5530 J . Am. Chem. SOC.

1992, 114, 5530-5534

gel (1 g, 25% ethyl acetate/hexane) afforded 45 (23.1 mg, 73%): IR 7.43-7.53(m,3 H, phenyl CH), 7.56-7.67 (m, 2 H, phenyl CH). Anal.
(neat) 2975,2925,1720,1700, 1600, 1460,1440,250,1180, 1040,760, Calcd for C,8H2005:C, 68.34;H, 6.37. Found: C, 68.54;H, 6.60.
690;'H NMR (270MHz, CDCIj) 6 0.92 (s, 3 H, CCHj), 1.21 (d, J =
7.3 Hz, 3 H, CHCHj), 1.31 (t, J = 7.1 Hz, 6 H, two OCH,CHj), Acknowledgment. This research was financially supported by
4.13-4.50(m,5 H, two OCH,CHj, CHCHj), 6.35 (s, 1 H, olefinic CH), the Ministry of Education, Science and Culture, Japan.

Electronic Stabilization of Nucleophilic Carbenes'

Anthony J. Arduengo, III,* H.V. Rasika Dias, Richard L. Harlow, and Michael Kline
Contribution No. 6107 from Du Pont Central Research, Experimental Station, Wilmington,
Delaware 19880-0328. Received January 14, 1992

Abstract: Four new stable nucleophilic carbenes have been synthesized and structurally characterized. The remarkable ability
of the imidazole nucleus to stabilize a carbene center at the C-2 position is demonstrated by the isolation of 1,3,4,5-tetra-
methylimidazol-2-ylidene. The isolation of three imidazol-2-ylidenes that bear aryl substituents is counter to speculations
based on previous reports.

Introduction IH N M R spectrum (thf-d,) shows only two resonances of equal

CarbenesZare two-coordinate carbon compounds that have two area at 2.01 and 3.48 for the methyls on carbon and nitrogen. The
nonbonding electrons and no formal charge3 on the carbon. These I3C N M R spectrum has a resonance at 6 213.7 similar to the value
types of two-coordinate carbon compounds essentially represent of 21 1.4 found for the carbene center of 3 (Table I).
carbon in an oxidation state of 11. Oxidation state I1 is well
represented in carbon chemistry by stable monocoordinated carbon
centers such as those in carbon monoxide (C=O) and isonitriles
( R - N 4 ) . In biochemistry, structures such as thiamine-derived
intermediates can be formulated as either zwitterions (ylides) or
i3H,
~ a r b e n e s .However,
~ in the absence of isolable model compounds,
the best characterization for these important intermediates remains 1 2
a matter for speculation. Stable compounds in the carbene Cooling a toluene solution of 2 gave crystals suitable for X-ray
category have been made only recently, and definite structural diffraction studies. The resulting structure for 2 is shown in Figure
and electronic information is now availablea5-' Apparently, the 1. Selected bond lengths and angles are given in Table 11. The
stability of these carbenes is derived from a combination of steric molecule sits on a crystallographic 2-fold axis. The five ring atoms
and electronic factors. These factors achieve the stability necessary are planar by symmetry, and the methyl carbons at nitrogen and
for isolation. We now describe the syntheses and structures of carbon deviate by 0.023 and 0.049 A, respectively, from the
four new stable carbenes. Structural features of these new molecular plane.
carbenes suggest that steric factors are unimportant in contributing The KANVAS~drawing in Figure 1 illustrates the unencumbered
to the stability of the imidazol-2-ylidenes. geometry of the carbene center in 2. The lack of significant steric
Results and Discussion hindrance in 2 starkly contrasts the previously synthesized stable
Most remarkably, carbene 2 (1,3,4,5-tetramethylimidazol-2- carbene, 1,3-di( l-adamantyl)imidazol-2-ylidene (3).5 The
ylidene) is obtained in 89% yield when 1,3,4,5-tetramethyl- structures of 2 and 3 are quite similar, but there are some slight
imidazolium chloride (1) is treated with 1 equiv of sodium hydride differences that are noteworthy. The valence angle at the carbene
and 5 mol % potassium tert-butoxide in tetrahydrofuran (thf) (eq center in 2 is 0.7' smaller than the same angle in 3. The ring
1). Carbene 2 is a colorless crystalline solid melting at 109-1 10 internal angle at nitrogen is 1.3' larger for 2 compared to 3. The
'C. A previously melted sample of 2 showed no depression of N1(3)-C2 bond distance is 0.7 pm shorter in 2 than in 3. The
the melting point upon remelting. Samples of 2 could be purified N1(3)-C5(4) bond distance is 1.2 pm longer and the ring C-C
by recrystallization from toluene or vacuum sublimation. The distance is 1.4 pm longer in 2 than in 3. These differences bring
the experimental structure of 2 very close to the calculated
( I ) Dedicated to Dr. H. E. Simmons, Jr. on the occasion of his retirement.
structure for the unsubstituted imidaz01-2-ylidene.~ This result
(2)The term 'carbene" was first used in connection with this type of supports our earlier assumption9 that small differences in the
structure in a Chicago taxi; see: Doering, W. v E.; b o x , L. H. J . Am. Chem. calculated structure for the unsubstituted imidazol-2-ylidene and
SOC.1956, 78, 4947 footnote 9. the experimental structure of 3 are the result of steric influences
( 3 ) The formal charge at an atom is determined by its valence bond of the 1-adamantyl substituent on the imidazole ring. Very similar
representation. The significance offormal charges has been discussed else-
where: Pauling, L. The Nafure of the Chemical Bond, 3rd ed.; Cornell trends can be seen among the structures observed for the 1,3-
University Press: Ithaca, NY, 1960; pp 8 and 9 and references therein. di( 1-adamantyl)imidazolium and 1,3-dimethylimidazolium ions
(4)For a recent paper on the generation of thiamine-related intermediates, and the structure calculated for the unsubstituted imidazolium
see: Bordwell, F. G.; Satish, A. V. J . A m . Chem. SOC.1991, 113, 985. For ion.
a more comprehensive review, see: Kluger, R. Chem. Reu. 1987, 87, 863.
( 5 ) Arduengo, A. J., 111; Harlow, R. L.; Kline, M . J . Am. Chem. SOC. We also have observed another sterically unencumbered
1991, 113, 361. carbene, 1,3-dimethylimidazol-2-ylidene(4), in solution. Although
(6)Bertrand et al. have reported a stable compound than can be charac-
terized either as a X'-phosphinocarbene or as X5-phosphaacetylene structures;
see: Igau, A.; Grutzmacher, H.; Baceiredo, A,; Bertrand, G. J . Am. Chem. (8)These drawings were made with the KANVAS computer graphics pro-
SOC.1988, 110, 6463 and Igau, A.; Baceiredo, A,; Trinquier, G.; Bertrand, gram. This program is based on the program SCHAKAL of E. Keller (Kris-
G. Angew. Chem., Inf. Ed. Engl. 1989, 28, 621. Recent theoretical models tallographisches Institute der Universitat Freiburg, Germany), which was
suggest that the best description is as a Xs-phosphaacetylene; see: Dixon, D. modified by A. J. Arduengo, I11 (Du Pont Central Research, Wilmington, DE)
A.; Dobbs, K. D.; Arduengo, A. J., 111; Bertrand, G. J. Am. Chem. SOC.1991, to produce the back and shadowed planes. The planes bear a 50-pm grid and
113, 8782. the lighting source is at infinity so that shadow size is meaningful.
( 7 ) Regitz, M . Angew. Chem., I n f . Ed. Engl. 1991, 30, 674. (9)Dixon, D. A,; Arduengo, A. J., 111 J. Phys. Chem. 1991, 95, 4180.

0002-786319211514-5530$03.00/0 0 1992 American Chemical Society

Electronic Stabilization of Nucleophilic Carbenes J . Am. Chem. Soc., Vol. 114, No. 14, 1992 5531

Table I. Selected N M R Chemical Shifts (ppm) in 2-4 and 7-90qb

nucleus 2 3 4 7 8 9
13C2 213.7 211.4' 215.2 219.7 215.8 216.3
13C4(5) 123.1 1 13.9' 120.5 121.3 118.8 119.2
IH4(5) 7.02 (6.9lC) 6.92 7.04 (6.48') 1.64 (6.96') 7.76 (6.68)'
"Nw -198.5 -160.5' -197.3 -178.9
''N~(3) -198 -161' -197.5 -1 80 -171 -174
'The numbering scheme for all compounds is as indicated for 2. thf-d, solution. References are tetramethylsilane or NH4+NO3-. c I n
benzene-&, solution.

Table 11. Selected Bond Lengths (um) and Anales (des) in 2,3. and 7-9"
property 2 3 7 8 9
r(c2-Nl(3)) 136.3 (1) 136.7 (2), 137.3 (2) 136.5 (41, 137.1 (4) 137.1 (2), 137.5 (2) 136.8 (2), 136.8 (2)
r(C4-Cs) 135.2 (2) 133.8 (3) 133.1 (5) 133.4 (2) 133.9 (2)
r(Nl(3)-c5(4)) 139.4 (1) 138.2 (2), 138.6 (2) 138.1 (4), 137.8 (4) 139.2 (2), 139.4 (2) 139.1 (2), 139.2 (2)
r(Ni(3,subst) 145.4 (1) 148.2 (2), 148.5 (2) 144.1 (4), 144.2 (4) 143.0 (2), 143.0 (2) 143.0 (2), 143.0 (2)
r(C4(5)-subst) 149.0 (1) 96.8 (20), 95.9 (22) 88.5 (36), 95.1 (48) 95.6 (16), 96.5 (19) 92.2 (17), 94.8 (16)
W'JI-C~-N~) 101.5 (1) 102.2 (2) 101.4 (2) 101.2 (1) 101.7 (1)
e(c5(4)-Nl(3)-c2) 113.47 (8) 112.1 (2), 112.3 (2) 112.8 (3), 112.8 (3) 112.9 ( l ) , 113.0 (1) 112.8 ( I ) , 112.8 (1)
B(N1(3)-C5(4)-C4(5)) 105.78 (5) 107.2 (2), 106.2 (2) 106.5 (3), 106.5 (3) 106.6 (2), 106.2 (1) 106.4 (I), 106.3 (1)
B(C,-NI(~)-SU~S~) 122.9 (1) 123.4 (2), 122.1 (2) 121.8 (2), 122.6 (2) 123.1 ( l ) , 122.9 (1) 122.6 ( I ) , 122.0 (1)
B ( N I ( ~ ) - C ~ ( ~ ) - S U ~ S122.8
~ ) (1) 124 ( l ) , 123 (1) 125 (3), 125 (2) 124 ( l ) , 123 (1) 123 ( l ) , 124 (1)
'The numbering scheme for all compounds is as indicated for 2.

The final stabilizing feature of 3 is the steric effect of the two

adamantyl substituents. This steric effect should hinder reaction
of the carbene center with external reagents. Prior to our discovery
of 2, it has not been possible to evaluate the relative importance
of the steric and electronic factors.
The only previous evidence which has bearing on the relative
importance of steric and electronic factors in stabilizing imid-
azol-Zylidenes is supplied by H.-W. Wanzlick," who recognized
the potential for an imidazole ring to stabilize a carbene center
at the 2-position. Wanzlick studied two specific imidazole de-
rivatives, 512 and 6.13

Figure 1. KANVAS* drawing of 2.

4 persists in solution for days without decomposition, it is an

unstable oily liquid when pure. The imidazole ring protons at C4(5)
in 4 exhibit a resonance at 6 6.92 in the IH N M R spectrum
(thf-d,). In the 13C N M R spectrum a resonance is found at 6
215.2 for the carbene center. The multitude of decomposition 5 6
products from 4 have not been characterized. In light of the stability of 2, it is puzzling that 5 and 6 were
not isolated as stable solids. Both 5 and 6 are expected to be solids,
so that their stability and isolation seem assured. It is possible
that there is some subtle electronic effect of the phenyl rings that
prevents the imidazole nitrogens from sufficiently stabilizing the
adjacent carbene center. To separate the u- and *-effects of the
N-aryl substituents, we decided to attempt the synthesis of two
aryl-substituted carbenes 7 and 8.

3 4
The stability of 3 was attributed to a combination of steric and
electronic factor^.^^^ The electronic factors operate in both the
r - and u-framework. In the *-framework, electron donation into
the carbene out-of-plane p-orbital by the electron-rich system
(N-C=C-N) leads to a moderation of the typical electrophilic
reactivity of carbenes. In the u-framework, additional stability
for the carbene electron pair may be gained from the u-elec-
tron-withdrawal effects on the carbene center by the more elec-
tronegative nitrogens. This u-effect would serve to moderate the
nucleophilic reactivity of a 1A' carbene. The combination of these
u- and *-effects serves to increase the singlet-triplet gap and
stabilize the singlet carbene over the more reactive triplet ~ t a t e . ~ J ~
(1 1 ) Wanzlick, H.-W. Angew. Chem., I n t . Ed. Engl. 1962, I, 75.
(10) More recently this "push-pull" synergistic effect has been invoked for (12) Schonherr, H.; Wanzlick, H. Chem. Ber. 1970, 103, 1037.
halocarbenes: Irikura, K. K.; Goddard, W. A,, 111; Beauchamp, J. L. J . A m . (13) Wanzlick, H.; Schonherr, H. Justus Liebigs Ann. Chem. 1970, 731,
Chem. SOC.1992, 1 1 4 , 4 8 . 176.
5532 J. Am. Chem. SOC.,Vol. 114, No. 14, 1992 Arduengo et al.

Figure 4. K A N V A S ~drawing of 9.
benzene as a colorless solid melting at 156-1 58 OC dec. The NMR
Figure 2. KANVAS* drawing of 7. spectra (thf-d,) of 8 reveal the carbene center at 6 215.79 and
the remaining imidazole ring protons at 6 7.64 (Table I). This
chemical shift for the imidazole ring protons at Cq5) is substantially
downfield of resonances for the same protons in 3,4, and 7. This
shift difference is most likely the result of anisotropy of the aryl
groups in 8 which can adopt a more nearly planar arrangement
than in 7. A similar chemical shift is observed for another
aryl-substituted imidazol-2-ylidene, 9, which bears no ortho
substituents (vide infra).I4
Crystals of 8 were obtained by allowing a warm saturated
benzene/diethyl ether solution to cool to room temperature. The
X-ray crystal structure of 8 is depicted in Figure 3, and selected
bond lengths and angles are given in Table 11. As in 7, the
Figure 3. KANVAS* drawing of 8. imidazole ring is essentially planar with no atom deviating from
the best plane by more that 0.003 A. Substituent atoms at both
The mesityl substituents of carbene 7 provide an opportunity nitrogens are also essentially coplanar with deviations of 0.012
to observe the a-effect of an aryl substituent since the o-methyls and 0.042 A. The two tolyl substituents are more nearly planar
will prevent conjugation between the phenyl rings and the nitrogen with the imidazole ring than in 7; however, they are still twisted
centers. On the other hand, thep-tolyl substituents of 8 will allow with interplane angles of 31' and 34O. The twists of the tolyl
a *-effect because the rings can assume a planar (conjugating) substituents are in the same direction as found in 7, so that again
arrangement. there is a pseudo 2-fold axis.
Carbene 7 ( 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) There does not seem to be any strong sensitivity of imidazol-
is obtained in 84% yield when 1,3-bis(2,4,6-trimethylphenyl)- 2-ylidene stability to the electronic character of N-aryl substituents.
imidazolium chloride is treated with 1 equiv of potassium tert- The substituent constant, up, for a 4-methyl group is -0.170.15
butoxide in thf. Carbene 7 is a colorless crystalline solid melting For a 4-chloro substituent up is 0.277.15 The pK,'s of the cor-
at 150-1 55 OC dec. Samples of 7 can be purified by recrystal- responding anilinium ions for p-toluidine and p-chloroaniline are
lization from hexane. The 'H N M R spectrum (thf-d,) of 7 shows 5.08 and 4.15, respectively.16 In spite of this difference of almost
a resonance for the imidazole ring protons at C4(5)of 7.04, which 1 order of magnitude in nitrogen basicity, the carbene with N-
is quite similar to the values in 3 (7.02 in thf-de) and 4 (6.92 in p-chlorophenyl substituents is as easily prepared and isolated as
thf-d,). The I3C N M R spectrum of 7 reveals the carbene reso- is 8.
nance at 6 219.69, similar to the carbene centers in 2-4 (Table F' F'
1).
Cooling a hexane solution of 7 gave crystals suitable for X-ray
diffraction studies. The X-ray crystal structure of 7 is depicted I
in Figure 2. Selected bond lengths and angles are given in Table
11. The imidazole ring is essentially planar, with no atom deviating
from the best plane by more than 0.005 A. Substituent atoms
"IA$. - "IN):
H N
KO'BU
thf
H N
(3)

\ CI' \
at both nitrogens are also essentially coplanar with deviations of
0.059 and 0.030 A. The two mesityl substituents are substantially
twisted with respect to the imidazole plane with interplane angles
of 80° and 71O. The orientation of the mesityl substituents is
Q CI CI

conrotatory, such that there is a pseudo 2-fold axis passing through 9

the carbene center.
The twists of the mesityl substituents in 7 prevent conjugation Carbene 9, 1,3-bis(p-chlorophenyl)imidazol-2-ylidene,is ob-
with the imidazole ring. The mesityl substituents substantially tained in 43% isolated yield when 1,3-bis(p-chlorophenyl)-
hinder the imidazole ring from above and below due to the four imidazolium chloride reacts with potassium tert-butoxide in thf
o-methyls. However, approach to the carbene center in the plane (eq 3). Carbene 9 crystallizes from warm benzene as a colorless
appears to be unencumbered as indicated in Figure 2. Carbene solid melting at 153-1 55 O C dec. Similar to 8, the NMR spectra
7 does not survive melting at 150 OC but is sufficiently stable to (thf-d,) of 9 reveal the carbene center at 6 216.28 and the re-
allow isolation and easy manipulation. It does not appear that
there is any special a-effect of aryl substituents that detracts from (14) A related set of chemical shift variations can be seen for the 2 6-
proton in styrene (6 5.59). 2,4,6-trimethylstyrene (6 5.21), and 3,3-di-
imidazol-2-ylidene stability. methyl-I-butene (6 4.78). These latter shifts were observed in CC,: Sadtler
The general compatibility of the imidazol-2-ylidene moiety with Proton NMR Spectra, Sadtler Research Laboratories, spectra no.'s 6408,
simple aryl substituents is demonstrated by the synthesis and 8899, and 53 18, respectively. It should be noted that 2,4,6-trimethylstyrene
isolation of carbene 8. Carbene 8, 1,3-bis(4-methylphenyl)- probably has more rotational freedom than 7 due to the absence of a second
a-substituent.
imidazol-2-ylidene, is isolated in 45% yield from reaction of ( 1 5 ) Swain, C. G.; Lupton, E. C., Jr. J. Am. Chem. SOC.1968,90,4328.
1,3-bis(4-methylphenyl)imidazoliumchloride with potassium (16) CRC Hundbook ojChemistry and Physics; Chemical Rubber Pub-
tert-butoxide in thf (eq 2). Carbene 8 crystallizes from warm lishing Company: Boca Raton, FL, 1986-1987; pp D159-160.
Electronic Stabilization of Nucleophilic Carbenes Vol. 114, No. 14, 1992 5533
J . Am. Chem. SOC.,
maining imidazole ring protons at 6 7.76 (Table I). The imidazole as precursors in our work were difficult to dry. Wanzlick has noted
ring protons again show a downfield shift due to the anisotropic a decomposition pathway for imidazol-Zylidenes involving water.'*
effects of the unhindered aryl substituents. We are continuing to explore the chemistry of these stable
Crystals of 9 were obtained by allowing a warm saturated nucleophilic carbenes.'* The range of substituents that can be
benzene solution to cool to room temperature. The X-ray crystal tolerated in the para positions of the N-arylimidazol-2-ylidenes
structure of 9 is depicted in Figure 4, and selected bond lengths is also under study.
and angles are given in Table 11. As in the previous structures,
the imidazole ring is essentially planar with no atom deviating Experimental Section
from the best plane by more than 0.003 A. Substituent atoms Reactions and manipulations were carried out under an atmosphere
at both nitrogens are also essentially coplanar with deviations of of dry nitrogen, either in a Vacuum Atmospheres dry box or using
standard Schlenk techniques. Solvents were dried (using standard pro-
0.072 and 0.049 A. The two p-chlorophenyl substituents have c e d u r e ~ ) distilled,
,~~ and deoxygenated prior to use, unless otherwise
inclinations with respect to the central imidazole ring similar to indicated. Glassware was oven-dried at 160 OC overnight. IH N M R
those in 8 (interplane angles of 28O and 39O). However, the twists spectra were recorded on a General Electric QE-300 spectrometer. IT,
of the p-chlorophenyl substituents are in an orientation opposite 14N, and I5N N M R spectra were recorded on a G E Omega 300 MHz
(disrotatory) that found in 7 and 8, so that there is no pseudo 2-fold WB spectrometer. N M R references are (CH,),Si (IH, I3C) and
axis but rather a pseudo mirror plane which is normal to the NH4+N03-.(I4N, I5N). Melting points were obtained on a Thomas-
imidazole ring. Hoover capillary apparatus and were not corrected. Elemental analyses
We have previously shown that theoretical models of the im- were performed by Oneida Research Services, Whitesboro, NY.
idazol-2-ylidenes exhibit a small valence angle a t the carbene 1,3,4,5-Tetramethylimidazol-2-ylidene(2). A 50-mL round-bottom
flask was charged with 1,3,4,5-tetramethyIimidazolium chloride (1)20
center as well as the long carbene-substituent bond distances which (5.25 g, 32.7 mmol), a stir bar, and 15 mL of thf. To this suspension
are characteristic of 1A' states for carbenes like :CH2and :CF2.9 was added oil-free sodium hydride (863 mg, 35.9 mmol) in a single
The structures of these four new stable carbenes all possess these portion. The suspension was stirred for 3 min to insure good mixing, and
same geometric features. The structures of the imidazol-Zylidenes 184 mg (1.64 mmol, 5 mol %) of potassium tert-butoxide in 5 mL of thf
show consistent differences from the structures of imidazolium was added as a single portion. The flask was capped with a septum, and
ions, as we have previously d i s c ~ s s e d .Typically,
~ imidazolium the rate of hydrogen evolution was monitored by piercing the septum with
ions have N-C-N angles in range the 108.3-109.7O, and the a hypodermic needle connected to an oil-filled bubbler. After 4 h the
lengths of the C2-N1(3)bonds range from 131.5 to 133.5 pm." reaction mixture was filtered through Celite, and the filtercake was
These differences between imidazolium (carbenium) ions and washed with thf (2 X 25 mL). The combined filtrate and washes were
concentrated under vacuum to give 3.46 g (89%) of 2 as a light yellow
imidazol-2-ylidenes show that the imidazol-2-ylidenes respond to solid. 1,3,4,5-Tetramethylimidazol-2-ylidene could be further purified
protonation as would be expected for 1A' carbenes. by recrystallization from thf or toluene to afford colorless crystals with
The exceptional stability observed for the adamantyl-substituted mp 109-110 "C: ' H N M R (thf-d,) 6 2.01 (s, CCH,, 6 H), 3.48 (s,
carbene (3) is at least partially derived from the steric hindrance NCH,, 6 H); "C N M R 6 8.98 (s, CCH,), 35.24 (bs, NCHJ), 123.05 (s,
offered by the adamantyl substituents. However, the electronic NCC), 213.73 (s, NCN); I5N N M R 6 -198.52 (reference NH41JN0,).
stabilization of the carbene center in imidazol-Zylidenes is suf- A sublimed sample of 2 gave satisfactory (f0.4%) C, H, and N analyses.
ficient to provide stable, easily isolable carbenes even in the absence 1,3-Dimethylimidazol-2-ylidene (4). A 300-mL round-bottom flask
of steric protection, as demonstrated by the isolation of 2, 8, and was charged with 1,3-dimethylimidazolium chloride20 (10.28 g, 77.57
9. mmol),2.05 g (85.4 mmol) of oil-free sodium hydride, a stir bar, and 150
mL of thf. The suspension was stirred for 3 min to insure good mixing,
Conclusions and 400 mg (3.6 mmol, 5 mol %) of potassium rert-butoxide in 10 mL
of thf was added as a single portion. The flask was capped with a septum,
All four new carbene structures show the small valence angle and the rate of hydrogen evolution was monitored by piercing the septum
at the carbene center which is characteristic of 1A' carbenes. The with a hypodermic needle connected to an oil-filled bubbler. After 4.25
long C2-N,(3)bond distance is also typical for imidazol-Zylidenes. h the reaction mixture was filtered through Celitie, and the filtercake was
Five substituent groups from alkyl (methyl and 1-adamantyl) to washed with thf (2 X 20 mL). The combined filtrate and washes were
aryl (mesityl, p-tolyl, and p-chlorophenyl) have been shown to concentrated under vacuum to give a light yellow viscous liquid. The oily
yield stable imidazol-2-ylidenes. In spite of the large variatioin liquid was transferred to a short-path distillation apparatus and flash
in steric bulk and electronic character, the imidazol-Zylidene distilled to give 4 as a mobile clear liquid. Approximately half of the
material remained in the distillation pot as a dark, extremely viscous oil.
moiety does not show any large structural variations. Contrary The fresh distillate of 4 gave the following N M R spectra (thf-d,): 'H.
to the results of Wanzlick et al., the isolation of stable carbenes 6 3.63 (s, CH,, 3 H), 6.92 (s, NCH, 2 H); "C, 6 36.1 (s, CH,),120.5
7-9 demonstrates that aryl substituents can be tolerated on the (s, NCC), 215.2 (s, NCN); 15N, 6 -197.28 (reference NH4IJNO3). In
imidazol-Zylidene nucleus without severely affecting the stability. thf solution the oily liquid 4 is somewhat stable and can be stored for
It is interesting to note that all three of the aryl-substituted several days at -30 OC without substantial decomposition. However, as
carbenes have melting points of approximately 155 OC with de- a neat liquid 4 darkens and becomes extremely viscous even at low tem-
composition. Possibly all of the aryl-substituted imidazol-2-yl- peratures. There appears to be a multitude of decomposition products
idenes undergo decomposition with similar activation energies. from 4,and they have not been identified. It was not possible to identify
The stability of the aryl-substituted imidazol-Zylidenes is not as N M R resonances for any material that might be the dimer.
great as that observed for the adamantyl-substituted compound 1,3-Bis(2,4,6-trimethylphenyl)imidazol-2-ylidene(7). A 200-mL
round-bottom flask equipped with a stir bar was charged with 10.0 g
3. (29.3 mmol) of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloridez0 and
The amazing stability of 2 proves that electronic stabilization 80 mL of thf. The resulting suspension was stirred for 15 min. Solid
of the carbene center in imidazol-2-ylidene is sufficient to produce potassium tert-butoxide (3.5 g, 31.2 mmol) was added to the suspension
stable species without the need of steric hindrance. Although 2, at room temperature in a single portion. A dark gray solution was
3, and 7-9 have indefinite stability in the solid state, 8 and 9 obtained immediately. The mixture was stirred for 20 min, and volatiles
decompose slowly in solution over a period of several days. We were removed under vacuum. The residue was extracted into warm
could not identify the dimer (olefin) among the decomposition toluene (2 X 50 mL) and filtered through Celite, and the solvent was
products. Why Wanzlick did not isolate carbenes 5 and 6 as stable removed in vacuo to provide small crystals of carbene 7 (7.55 g, 84%).
solids is not known, but we found that the imidazolium salts used
(18) Arduengo, A. J., III; Kline, M.; Calabrese, J. C.; Davidson, F. J. Am.
Chem. SOC. 1991, 113, 9704.
(17) For structures of representative imidazolium ions, see: (a) 1.3-di- (19) Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purification of
methylimidazolium chloride (supplementary material, this work). (b) 1,3- Laboratory Chemicals; Pergamon: New York, 1985.
di( 1-adamanty1)imidazoliumtetraphenylborate (ref 5 , supplementary mate- (20) These 1,3-disubstituted imidazolium chlorides are available by es-
rial). (c) Langer, V.;Huml, K.; Reck, G. Acta Crystallogr., Sect. B 1982, tablished procedures: Arduengo, A. J., I11 U S . Patent 5 077 414, 1991.
38, 298. (d) Luger, P.; Ruban, G. Z.Kristallogr. 1975, 142, 177. (e) 1,3-Dimethylimidazolium chlorides are also available by alkylation of the
Abdul-Sada, A. K.; Greenway, A. M.; Hitchcock, P. B.; Mohammed, T. J.; appropriately substituted imidazole with 1.1 equiv of methyl chloride in thf
Seddon, K. R.; Zora, J. A. J. Chem. SOC.,Chem. Commun. 1986, 1753. at room temperature (sealed bomb).
5534 J . Am. Chem. SOC.,Vol. 114, No. 14, 1992 Arduengo et al.
Crude 7 was recrystallized from hexane to obtain colorless crystals: mp structure was solved by direct methods (SHELXS) and refined by full-
150-155 O C dec; ' H NMR (thf-d,) 6 2.02 (s, 2,6-CH3, 12 H), 2.30 (s, matrix least-squares on F. Carbons and nitrogens were refined with
4-CH3, 6 H), 6.94 (s, ArH, 4 H), 7.04 (s, NCH, 2 H); ''C NMR 6 18.04 anisotropic thermal parameters. Hydrogens were refined with isotropic
(s, 2,6-CH3), 21.04 (s, 4-CH3), 121.28 (s, NCC), 129.69 (s, Mes C-3,5), thermal parameters. The largest residual electron density in the final
135.73 (s, Mes C-2,6), 137.55 (s, Mes C-4), 139.73 (s, Mes C-l), 219.69 difference Fourier map was 0.16 e/A'. The data/parameter ratio was
(s, NCN); I5N NMR 6 -178.85 (reference NH,''NO3). A recrystallized 5.08. The final R factors were R = 0.049 and R, = 0.039. Further
sample of 7 gave satisfactory (f0.4%) C, H, and N analyses. details of the crystal structure are available in the supplementary ma-
1,3-Bis(4-methylpbenyl)imidazol-2-ylidene(8). A 100-mL round- terial.
bottom flask equipped with a stir bar was charged with 1.61 g (5.65 Crystal data for 8 at -85 OC with Mo Ka radiation: a = 785.9 (2),
mmol) of 1,3-bis(4-methylphenyI)imidazoliumchloride" and 50 mL of b = 941.9 (2), c = 1879.7 (4) pm; @ = 100.45 (2)O; monoclinic, P2,/n;
thf. The resulting suspension was stirred for 15 min. Potassium rert- Z = 4; p(Mo) = 0.67 cm-I; 1745 unique reflections with I > 241). The
butoxide (0.650 g, 5.76 mmol) in 5 mL of thf was added to the suspension structure was solved by direct methods (SHELXS) and refined by full-
at room temperature in a single portion. The mixture was stirred for 20 matrix least-squares on F. Carbons and nitrogens were refined with
min. The volatiles were removed under reduced pressure, and the residue anisotropic thermal parameters. Hydrogens were refined with an iso-
was extracted into warm benzene (50 mL). The benzene solution was tropic thermal parameter. The largest residual electron density in the
filtered through Celite. The filtrate was concentrated in vacuo and final difference Fourier map was 0.16 e/A3 near the carbene center. The
diluted with hexane to induce crystallization. The crystalline product was data/parameter ratio was 7.02. The methyl group on the phenyl attached
collected by filtration and rinsed with diethyl ether (2 X 1 mL) then to N-3 was refined with a 2-fold rotational disorder and a 0.5 occupancy
hexane (2 mL) and dried under vacuum to afford 0.640 g (45%) of 8. for each conformer. The final R factors were R = 0.038 and R, = 0.033.
Crystals of 8 began to soften at 152 OC and melted at 156-158 OC dec: Further details of the crystal structure are available in the supplementary
'H NMR (thf-d,) 6 2.34 (s, CH3,6 H), 7.20 (dm, JHH = 8.74 Hz, m-CH, material.
4 H), 7.64 (s, NCH, 2 H), 7.79 (dm, JHH = 8.48 Hz, 0-CH, 4 H); I'C Crystal data for 9 at -70 OC with Mo K a radiation: a = 2539.9 (5),
NMR 6 20.87 (s, CH,),118.78 (s, NCC), 121.06 (s, Ar C-3,5), 130.19 b = 891.6 (3). c = 1143.2 (2) pm; @ = 97.62 (1)'; monoclinic, C2/c; Z
(s, Ar C-2,6), 136.12 (s, Ar C-4), 140.98 (s, Ar C-1), 215.79 (br s, = 8; @(Mo)= 4.91 cm-I; 2262 unique reflections with I > 341). The
NCN); l4N NMR 6 -171 (reference NH414N03). Anal. Calcd for structure was solved by direct methods (SHELXS) and refined by full-
CI7Hl6N2:C, 82.22; H, 6.49; N, 11.28. Found: C, 82.24; H, 6.49; N, matrix least-squares on F. Carbons, chlorines, and nitrogens were refined
10.77. with anisotropic thermal parameters. Hydrogens were refined with an
1,3-Bis(4-chlorophenyl)imidazol-2-ylidene ( 9 ) . A 100" round- isotropic thermal parameter. The largest residual electron density in the
bottom flask equipped with a stir bar was charged with 0.500 g (1.53 final difference Fourier map was 0.23 e/A' near one of the meta carbons
mmol) of 1,3-bis(4-chlorophenyI)imidazolium chloride*O and 20 mL of of a p-chlorophenyl substituent. The data/parameter ratio was 10.65.
thf. The resulting suspension was stirred for 15 min. Potassium tert- The final R factors were R = 0.030 and R, = 0.030. Further details of
butoxide (0.189 g, 1.68 mmol) in 5 mL of thf was added to the suspension the crystal structure are available in the supplementary material.
at room temperature in a single portioin. The mixture was stirred for Crystal data for 1,3-dimethylimidazolm chloride at -70 OC with Mo
20 min. The volatiles were removed under reduced pressure, and the Ka radiation: a = 865.2 (6), b = 785.8 (2), c = 1053.9 (8) pm; @ =
residue was extracted into warm benzene (50 mL). The benzene solution 106.34 (3)O; monoclinic, P2,/n;Z = 4; ~ ( M o = ) 4.54 cm-I; 1212 unique
was filtered through Celite. The filtrate was concentrated in vacuo and reflections with I > 3 4 . The structure was solved by direct methods
diluted with hexane to induce crystallization. The crystalline product was (MULTAN) and refined by full-matrix least-squares on F. Carbons,
collected by filtration and rinsed with diethyl ether (2 X 1 mL) then chlorines, and nitrogens were refined with anisotropic thermal parame-
hexane (2 mL) and dried under vacuum to afford 0.190 g (43%) of 9 ters. Hydrogens were refined with an isotropic thermal parameter. The
(softened at 150 OC, melted with decomposition at 153-155 "C): IH largest residual electron density in the final difference Fourier map was
NMR (thf-d,) 6 7.42 (dm, JHH = 9.12 Hz, m-CH, 4 H), 7.76 (s, NCH, 0.15 e/A3 near one of the ring carbons. The data/parameter ratio was
2 H), 7.93 (dm, JHH = 8.85 Hz, o-CH, 4 H); I3C NMR 6 119.24 (s, 11.12. The final R factors were R = 0.029 and R, = 0.035. Further
NCC), 122.54 (s, Ar C-3,5), 129.89 (s, Ar C-2,6), 132.22 (s, Ar C-4), details of the crystal structure are available in the supplementary ma-
141.69 (s, Ar C-l), 216.28 (br s, NCN); I4N N M R 6 -174. A sample terial.
of 9 gave satisfactory (&0.4%) C, H, and N analyses.
Crystal Data for 2 at -100 "C with Mo Ka radiation: a = 977.7 (2), Acknowledgment is made to Dr. T. Fukunaga for helpful dis-
b = 692.9 (2), c = 1060.5 (2) pm; @ = 94.00 (2)"; monoclinic, C2/c; Z cussions. The excellent technical assistance of H. A. Craig, L.
= 4; p(Mo) = 0.66 cm-l; 758 unique reflections with I > 341). The F. Lardear, and W. F. Marshall made much of this work possible.
structure was solved by direct methods (SHELXS) and refined by full- F. Davidson kindly provided the multinuclear NMR spectra.
matrix least-squares on F. Carbons and nitrogen were refined with
anisotropic thermal parameters. Hydrogens were refined with isotropic Supplementary Material Available: A complete description of
thermal parameters. The largest residual electron density in the final the X-ray crystallographic structure determinations on 1,3,4,5-
difference Fourier map was 0.23 e/A3 near C-4(5). The data/parameter tetramethylimidazol-2-ylidene(2), 1,3-bis(2,4,6-trimethyl-
ratio was 11.45. The final R factors were R = 0.040 and R, = 0.044.
Further details of the crystal structure are available in the supplementary phenyl)imidazol-2-ylidene (7), 1,3-di(p-tolyl)imidazol-2-ylidene
material. (8), 1,3-di(p-chlorophenyl)imidazol-2-ylidene(9), and 1,3-di-
Crystal data for 7 at -100 OC with Mo Ka radiation: a = 835.1 (2), methylimidazolium chloride including experimental procedures,
b = 1301.2 (3), c = 880.0 (2) pm; @ = 109.39 (1)O; monoclinic, P2,; 2 tables of data, and ORTEP structure drawings (21 pages).
= 2; ~ ( M o =) 0.61 cm-'; 1542 unique reflections with I > 241). The Ordering information is given on any current masthead page.