO -C H )(Ph) ]Cl RuCH-Ph (9a). Inside a drybox,
a condenser, and the mixture was heated at 60 °C for 24 h. The
solvent was evaporated, and the crude was passed through a silica gel
column using CH Cl /CH OH = 10:1 v/v as eluent to yield a green
(
3
3
6
4
2
2
5
1
00 mg (0.123 mmol) of (PCy ) Cl RuCHPh and 63 mg (0.183
3
2
2
3
2
2
3
mmol 1.5 equiv) of 2-(diphenylphosphanyl)benzenesulfonic acid
were weighed in a vial, and 5 mL of CH Cl was added. The solution
1
solid (25 mg, 0.030 mmol, yield = 41%). H NMR (300 MHz,
3
3
3
2
2
acetone) δ 16.75 (ddd, J = 4.1, J = 2.3 Hz, 1H), 7.82 (t, J =
HP
HH
HH
was stirred at room temperature for 30 min. The solution was filtered
on Celite, and the solvent evaporated. Ether was then added on the
crude, and the solution was stirred for another 60 min. The mother
liquid was taken off, and the crude was dried in vacuo to yield the
desired product as a green solid (42.5 mg, 0.0502 mmol, 42%). H
NMR (300 MHz, CDCl ): δ 17.40 (dd, J = 16.3, J = 9.7 Hz,
H), 8.06−7.89 (m, 5H), 7.51−7.30 (m, 5H), 7.25 (t, J = 7.6 Hz,
H), 7.15 (d, J = 7.7 Hz, 1H), 7.07 (dd, J = 16.8, J = 7.9 Hz,
H), 6.98−6.88 (m, 2H), 6.53 (t, J = 8.6 Hz, 1H), 2.02 (dd, J
2.7, J = 11.3 Hz, 3H), 1.82 (s, 4H), 1.74 (d, J = 11.3 Hz, 4H),
3
7
.2 Hz, 1H), 7.72 (d, J = 11.9 Hz, 1H), 7.66−7.58 (m, 1H), 7.38
HP
3
3
(
1
d, J = 8.2 Hz, 2H), 7.35−7.27 (m, 2H), 7.16 (t, J = 7.5 Hz,
HH
HH
31
H), 4.27 (s, 3H), 1.83−0.46 (m, 22H). P NMR (122 MHz,
acetone): δ 65.11.
1
(
PPh )[P(-6-SO -C H )(Ph) ]Cl-Ru(Ind) (3a). Inside a glovebox,
3
3
6
4
2
3
3
3
HP
HH
[
RuCl (PPh ) ] (100 mg, 0.104 mmol, 1 equiv), 1,1-diphenyl-2-
2 3 3
3
1
1
4
2
1
1
HH
propyn-1-ol (33 mg, 0.156 mmol, 1.5 equiv), and 43 mg (0.125 mmol
.2 equiv) of ligand oa were weighed in a 50 mL Schlenk flask. After
adding 10 mL of CH Cl , the mixture was brought to reflux for 60
3
3
3
HH
HP
HH
1
3
3
=
HH
HP
2
2
3
3
HP
HP
min. The solvent was evaporated, and the green crude (73 mg, 0.079
mmol, 75%) was purified through column chromatography on silica
gel (CH Cl /diethyl ether = 87:13 v/v) (63 mg, 65%). Crystals were
3
.65−1.41 (m, 13H), 1.33 (s, 4H), 1.24−0.91 (m, 8H), 0.79 (d, J
=
HP
2.7 Hz, 1H). 31P NMR (122 MHz, CDCl ): δ 49.17 (d, J = 29.4
2
3
PP
2
2
2
1
Hz), 15.73 (d, J = 29.4 Hz). Anal. Calcd for RuC H P SO Cl·
PP 43 53 2 3
+
obtained by slow diffusion of diethyl ether in CH Cl . H NMR (300
2
2
3
CH Cl : C, 56.62; H, 5.94. Found: C, 56.43; H, 6.01. HRMS [ESI ]
2 2
MHz, CDCl ): δ 9.27 (d, J = 7.0 Hz, 1H), 8.26−8.17 (m, 2H), 7.95
3
HH
+
3
3
RuC H P SO Cl: calcd 813.2234 [M − Cl] , found 813.2199 [M −
(
(
(
dd, J = 6.4, J = 4.4 Hz, 1H), 7.69−7.34 (m, 19H), 7.29−6.95
43 53
2
3
HH
HH
+
3
3
3
Cl] .
m, 13H), 6.62 (ddd, J = 29.0, J = 14.8, J = 6.2 Hz, 3H), 5.36
HP
HP
HH
s, 1H). 13C NMR (75 MHz, CDCl ): δ 148.92−147.39 (m), 135.51−
(PCy )[P(-6-SO -C H )(Cy) ]Cl RuCH-Ph (9b). Inside a drybox,
3
3
6
4
2
2
3
9
2
0 mg (0.108 mmol, 1.0 equiv) of catalyst 1b and 67 mg (0.238 mmol,
1
1
1
1
34.76 (m), 134.41−134.03 (m), 133.50−133.11 (m), 131.48 (s),
30.14 (s), 129.80−129.62 (m), 129.28 (s), 128.75 (s), 128.68−
28.58 (m), 128.56−128.48 (m), 127.91 (d, J = 9.8 Hz), 126.94 (s),
.2 equiv) of PCy were weighed in a vial, and 5 mL of CH Cl was
3
2
2
added. The suspension was stirred at room temperature for 60 min.
The solution was filtered on Celite and the solvent evaporated. The
resulting green solid was found to be a mixture of catalyst 1b and 9b,
3
1
18.43 (s), 68.37−62.15 (m), 17.17−14.06 (m). P NMR (122 MHz,
2
2
CDCl ): δ 48.87 (d, J = 34.6 Hz), 19.90 (d, J = 34.6 Hz). Anal.
3
PP
PP
1
Calcd for RuC H P SO Cl·0.5Et O·0.5H O (1 molecule of Et O
which were not readily separated by column chromatography ( H
51
39
2
3
2
2
2
NMR yield 60%). 31P NMR (122 MHz, CDCl
): δ 26.37 (d, JPP
2
=
was found in the solid-state structure of 1a): C, 65.19; H, 4.61. Found:
3
+
2
C, 65.18; H, 4.62. HRMS [ESI ] RuC H P SO Cl: calcd 895.940632
239.8 Hz), 7.65 (d, J = 239.8 Hz).
General Procedure for RCM Tests. Inside a drybox, 1.7 mg of
catalyst 1b was weighed in a vial, and 1 mL of CDCl added (c = 2 ×
10 mol/L). In a separate vial, 10 (48 mg, 0.2 mmol) was added to 1
mL of CDCl . The combined solutions ([10]:[1b] = 100) were stirred
at 60 °C on a “Heat on Block” System carousel 12 Plus from Radleys
Technologies. The conversion of 10 into diethyl-3-cyclopentene-1,1-
51
39
2
3
PP
+
+
[
M − Cl] , found 895.05554 [M − Cl] .
P(-6-SO -C H )(Ph) ] RuCCCPh (4a). RuC H P S O
[
3
6
4
2 2
2
36 28
2
2
6
3
−3
(
100 mg, 0.127 mmol) and 1,1-diphenyl-2-propyn-1-ol (39.9 mg,
.191 mmol, 1.5 equiv) were weighed inside a glovebox in a 50 mL
0
3
Schlenk flask. A 10 mL amount of THF was added, and the reaction
mixture was heated overnight under reflux under N . The solvent was
evaporated, and the crude was purified through column chromatog-
raphy on silica gel (CH Cl /diethyl ether = 87:13 v/v) to give the
desired product as a red compound (106.7 mg, 0.109 mmol, 86%).
Crystals were obtained by slow diffusion of diethyl ether in CH Cl .
H NMR (300 MHz, CDCl ): δ 8.42 (s, 1H), 8.24 (s, 1H), 7.98 (s,
2
1
dicarboxylic acid was followed by H NMR. The conversion was
2
2
calculated by integrating the 1H resonance corresponding to the
product at 2.94 ppm and the resonance of the starting material at 2.58
ppm.
2
2
1
3
General Procedure for ROMP Tests. Inside a vial, 1 mg of
catalyst 1b (0.0012 mmol, 1 equiv) was dissolved in 1 mL of CDCl3.
In a 10 mL round-bottom flask, 130 mg of 14 (1.2 mmol, 1000 equiv)
was combined with the catalytic solution, and the mixture was heated
for 1 h at 60 °C. The reaction was stopped by adding 1 mL of ethyl
vinyl ether. The polymer was collected by methanol precipitation.
General Procedure for CM Tests. Inside a vial, 1.1 mg of catalyst
b (0.0012 mmol, 1 equiv) was dissolved in 1 mL of CDCl . In a small
vial, 20 μL of 15 (0.127 mmol, 100 equiv) was stirred at 60 °C on
“Heat on Block” System carousel 12 Plus. The conversion was
1
H), 7.79−7.38 (m, 10H), 7.36−6.94 (m, 14H), 6.91−5.86 (m, 11H).
3
1
P NMR (122 MHz, CDCl ): δ 44.58−42.18 (m), 40.88 (s), 38.62
3
(
s), 26.63−23.90 (m). Anal. Calcd for RuC H P S O ·0.55CH Cl :
51
38
2
2
6
2
2
C, 62.89; H, 3.93. Found: C, 60.66; H, 3.86. Anal. Calcd for
RuC H P S O ·0.6CH Cl ·0.4Et O: C, 60.59; H, 4.13. Found: C,
0.59; H, 4.14. HRMS [ESI ] RuC H P S O : calcd 975.0706 [M +
51
38
2
2
6
2
2
2
+
6
51 38 2 2 6
+
+
H] , found 975.0681 [M + H] .
P(-6-SO -C H )(Ph) ] Ru(Ind) (5a). In a 50 mL round-botton
1
3
[
3
6
4
2 2
flask, 132 mg (0.168 mmol) of 4a was added to 10 mL of CH Cl . The
2
2
mixture was cooled to −78 °C, and CF SO H (126 mg, 0.841 mmol, 5
1
3
3
measured by H NMR analysis of the mixture.
equiv) was added. The mixture was stirred for 2 h at −78 °C. Alumina
oxide basic grade I (0.5 g) was added, the mixture was stirred for
another 10 min, and the solution was filtered off. The crude was
concentrated and passed through a silica gel column (CH Cl /ether:
ASSOCIATED CONTENT
■
2
2
*
S
Supporting Information
1
1
00/15) to yield a green solid (161.3 mg, 0.165 mmol, 98%). H
NMR (300 MHz, CDCl ): δ 9.03 (d, J = 7.3 Hz, 1H), 8.02 (d, J
6.7 Hz, 2H), 7.53 (d, J = 13.2 Hz, 4H), 7.45 (dd, J = 15.3,
JHH = 7.6 Hz, 4H), 7.27 (q, J = 7.5 Hz, 5H), 7.21−7.11 (m, 8H),
3
3
Procedure for variable-temperature NMR experiments, NMR
spectra, MS spectra, and CIF files. This material is available free
of charge via the Internet at http://pubs.acs.org.
3
HH
HH
3
3
=
HP HP
3
3
HH
F
dx.doi.org/10.1021/om500212x | Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
(
28) Sundararaju, B.; Tang, Z.; Achard, M.; Sharma, G. V. M;
AUTHOR INFORMATION
■
*
Toupet, L.; Bruneau, C. Adv. Synth. Catal. 2010, 352, 3141−3146.
29) Piche, L.; Daigle, J.-C.; Rehse, G.; Claverie, J. P. Chem.Eur. J.
2012, 18, 3277−3285.
30) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997,
19, 3887−3897.
31) Sanford, M. S.; Love, J. A.; Grubbs, R. H. J. Am. Chem. Soc.
001, 123, 6543−6554.
(32) Zhou, X.; Jordan, R. F. Organometallics 2011, 30, 4632−4642.
33) Zhou, X.; Bontemps, S.; Jordan, R. F. Organometallics 2008, 27,
821−4824.
34) Vela, J.; Lief, G. R.; Shen, Z.; Jordan, R. F. Organometallics 2007,
6, 6624−6635.
35) Furstner, A.; Guth, O.; Du
B.; Mynott, R. Chem.Eur. J. 2001, 7, 4811−4820.
36) Harlow, K. J.; Hill, A. F.; Wilton-ely, J. D. E. T. J. Chem. Soc.,
Dalton Trans. 1999, 2, 285−291.
37) Jafarpour, L.; Stevens, E. D.; Nolan, S. P. Organometallics 1999,
Corresponding Author
E-mail: claverie.jerome@uqam.ca.
(
(
1
(
2
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
(
4
(
2
Prof. Glenn Yap (University of Delaware) is acknowledged for
X-ray crystallographic analysis. This work was supported by the
NSERC Discovery Program, using an infrastructure supported
by the NanoQuebec Major Infrastructure Program and the
́
FRQNT Center Fund.
(
̈
̈
ffels, A.; Seidel, G.; Liebl, M.; Gabor,
(
REFERENCES
■
(
(
(
(
(
(
1) Grubbs, R. H. Tetrahedron 2004, 60, 7117−7140.
2
(
, 5416−5419.
2) Grubbs, R. H. Angew. Chem., Int. Ed. 2006, 45, 3760−3765.
38) Castarlenas, R.; Vovard, C. J. Am. Chem. Soc. 2006, 4079−4089.
39) Werner, H.; Bosch, M.; Schneider, M. E.; Hahn, C.; Kukla, F.;
̈
3) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012−3043.
(
4) Fogg, D.; Conrad. Curr. Org. Chem. 2006, 10, 185−202.
Manger, M.; Windmu
Chem. Soc., Dalton Trans. 1998, 3549−3558.
40) Kabro, A.; Ghattas, G.; Roisnel, T.; Fischmeister, C.; Bruneau,
C. Dalton Trans. 2012, 41, 3695−3700.
41) Antonucci, A.; Bassetti, M.; Bruneau, C.; Dixneuf, P. H.;
̈
̈
ller, B.; Weberndorfer, B.; Laubender, M. J.
5) Deraedt, C.; D’Halluin, M.; Astruc, D. Eur. J. Inorg. Chem. 2013,
4
(
(
881−4908.
(
6) Endo, K.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 133, 8525−8527.
7) Keitz, B. K.; Endo, K.; Herbert, M. B.; Grubbs, R. H. J. Am. Chem.
(
Soc. 2011, 133, 9686−9688.
8) Keitz, B. K.; Endo, K.; Patel, P. R.; Herbert, M. B.; Grubbs, R. H.
J. Am. Chem. Soc. 2012, 134, 693−699.
9) Cannon, J. S.; Grubbs, R. H. Angew. Chem., Int. Ed. 2013, 52,
001−9004.
10) Endo, K.; Herbert, M. B.; Grubbs, R. H. Organometallics 2013,
2, 5128−5135.
11) Hartung, J.; Grubbs, R. H. J. Am. Chem. Soc. 2013, 135, 10183−
0185.
12) Khan, R. K. M.; O’Brien, R. V.; Torker, S.; Li, B.; Hoveyda, A.
H. J. Am. Chem. Soc. 2012, 134, 12774−12779.
13) Khan, R. K. M.; Zhugralin, A. R.; Torker, S.; O’Brien, R. V.;
Lombardi, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 2012, 134, 12438−
2441.
14) Rosebrugh, L. E.; Herbert, M. B.; Marx, V. M.; Keitz, B. K.;
Grubbs, R. H. J. Am. Chem. Soc. 2013, 135, 1276−1279.
15) Rosebrugh, L. E.; Marx, V. M.; Keitz, B. K.; Grubbs, R. H. J. Am.
Chem. Soc. 2013, 135, 10032−10035.
16) Vougioukalakis, G. C.; Grubbs, R. H. Chem. Rev. 2010, 110,
746−1787.
17) Occhipinti, G.; Bjørsvik, H.-R.; To
Organometallics 2007, 26, 5803−5814.
18) Chang, S.; Jones, L.; Wang, C.; Henling, L. M.; Grubbs, R. H.
Organometallics 1998, 17, 3460−3465.
19) Snelgrove, J. L.; Conrad, J. C.; Eelman, M. D.; Moriarty, M. M.;
Yap, G. P. A.; Fogg, D. E. Organometallics 2005, 24, 103−109.
20) Snelgrove, J. L.; Conrad, J. C.; Yap, G. P. A.; Fogg, D. E. Inorg.
Chim. Acta 2003, 345, 268−278.
21) Blacquiere, J. M.; McDonald, R.; Fogg, D. E. Angew. Chem., Int.
Ed. 2010, 49, 3807−3810.
22) Torker, S.; Muller, A.; Sigrist, R.; Chen, P. Organometallics 2010,
9, 2735−2751.
23) Torker, S.; Mu
762−3766.
24) Nakamura, A.; Anselment, T. M. J.; Claverie, J.; Goodall, B.;
Pasquini, C. Organometallics 2010, 29, 4524−4531.
(
(
(
́
42) Solin, N.; Szabo, K. J. Organometallics 2001, 20, 5464−5471.
43) (a) Simal, F.; Demonceau, A.; Noels, A. F.; Knowles, D. R. T.;
O’Leary, S.; Maitlis, P. M.; Gusev, O. J. Organomet. Chem. 1998, 558,
(
9
(
3
(
1
(
1
1
(
63−170. (b) Noels, A. F.; Demonceau, A. J. Phys. Org. Chem. 1998,
1, 602−609.
44) Koh, M. J.; Khan, R. K. M.; Torker, S.; Hoveya, A. H. Angew.
Chem., Int. Ed. 2014, 53, 1968−1972.
45) Pump, E.; Fischer, R. C.; Slugovc, C. Organometallics 2012, 31,
972−6979.
46) Hansen, S. M.; Rominger, F.; Metz, M.; Hofmann, P. Chem.
Eur. J. 1999, 5, 557−566.
47) Credendino, R.; Poater, A.; Ragone, F.; Cavallo, L. Catal. Sci.
Tech. 2011, 1, 1287.
48) Bieniek, M.; Michrowska, A.; Usanov, D. L.; Grela, K. Chem.
Eur. J. 2008, 14, 806−818.
49) Stephenson, T. A.; Wilkinson, G. J. Inorg. Nucl. Chem. 1966, 28,
45−956.
50) Evans, I. P.; Spencer, A.; Wilkinson, G. J. Chem. Soc., Dalton
Trans. 1973, 204−209.
51) Piche, L.; Daigle, J.-C.; Poli, R.; Claverie, J. P. Eur. J. Inorg. Chem.
010, 29, 4595−4601.
52) Ito, S.; Munakata, K.; Nakamura, A.; Nozaki, K. J. Am. Chem.
Soc. 2009, 131, 14606−14607.
53) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996,
18, 100−110.
54) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoveyda, A.
H. J. Am. Chem. Soc. 1999, 121, 791−799.
(
6
(
(
(
1
(
(
(
(
9
(
(
1
(
̈
rnroos, K. W.; Jensen, V. R.
(
2
(
(
(
(
1
(
(
(
(
2
(
3
̈
̈
ller, A.; Chen, P. Angew. Chem., Int. Ed. 2010, 49,
(
Jordan, R. F.; Mecking, S.; Rieger, B.; Sen, A.; van Leeuwen, P. W. N.
M.; Nozaki, K. Acc. Chem. Res. 2013, 46, 1438−1449.
(
25) Jiang, F.; Yuan, K.; Achard, M.; Bruneau, C. Chem.Eur. J.
2
013, 19, 10343−10352.
26) Sundararaju, B.; Achard, M.; Demerseman, B.; Toupet, L.;
Sharma, G. V. M.; Bruneau, C. Angew. Chem., Int. Ed. 2010, 49, 2782−
785.
27) Piche, L.; Daigle, J.-C.; Claverie, J. P. Chem. Commun. 2011, 47,
836−7838.
(
2
(
7
G
dx.doi.org/10.1021/om500212x | Organometallics XXXX, XXX, XXX−XXX