An [(NHC)(NHCEWG)RuCl2(CHPh)] complex for the efficient formation of sterically hindered olefins by ring-closing metathesis

Article abstract of DOI:10.1002/anie.200900935

NHC with EWGs for RCM: Ruthenium complexes with two N-heterocyclic carbenes (NHCs), one of them substituted with electron-withdrawing groups (EWGs), are highly efficient (pre) catalysts for the synthesis of tetrasubstituted olefins and trisubstituted olef

Full text of DOI:10.1002/anie.200900935

Angewandte
Chemie
DOI: 10.1002/anie.200900935
Homogeneous Catalysis
An [(NHC)(NHCEWG)RuCl2(CHPh)] Complex for the Efficient
Formation of Sterically Hindered Olefins by Ring-Closing
Metathesis**
Tim Vorfalt, Steffen Leuthꢀußer, and Herbert Plenio*
We recently learned that N,N’-diarylimidazolin-2-ylidenes
with electron-withdrawing substituents, such as 4-toluenesul-
fonyl-substituted aryl groups, have electron-donating proper-
ties that are comparable to tricyclohexylphosphine, PCy3.[1,2]
In second-generation catalysts for olefin metathesis,[3–5] the
latter ligand is important, as dissociation of PCy3 is the
initiating step for olefin metathesis.[6] Consequently, the
synthesis of complexes derived from 1 (Scheme 1) with an
complex should increase the stability of such complexes
towards oxidation and also avoid degradation pathways that
can arise in the presence of phosphine ligands.[7]
Complexes of the type [(NHC)2RuCl2(CHPh)], such as 2,
were reported as early as 1998 to be catalytically active in the
ring-opening metathesis polymerization (ROMP) of 2-nor-
bornene and cyclooctadiene.[8] Additional work by Grubbs
et al. with the complex 3 later revealed poor activities in
various RCM and ROMP reactions.[9] Those later studies,
together with the knowledge that NHC ligands bind more
strongly to metal centers than phosphines, may have been the
reason why such complexes have been studied only scarcely in
recent years. Modest ring-closing metathesis (RCM) and
ROMP activities were reported by He et al. with
[(NHC)2RuCl2(CHPh)] (NHC = N,N’-diarylimidazol-2-yli-
dene)[10] and by Ledoux, Verpoort et al.[11] for [(NHC)2RuCl2-
=
(CHPh)] (NHC N,N’-aryl,alkyl-imidazol-2-ylidene) com-
plexes. The latter authors also realized that in certain
[(NHC)2RuCl2(CHPh)] complexes, one NHC ligand can be
replaced by other ligands.[12]
These results led us to believe that such complexes also
provide new opportunities. The synthesis of tetrasubstituted
olefins by olefin metathesis still poses significant problems
with ruthenium-based catalysts.[13–17] The conditions used for
an example from Grubbs et al. illustrates some problems:[18]
Elevated temperatures (60–808C), high catalyst loading
(5 mol%), and extended reaction times (24 h) are required
for the RCM of such olefins; even under such conditions,
several olefins are incompletely converted, and others do not
react at all. In 2007, Clavier and Nolan reported indenylidene-
based ruthenium complexes; at 808C, 2.5–5 mol% of catalyst
are required to effect the 89–97% conversion into various
tetrasubstituted olefins.[19] In 2008, several groups reported
improvements: a) by reducing the steric bulk of the NHC
Scheme 1. Ruthenium NHC complexes for olefin metathesis. Cy=cy-
clohexyl.
electron-deficient N-heterocyclic carbene (NHC) ligand
instead of PCy3 appears to be an interesting target. The
obvious motivation is that NHC ligands with diminished
donor capacity might be more willing to act as leaving groups,
just as PCy3 does in second-generation complexes. Further-
more, the absence of a phosphine ligand in the ruthenium
ligand,[20,21] b) by designing NHC ligands with inhibited
[22]
À
rotation of the N-aryl groups to diminish C H activation,
and c) by using solvents of low dielectric constant, such as
hexafluorobenzene or octafluorotoluene.[23,24]
Herein we report a new type of ruthenium complex with
mixed NHC ligands, one of them being electron-rich, the
other one being (relatively) electron-deficient. The latter
ligand should be released from ruthenium to generate the
catalytically active species.
[*] Dipl.-Ing. T. Vorfalt, Dr. S. Leuthꢀußer, Prof. Dr. H. Plenio
Anorganische Chemie im Zintl-Institut, Technische Universitꢀt
Darmstadt
Petersenstrasse 18, 64287 Darmstadt (Germany)
E-mail: plenio@tu-darmstadt.de
First, facile synthetic access to NHC ligands substituted
with electron-withdrawing groups was required. The nitro
group is a strongly electron-withdrawing substituent that is
easily introduced into aromatic systems. The N,N’-dimesityl-
imidazolinium salt was converted into the tetranitrated
[**] This work was supported by the DFG and the TU Darmstadt.
NHC=N-heterocyclic carbene. NHCEWG =N-heterocyclic carbene
with electron-withdrawing groups.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.200900935.
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5191

Communications
imidazolinium salt 5 in about 90% yield by employing a
Consequently, all of the screening reactions were carried out
at 808C.
mixture of concentrated sulfuric and nitric acid (Scheme 2).
To probe the electron-releasing capacity of the NHC
ligand 5, the synthesis of the complexes [(5)IrCl(cod)] (cod =
The RCM of diethyl diallylmalonate and diallyltosyl-
amide was performed as an initial test for the reactivity of 6 at
elevated temperatures (Table1, entries 1, 2). At 808C,
0.1 mol% of complex 6 is sufficient to effect the quantitative
conversion (99%) of both substrates within 60 min. Following
these two simple RCM transformations, we attempted the
synthesis of a trisubstituted alkene (Table1, entry 3) with
intermediate bulk. Initially 0.5 mol%, then 0.25 mol%, and
finally 0.1 mol% of complex 6 were employed. Quantitative
conversion was observed for all reactions, even when using as
little as 0.1 mol% of complex 6. This compares well with a
specialized Grubbs–Hoveyda complex recently reported,
which produces 93% conversion of this substrate at 608C
with a tenfold higher catalyst loading of 1 mol%.[22]
Scheme 2. Synthesis of nitrated imidazolinium salt 5. Reagents and
conditions: a) H2SO4/HNO3; 18 h, 08C.
To enable the proper evaluation of the catalytic activity of
6, we screened three additional ruthenium complexes under
the same conditions as 6: a Grubbs first-generation complex,
the Grubbs second-generation complex 1, and the Grubbs–
Hoveyda complex 4. The results for the Grubbs first-
generation complex are not listed in Table1, as no conversion
was observed for any of the eight reactions (entries 4–11)
under the conditions specified in Table1. From the data listed
in Table1, it is also apparent that the performance of the
Grubbs second-generation complex 1 can not match that of
the bis(NHC) complex 6. Observed conversions range
between 2–52% (Table1, entries 4–11) at 0.5 mol% loading
and 808C. But for entry 11, even 0.25 mol% of 6 is sufficient
to effect full conversion. Even a drastically increased catalyst
loading for 1 of 2.5 mol% (Table1, entries 4, 7, 9, 10) cannot
match the performance of complex 6. The small increase in
conversion between 0.5 and 2.5 mol% loading indicates that
the decomposition of 1 is limiting the catalytic activity. The
performance of 4 for a few substrates gives respectable
results, but less-efficient RCM reactions are nonetheless
observed for entries 9, 10, and 11 (90%, 60%, and 58%
conversion), whereas for all other reactions (Table1,
entries 4–8), 6 performs much better than 4. The reaction in
entry 7 using 6, 1, and 4 was followed by recording the time–
conversion curves for each catalyst (see the Supporting
Information). Within the first few minutes of the reaction, 1
converts a significant amount of reactant, whereas both 6 and
4 remain latent. Those two complexes only start to produce
product after about 10 min, with 6 being much faster than 4.
The superior performance of complex 6 can be demon-
strated more convincingly by comparing the conversion data
for this complex with data provided by other groups for other
ruthenium complexes, as those data were presumably
obtained under optimized conditions for the respective
catalytic system. The tetrasubstituted alkene substrates
screened (Table1, entries 4–11) were tested by several other
groups using modified Grubbs second-generation com-
plexes,[18,20,21,28] Grubbs–Hoveyda species,[29] and indenyli-
dene catalysts.[19,30] Typical conditions employed by those
groups are 5 mol% of ruthenium complex at 608C or 2.5–
5 mol% at 808C. In contrast, between 0.25–1.0 mol% of
complex 6 are sufficient to obtain excellent yields of various
tetrasubstituted alkenes (Table1, entries 4–11, except for
1,5-cyclooctadiene) and [(5)IrCl(CO)2] was undertaken.
[(5)IrCl(cod)] is available by standard routes,[1] whereas the
synthesis of [(5)IrCl(CO)2] failed. To quantify the electron
donation of the NHC ligand 5, the redox potential of
[(5)IrCl(cod)] was determined to be E1/2 = 1.041 V, which is
significantly more anodic than that of the 4-toluenesulfonyl-
substituted complex (E1/2 = 0.910 V) previously reported.[1]
Plotting the redox potentials of several [(NHC)IrCl(cod)]
complexes against the respective nav(CO) values (see the
Supporting Information; based on data recently reported)[1]
allows an extrapolation of the nav(CO) values for the hypo-
thetical complex [(5)IrCl(CO)2] to 2034.5 cmÀ1. This value lies
between the nav(CO) of [(PiPr3)IrCl(CO)2] (2032 cmÀ1) and
[(PEt3)IrCl(CO)2] (2038 cmÀ1),[25] thus placing NHC ligand 5
among the least electron-donating NHC ligands reported to
date.[26,27]
The tetranitrocarbene 5, generated in situ from the
tetranitroimidazolinium salt, was used to synthesize the
[(NHC)(NHCEWG)RuCl2(CHPh)] complex 6 in 49% yield
(Scheme 3).
Scheme 3. Synthesis of complex 6. Reagents and conditions:
a) KOtBu, 5·H2SO4/HNO3, toluene; 20 min, 808C.
Complex 6 was tested in the RCM of various alkenes. The
screening results are summarized in Table 1. Complex 6 does
not display significant olefin metathesis activity at room
temperature, which was established by the RCM of diallylto-
sylamide. Employing a 0.5 mol% loading of 6 led to no
product formation at all after 24 h at 258C, and even after 24 h
at 508C, only 20% of product was formed. The catalyst
displays significant activity only at temperatures above 608C.
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Table 1: Ring-closing metathesis to form tetrasubstituted olefins.[a]
It is our working hypothesis that
the diminished electron-donating
properties of the tetranitrated
NHC 5 turn this ligand into a
better leaving group.[32] This pro-
posal was tested by screening two
RCM reactions of sterically
demanding substrates (Table1,
entries 5 and 10, indicated by foot-
note [d]) with 0.5 mol% of complex
3, which has two conventional NHC
ligands. In the first reaction
(Table1, entry 5), complex 6 gives
virtually quantitative conversion,
whereas the use of 3 results in
virtually no product formation. In
the second example (Table1,
entry 10), complex 6 again displays
drastically higher efficiency than 3.
This supports our idea that less
electron-donating NHC ligand 5 is
a better leaving group. It is, how-
ever, likely that the increased steric
bulk of the hexasubstituted N-aryl
groups of NHC 5 also contribute to
its leaving group quality by impos-
ing some steric strain in ruthenium
complex 6.
To provide additional evidence
for the ability of NHC ligands to act
as leaving groups, we probed the
substitution of the tetranitro NHC
in complex 6 and the mesityl NHC
in complex 3 ligands by pyridine.
The related reaction for the Grubbs
second-generation complex leading
to the replacement of a PCy3 ligand
by pyridine is known to be facile,
and the formation of the green
Entry Metathesis reaction
Catalyst loading [mol%]
6
1
4
1
0.1[b]
99%
–
–
2
3
0.1[b]
99%
–
–
–
–
0.1
99%
99%
99% (>95%)
0.25[b]
0.5[b]
0.5
48%
65%
78% (75%)
–
3% 6%
–
–
19%
0.5[c]
1.0
–
–
–
4
2.5
0.5
98% (>95%) 11% 28%
3% (–)
5
6
0.5[d]
–
–
0.5
26% (>20%) 2% 3%
0.5
2.5
98% ([e])
–
23% 68%
31%
7
8
–
0.5
80% ([e])
25% 25%
25% 64%
0.25
0.5
2.5
64%
9
99% (>95%) 26% 90%
–
35%
–
0.5
60%
14%
–
–
-
1.0
87% (87%)
7%[d] (–)
–
50%
–
–
10
0.5[d]
2.5
23%
0.25
0.5
99% (>95%) 37% 58%
99% 52% 99%
11
[a] General procedure for metathesis screen: 0.4 mmol substrate (0.02m in toluene), toluene stock
solution of 6, 1,or 4; 3 h at 808C. Conversion determined by GC analysis (yields of isolated product in
brackets); all GC peaks characterized by GC/MS; isolated RCM products identified by NMR
spectroscopy. Ts=4-toluenesulfonyl. [b] 60 min. [c] Five times 0.1 mol%. [d] [(NHC)2RuCl2(CHPh)], 3.
[e] Products too volatile for isolation.
complex
[(NHC)RuCl2-
(CHPh)(py)2] is complete within a
few minutes at room temperature.
Such ligand substitution reactions
involve significant color changes,
entry 6). The results reported herein also compare favorably
with the conversion data recently reported for a RCM in
hexafluorobenzene using 1–5 mol% of catalyst.[23] None of
the lactone (Table1, entry 6) was formed when using 5 mol%
of a Grubbs catalyst.[20] D’Annibale et al. reported a 40%
yield of this product when employing two times 10 mol% (to
give 20 mol%) of second-generation catalyst.[31] For the
formation of a cycloheptene derivative (Table1, entry 10)
the use of 5 mol% in a set of five different ruthenium
complexes enables conversions in the range of 34–87% at
and can thus be monitored conveniently by UV/Vis spectros-
copy. For complex 6 dissolved in pyridine, the replacement of
NHC 5 is fast and requires less than 4 min at 608C. For the
symmetrical complex 3 this reaction is much slower and takes
more than 1 h under the same reaction conditions. The
absence of a well-defined isosbestic point in the high-temper-
ature experiments is indicative of some decomposition of the
pyridine complex. Consequently, the same experiment was
repeated at 258C (Figure 1). The absorption maximum lmax
=
339 nm is due to complex 6, and the new lmax at 365 nm fits
well with the lmax = 368 nm for an isolated sample of
[(NHC)RuCl2(CHPh)(py)2]. The reaction of pyridine with
complex 3 is much slower at 258C; after 60 minutes, the
absorption band at 335 nm shows only little change, and at
least 600 minutes are required until the reaction with pyridine
608C.[18,20] The formation of
a tetrasubstituted alkene
(Table1, entry 11). was recently reported with various ruthe-
nium complexes using 2 mol%, 24 h at 408C in 80% yield,[30]
or 1 mol% at 708C in 99% yield,[29] or with 1 mol% at 808C
in 99% yield.[23]
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Communications
[4] M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron
Lett. 1999, 40, 2247.
[5] U. Frenzel, T. Weskamp, F. J. Kohl, W. C. Schattenmann, O.
Nuyken, W. A. Herrmann, J. Organomet. Chem. 1999, 586, 263.
[6] M. S. Sanford, J. A. Love, R. H. Grubbs, J. Am. Chem. Soc. 2001,
123, 6543.
[7] S. H. Hong, A. G. Wenzel, T. T. Salguero, M. W. Day, R. H.
Grubbs, J. Am. Chem. Soc. 2007, 129, 7961.
[8] T. Weskamp, W. C. Schattenmann, M. Spiegler, W. A. Herr-
mann, Angew. Chem. 1998, 110, 2631; Angew. Chem. Int. Ed.
1998, 37, 2490.
[9] T. M. Trnka, J. P. Morgan, M. S. Sanford, T. E. Wilhelm, M.
Scholl, T.-L. Choi, S. Ding, M. W. Day, R. H. Grubbs, J. Am.
Chem. Soc. 2003, 125, 2546.
[10] W. Zhang, C. Bai, X. Lu, R. He, J. Organomet. Chem. 2007, 692,
3563.
[11] N. Ledoux, B. Allaert, A. Linden, P. V. D. Voort, F. Verpoort,
Organometallics 2007, 26, 1052.
Figure 1. UV/Vis spectra of the NHC substitution reaction for 6
[12] N. Ledoux, A. Linden, B. Allaert, H. V. Mierde, F. Verpoort,
Adv. Synth. Catal. 2007, 349, 1692.
(4ꢁ10À5 m) in pyridine solvent. Each trace corresponds to 10 min
reaction time.
[13] A. Michrowska, R. Bujok, S. Harutyunyan, V. Sashuk, G.
Dolgonos, K. Grela, J. Am. Chem. Soc. 2004, 126, 9318.
[14] Q. Yao, Y. Zhang, J. Am. Chem. Soc. 2004, 126, 74.
[15] A. Fꢁrstner, L. Ackermann, B. Gabor, R. Goddard, C. W.
Lehmann, R. Mynott, F. Stelzer, O. R. Thiel, Chem. Eur. J. 2001,
7, 3236.
[16] H. Weychardt, H. Plenio, Organometallics 2008, 27, 1479.
[17] L. Ackermann, A. Fꢁrstner, T. Weskamp, F. J. Kohl, W. A.
Herrmann, Tetrahedron Lett. 1999, 40, 4787.
[18] J. M. Berlin, K. Campbell, T. Ritter, T. W. Funk, A. Chlenov,
R. H. Grubbs, Org. Lett. 2007, 9, 1339.
[19] H. Clavier, S. P. Nolan, Chem. Eur. J. 2007, 13, 8029.
[20] I. C. Stewart, T. Ung, A. A. Pletnev, J. M. Berlin, R. H. Grubbs,
Y. Schrodi, Org. Lett. 2007, 9, 1589.
[21] I. C. Stewart, C. J. Douglas, R. H. Grubbs, Org. Lett. 2008, 10,
441.
[22] C. K. Chung, R. H. Grubbs, Org. Lett. 2008, 10, 2693.
[23] D. Rost, M. Porta, S. Gessler, S. Blechert, Tetrahedron Lett. 2008,
49, 5968.
[24] C. Samojowicz, M. Bieniek, A. Zarecki, R. Kadyrov, K. Grela,
Chem. Commun. 2008, 6282.
[25] A. R. Chianese, X. Li, M. C. Janzen, J. W. Faller, R. H. Crabtree,
Organometallics 2003, 22, 1663.
is finished. In contrast to the reaction of 6 with pyridine, there
is also no clear evidence for the formation of [(NHC)RuCl2-
(CHPh)(py)2] from 3 and pyridine.
In conclusion, the tetranitrated NHC 5·HNO3/H2SO4 can
be synthesized in excellent yields by direct nitration of the
respective imidazolinium salt. The electron-donating capacity
of 5 is comparable to that of PiPr3 and PEt3, placing it among
the least electron-donating NHC ligands. A UV/Vis experi-
ment provides evidence for the tetranitro NHC being a better
leaving group than the mesityl NHC ligand. The easily
synthesized complex 6, of the general type [(NHC)-
(NHCEWG)RuCl2(CHPh)], is a highly efficient pre-catalyst
for the ring-closing metathesis of substituted alkenes; the
formation of tetrasubstituted alkenes require loadings of only
0.25–1 mol%, and for a trisubstituted alkene, as little as
0.1 mol% is sufficient. We are currently studying the activity
of complex 6 in other olefin metathesis reactions as well as
modifying the nature of both NHC ligands to obtain even
more active catalysts.
[26] D. M. Khramov, V. M. Lynch, C. W. Bielawski, Organometallics
2007, 26, 6042.
[27] W. A. Herrmann, J. Schꢁtz, G. D. Frey, E. Herdtweck, Organo-
metallics 2006, 25, 2437.
[28] A. Fꢁrstner, O. R. Thiel, L. Ackermann, H.-J. Schanz, S. P.
Nolan, J. Org. Chem. 2000, 65, 2204.
Received: February 17, 2009
Published online: June 3, 2009
[29] M. Bieniek, A. Michrowska, D. L. Usanov, K. Grela, Chem. Eur.
J. 2008, 14, 806.
[30] D. Rix, F. d. Caijo, I. Laurent, F. Boeda, H. Clavier, S. P. Nolan,
M. Mauduit, J. Org. Chem. 2008, 73, 4225.
[31] A. DꢂAnnibale, L. Ciaralli, M. Bassetti, C. Pasquini, J. Org.
Chem. 2007, 72, 6067.
[32] J. A. Love, M. S. Sanford, M. W. Day, R. H. Grubbs, J. Am.
Chem. Soc. 2003, 125, 10103.
Keywords: homogeneous catalysis · N-heterocyclic carbenes ·
metathesis · ring-closing metathesis · ruthenium
.
[1] S. Leuthꢀußer, D. Schwarz, H. Plenio, Chem. Eur. J. 2007, 13,
7195.
[2] S. Leuthꢀußer, V. Schmidts, C. M. Thiele, H. Plenio, Chem. Eur.
J. 2008, 14, 5465.
[3] J. K. Huang, E. D. Stevens, S. P. Nolan, J. L. Petersen, J. Am.
Chem. Soc. 1999, 121, 2674.
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