Polyhedron 49 (2013) 200–206

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Polyhedron
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Coordination diversity of Ag(I) and Hg(II) towards symmetrically and

non-symmetrically substituted imidazol-2-ylidenes: Synthesis, crystal
structures, nitrile reactivity, and Hofmann-type elimination studies
Abbas Washeel Salman, Rosenani A. Haque ⇑, Srinivasa Budagumpi 1, H. Zetty Zulikha
The School of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Two mesityl bridged bis-1H-imidazolium salts having bromide/hexafluorophosphate counter ions have
Received 31 May 2012 been prepared, compared with similar ortho-xylyl bridged salts and characterized by various spectral
Accepted 2 September 2012 and X-ray diffraction techniques. The salt having 2-cyanoethyl substituents undergoes hydrolysis to pro-
Available online 23 September 2012
duce compartmental 1H-imidazolium salts. Further, these salts are involved in the Hofmann-type elim-
ination to produce bis-imidazole and Ag(I)- and Hg(II)-coordination compounds when treated with Ag2O
Keywords: and Hg(OAc)2 in different ratios. Furthermore, a 3-nitrile-substituted imidazolium salt was prepared and
Hofmann elimination
treated with the aforementioned metal sources to evaluate the elimination reaction. However, it forms
Hg(II)-coordination
N-Heterocyclic carbene
stable N-heterocyclic carbene (NHC) complex without eliminating any of the cyano-substitutions. Both,
Silver(I)-coordination imidazolium salts and Ag(I)- and Hg(II)-coordination/NHC complexes have been characterized by 1H
X-ray diffraction and, 13C NMR, FTIR spectral, and elemental and single crystal X-ray diffraction analyses.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Nitrogen-functionalized imidazole or benzimidazole based N-
heterocyclic carbenes (NHCs) play important roles in the formation
of catalytically active nickel(II), palladium(II), rhodium(II) and plat-
inum(II) complexes and they have been used extensively as scaf-
folds for catalyst development [1,2]. The rapid assembly of
molecular diversity is an important goal in the preparation of cat-
alytically active species. In this context, silver(I)–NHC complexes
are important for the preparation of active species in homogeneous
catalysis by transmetallation to other transition metal–NHC com-
plexes [3]. These NHC precursors act as ligands and are excellent
choices due to their stable coordination to the metal center via
deprotonation. The type of metal–carbene carbon bonding depends
on the nature of the metal ion/atom and the substituents on the
heterocycle. Particularly, numerous imidazole based NHC ligands
have been prepared to control the reactivity and selectivity of
the derived complexes in catalysis.
The conversion of a halogen-stabilized imidazolium salt into
bulkier anion stabilized species can be achieved using a strongly
basic ion exchange resin [4]. This anion exchange will certainly af-
⇑ Corresponding author. Tel.: +60 19 4118 262, +60 4 653 3578.
E-mail address: rosenani@usm.my (R.A. Haque).
1
Current Address: Department of Chemistry, Faculty of Science, Universiti
Teknologi Malaysia, 81310 UTM Skudai, Johor, Malaysia.
fects the stability and reactivity of the imidazole nitrogen atoms.
For example, in the Hofmann elimination reaction, a quaternary
ammonium iodide is converted into its hydroxide counterpart
using a strongly basic ion exchange resin. Further, the hydroxide-
stabilized salt is decomposed into an amine and an olefin under
an atmosphere of nitrogen introduced on pressure equalization.
Recently, we have described the synthesis and successful char-
acterization of a series of aryl–alkyl and heterocycle bridged 1H-
bis-imidazolium derivatives showing formation of N-coordinated
Ag(I)/Hg(II) complexes (Scheme 1) [5]. The Hofmann elimination
reaction illustrates a general method for preparing olefins by the
elimination of an amine and a b-hydrogen atom in the presence
of a base, such as silver oxide [6]. This method is more suitable
for adaptation to large-scale laboratory preparation than the Wittig
modification, where hazardous liquid ammonia is used as a base.
Conversely, olefins can be formed from the nitrogenous salts even
in absence of a base; however, this formation depends on the nat-
ure and reactivity of the eliminated group.
On the other hand, NHC precursors of imidazole and benzimid-
azole derivatives can also undergo Hofmann-type elimination sim-
ilar to quaternary ammonium salts [7]. NHC precursors are being
more reactive than the quaternary ammonium salts; hence rapid
elimination is possible even in the absence of a base. In connection
with our studies and others on synthesis of biomimetic N-substi-
tuted imidazoles and their Ag(I)/Hg(II)–NHC complexes [8–10], we
needed an imidazole series with a variety of nitrile-functionalities

0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.09.020
 A.W. Salman et al. / Polyhedron 49 (2013) 200–206
Scheme 1. Synthetic route for the preparation of salts 3a and 4a, and silver(I)/mercury(II) complexes 5a–c.
suitable for large scale preparation. Eventually, we found an unprec-
edented elimination of a propionitrile group from the salt, even in
the absence of a base. Herein, we present interesting examples of
Hofmann-type elimination reactions observed in aryl–alkyl bridged
imidazole-based compartmental NHC precursors and their mode of
coordination with Ag(I) and Hg(II).
2. Experimental
2.1. Materials, methods, and instruments
All chemicals and solvents were obtained from commercial
sources and used without further purifications. The imidazole,
Ag2O, Hg(OAc)2, 3-bromopropionitrile and 3-bromomethyl benz-
omitrile were purchased from Sigma–Aldrich. 1,3-Dibromomethyl
mesitylene and 1,3-bis(10 -imidazole) mesitylene were prepared
according to the literature [11,12] method with slight modifica-
tions. The FT-IR spectra of the compounds were recorded in potas-
sium bromide disks using a Perkin Elmer 2000 system
spectrometer in the range 4000–400 cm1. The NMR spectra were
recorded in d6-DMSO using Bruker 500 MHz Ascend and and
Avance 300 MHz spectrometers at ambient temperature with
TMS as an internal reference. The instruments are available in
the School of Chemical Sciences, Universiti Sains Malaysia. All the
compounds were analyzed for C, H, and N using a PerkinElmer
2400 Series II microanalyzer. The X-ray diffraction data were col-
lected using a Bruker SMART APEX2 CCD area-detector diffractom-
eter. Calculations, structure refinement, molecular graphics and
the material for publication were performed using the SHELXTL and
PLATON (Spek, 2009) software packages.
201
2.2. Synthesis of imidazolium salts 2,4-bis(N-cyanoethylimidazolium-
1-ylmethyl)-1,3,5-trimethylbenzene dibromide (2b) and 2,4-bis(3-H-
1-ylmethyl)-1,3,5-trimethylbenzene dibromide (3b) [5]
The salt 2b was prepared from the reaction of 1,3-bis(imidazole-
1-ylmethyl)-mesitylene 1b (0.281 g, 1 mmol) with 3-bromopropio-
nitrile (0.268 g, 2 mmol) in acetonitrile (30 mL) at 80 °C for 20 h.
The resulted solid isolated by decantation then washed with diethyl
ether (2  5 mL) and dried in desiccator to give the product 2b as
off-white solid in 78% yield. FTIR (KBr disc) cm1: 2865, 2930
m(C–H, aliphatic and aromatic), 2223 m(C„N), 1610 m(C@N, imidaz-
ole). 1H NMR (300 MHz, d6-DMSO): d 2.24 (3H, s, Ar-CH3), 2.28 (6H,
s, 2  Ar-CH3), 3.34 (4H, t, 2  CH2-CN), 3.92 (4H, t, 2  N-CH2), 5.47
(2H, s, 2  benzylic CH2), 7.16 (1H, s, ArH), 7.53 (2H, t, 2  imidazo-
lium H50 ), 7.67 (2H, t, 2  imidazolium H40 ) and 8.92 (2H, s, 2  imi-
dazolium H20 ). 13C{1H} NMR (75.5 MHz, d6-DMSO): d 16.3 (CH3-Ar),
20.2 (2  CH3-Ar), 47.8 (CH2-CN), 48.8 (CH2-N), 49.0 (benzylic CH2),
120.9 (2  CN), 122.6 (imidazolium C50 & C40 ), 129.4 (Ar-CH), 132.1
(2  ArC), 135.7 (imidazolium C20 ), 139.8 (2  Ar-CH3) and 140.5
(Ar-CH3). The salt 3b resulted from 2b as yellow crystals after
attempting to grow suitable crystals for X-ray analysis by slow
evaporation in acetonitrile at ambient temperature for several days.
FTIR (KBr disc) cm1: 2860, 2932 m(C–H, apliphatic and aromatic),
1617 m(C@N, imidazole). 1H NMR (300 MHz, d6-DMSO): d 2.25 (3H,
s, Ar-CH3), 2.29 (6H, s, 2  Ar-CH3), 5.48 (2H, s, 2  benzylic CH2),
7.20 (1H, s, ArH), 7.54 (2H, t, 2  imidazolium H50 ), 7.69 (2H, t,
2  imidazolium H40 ) and 8.92 (2H, s, 2  imidazolium H20 ).
13
C{1H} NMR (125.0 MHz, d6-DMSO): d 15.4 (CH3-Ar), 19.4
(2  CH3-Ar), 47.0 (benzylic CH2), 120.2, 121.7 (imidazolium C50
and C40 ), 128.6 (Ar-CH), 131.2 (2  ArC), 134.9 (imidazolium C20 ),
202 A.W. Salman et al. / Polyhedron 49 (2013) 200–206
138.9 (2  Ar-CH3) and 139.6 (Ar-CH3). Anal. Calc. for C17H22N4Br2:
C, 46.2; H, 5.0; N, 12.7. Found: C, 46.3; H, 5.3; N, 12.6%.
2.3. Synthesis of imidazolium salt 2,4-bis(3-H-1-ylmethyl)-1,3,5-
trimethylbenzene dihexafluorophosphate (4b)
The salt 3b (1 mmol) was directly converted into their PF6 coun-
terpart 4b by the metathesis reaction using KPF6 (2.5 mmol) in
methanol (20 mL). The mixture was stirred for 2 h and left to stand
overnight. The white precipitate was collected, washed with dis-
tilled water and dried at room temperature. Yield: 93.4%. 1H and
13
C NMR spectra of 4b in d6-DMSO were almost similar to the
respective bromide salt.
2.4. Synthesis of silver(I) complex bis-[2,4-bis(3-H-1-ylmethyl)-1,3,5-
trimethylbenzene] disilver(I) bromide (6a)
Complex 6a was prepared in a similar way to 5a [5], from 3b
(0.571 g, 1 mmol) and Ag2O (0.58 g, 2.5 mmol) in acetonitrile
(30 mL). Yield: 81.6%, M.P.: 238 °C. FTIR (KBr disc) cm1: 2868,
2938 m(C–H, aliphatic and aromatic), 1593 m(C@N, imidazole). 1H
NMR (300 MHz, d6-DMSO): d 2.12 (6H, s, Ar-CH3), 2.72 (6H, s,
2  Ar-CH3), 5.81 (4H, s, 2  benzylic CH2), 7.32 (1H, s, ArH), 7.73
(2H, t, 2  imidazolium H50 ), 7.91 (2H, t, 2  imidazolium H40 )
and 8.44 (2H, s, 2  imidazolium H20 ). 13C{1H} NMR (75.0 MHz,
d6-DMSO): d 13.8 (CH3-Ar), 17.9 (2  CH3-Ar), 51.3 (benzylic
CH2), 126.6, 127.9 (imidazolium C50 and C40 ), 129.6, 132.1
(2  ArC), 138.1 (imidazolium C20 ), 138.6 (2  Ar-CH3) and 139.3
(Ar-CH3). Analytical data of the complex was in good agreement
with the reported results [14].
2.5. Synthesis of silver(I) complex bis-[2,4-bis(3-H-1-ylmethyl)-1,3,5-
trimethylbenzene] disilver(I) hexafluorophosphate (6b)
Complex 6b was prepared in a similar way to 5a, from 4b
(0.529 g, 1 mmol) and Ag2O (0.58 g, 2.5 mmol) in acetonitrile
(30 mL). Yield: 88.6%, M.P.: 238 °C. Characterization data of 6b
using FTIR and 1H and 13C NMR spectral techniques was almost
same as 5a. Anal. Calc. for C34H40N8Ag2P2F12: C, 38.3; H, 3.8; N,
10.5. Found: C, 38.7; H, 3.3; N, 11.0%.
2.6. Synthesis of mercury(II) complex bis-[2,4-bis(3-H-1-ylmethyl)-
1,3,5-trimethylbenzene] dimercury(II) hexafluorophosphate (6c)
Complex 6c was prepared in a similar way to 5c, from 4b
(0.529 g, 1 mmol) and Hg(OAc)2 (0.479 g, 1.5 mmol) in acetonitrile
(30 mL). Yield: 71.3%, M.P.: 241.3 °C. FTIR (KBr disc) cm1: 2860,
2931 m(C–H, aliphatic and aromatic), 1590 m(C@N, imidazole). 1H
NMR (300 MHz, d6-DMSO): d 2.12 (6H, s, Ar-CH3), 2.68 (6H, s,
2  Ar-CH3), 5.80 (4H, s, 2  benzylic CH2), 7.45 (1H, s, ArH), 7.81
(4H, t, 2  imidazolium H50 ), 7.89 (4H, t, 2  imidazolium H40 )
and 8.71 (2H, s, 2  imidazolium H20 ). 13C{1H} NMR (75.0 MHz,
d6-DMSO): d 11.3 (CH3-Ar), 18.7 (2  CH3-Ar), 52.1 (benzylic
CH2), 125.3, 127.4 (imidazolium C50 and C40 ), 128.6, 130.6
(2  ArC), 140.5 (imidazolium C20 ), 137.0 (2  Ar-CH3) and 137.7
(Ar-CH3). Anal. Calc. for C34H40N8Hg2P4F24: C, 26.5; H, 2.6; N, 7.3.
Found: C, 30.0; H, 2.3; N, 7.4%.
2.7. Synthesis of 1,3-bis-(3-cyanomethylbenzene)imidazolium
hexafluorophosphate (7)
Imidazole (0.34 g, 5 mmol) and KOH (0.45 g, 8 mmol) were stir-
red for 30 min in DMSO (30 mL). 3-Bromomethyl benzonitrile
(0.98 g, 5 mmol) was added in one portion and stirring was contin-
ued at room temperature for further 2 h. After the solvent was re-
moved under reduced pressure, water (400 mL) was added. The
aqueous phase was extracted with CH2Cl2 (4  25 mL) and organic
phase was taken. The residue was obtained after solvent removal
under reduced pressure. The resulting residue was dissolved in
1,4-dioxane and another portion of 3-bromomethyl benzonitrile
(0.98 g, 5 mmol) was added. The reaction mixture was heated un-
der reflux for overnight. The white precipitate obtained was fil-
tered off and washed with fresh dioxane and left to dry at
ambient temperature. Further, the resulting bromide salt (0.43 g,
1.1 mmol) was converted quantitatively to its hexafluorophos-
phate counterpart by metathesis reaction using KPF6 (0.2 g,
1.1 mmol) in 25 mL of methanol. The precipitate formed was col-
lected and washed with distilled water (2  3 mL), recrystallized
from acetonitrile to give white solid. Yield: 90.48%, M.P: 184–
184.5 °C. FTIR (KBr disc) cm1: 3085, 2865 m(C–H, aliphatic and
aromatic), 2236 m(C„N, nitrile), 1617 m(C@N, imidazole). 1H
NMR (500 MHz, d6-DMSO): d 5.47 (4H, s, 2  benzylic CH2), 7.63
(2H, t, Ar–H), 7.77 (4H, t, Ar–H), 7.82 (2H, d, imidazole 4H), 7.89
(2H, d, imidazole 5H), 9.31 (1H, s, imidazolium H20 ). 13C{1H}
NMR (125.0 MHz, d6-DMSO): d 51.3 (benzylic CH2), 111.93
(C„N), 118.31, 122.93, 130.25, 132.09, 133.35, 135.76 (Ar–C),
136.75 (imidazolium C20 ). Anal. Calc. for C16H16N4P1F6: C, 51.2; H,
3.6; N, 12.6. Found: C, 51.3; H, 2.9; N 12.5%.
2.8. Synthesis of silver(I) complex bis-[1,3-bis-(3-
cyanomethylbenzene)imidazolium] silver(I) hexafluorophosphate (8a)
Complex 8a was prepared in a similar way to 5a, from 7
(0.892 g, 2 mmol) and Ag2O (0.229 g, 1 mmol) in methanol
(30 mL). Yield: 81.87%, M.P.: 199.5–200.0 °C. FTIR (KBr disc)
cm1: 2932, 2872 m(C–H, apliphatic and aromatic), 2231 m(C„N,
nitrile), 1674 m(C@N, imidazole). 1H NMR (500 MHz, d6-DMSO): d
5.33 (4H, s, 2  benzylic CH2), 7.44 (2H, t, Ar–H), 7.56 (4H, t, Ar–
H), 7.68 (2H, d, imidazole 4H), 7.75 (2H, d, imidazole 5H).
13
C{1H} NMR (125.0 MHz, d6-DMSO): d 53.96 (benzylic CH2),
111.64 (C„N), 118.26, 122.93, 128.73, 130.12, 133.79, 134.52
(Ar–C), 180.58 (Ag-imidazolium C20 ). Anal. Calc. for C38H28N8-
AgPF6: C, 53.7; H, 3.3; N, 13.2. Found: C, 54.1; H, 2.9; N, 13.5%.
2.9. Synthesis of mercury(II) complex bis-[1,3-bis-(3-
cyanomethylbenzene)imidazolium] mercury(II) hexafluorophosphate
(8b)
Complex 8b was prepared in a similar way to 8a, from 7
(0.892 g, 2 mmol) and Hg(OAc)2 (0.319 g, 1 mmol) in methanol
(30 mL). Yield: 73.98%, M.P.: 208–208.7 °C. FTIR (KBr disc) cm1:
2930, 2864 m(C–H, aliphatic and aromatic), 2237 m(C„N, nitrile),
1671 m(C@N, imidazole). 1H NMR (500 MHz, d6-DMSO): d 5.45
(4H, s, 2  benzylic CH2), 7.49 (2H, t, Ar–H), 7.61 (4H, t, Ar–H),
7.73 (2H, d, imidazole 4H), 7.86 (2H, d, imidazole 5H). 13C{1H}
NMR (125.0 MHz, d6-DMSO): d 52.57 (benzylic CH2), 111.06
(C„N), 118.90, 123. 30, 129.83, 132.10, 134.03, 135.82 (Ar–C),
167.71 (Hg-imidazolium C20 ). Anal. Calc. for C38H28N8HgPF6: C,
42.0; H, 2.6; N, 10.3. Found: C, 42.1; H, 2.7; N, 10.1%.
3. Results and discussion
3.1. Syntheses
Introduction of an N-alkyl-aryl spacer in the imidazole bearing a
free NH group usually enhances the reactivity of the other nitrogen
atom to react with different or the same alkylating agent to give
the desired bis-alkylated imidazolium salt. Conversely, an N-
substituted azole with an alkyl group having an electron-with-
drawing b-substituent preferentially undergoes dequarternization
and is eliminated from the salt in the presence of a strong base.
 A.W. Salman et al. / Polyhedron 49 (2013) 200–206
Even though the elimination of electron-withdrawing b-substitu-
ents from 1,3-disubstituted imidazolium and benzimidazolium
salts has been reported [15], no systematic or useful methods have
yet been described for the Hofmann or Hofmann-type elimination
reactions of quaternary ammonium or azolium salts.
Furthermore, a ‘cage-like’ compartmental bis-imidazolium salt
bearing an aryl–alkyl bridging module can be assembled by com-
bining two flexible bromo derivatives having electron withdrawing
b-substituents with an aryl–alkyl separated bis-imidazole. How-
ever, the difficulty arises in how to avoid the reactivity of the
b-substitutents which readily undergoes hydrolysis to form the
eliminated products. Scheme 2 depicts the formation of imidazoli-
um salts 2b, 3b and 4b from an aryl–alkyl bridged imidazole-based
precursor. The synthetic route to the imidazole precursor 1b has
been previously reported [16]. A series of bis-imidazole and bis-
imidazolium salts 1–4 was synthesized in quantitative yields for
derivatives with ortho-substituents on the N-aryl–alkyl group
and yields in the range 66–78% for 2b–4b. However, salt 3b was
formed from 2b as yellow crystals after attempting to grow suit-
able crystals for X-ray diffraction analysis by slow evaporation at
ambient temperature for several days. Further, salt 3b was con-
verted to corresponding PF6 salt by metathesis reaction with
KPF6 give 4b as white precipitate. The intriguing aspect of the for-
mation of 1b has shown unambiguously when 3b and 4b were
treated with Ag2O or Hg(OAc)2 in acetonitrile in an equimolar ratio.
However, silver(I) complexes 6a/b and mercury(II) complex, 6c
Scheme 2. Synthetic route for the preparation of salts 3b and 4b, and silver(I)/mercury(II) complexes 6a–c.
203
were obtained when Ag2O and Hg(OAc)2 was used in excess,
respectively (Scheme 2). These imidazolium salts and Ag(I)/Hg(II)
complexes were prepared in an analogues manner to that of 1a–
4a and 5a–c, respectively [5]. In order to compare the reactivity
of mentioned cyano-functionalized derivatives, a bis-benzonitrile
substituted imidazolium salt 7 was prepared by the reaction of
imidazole and 3-bromomethyl benzonitrile in 1:2 ratio. So ob-
tained bromide salt was qualitatively converted into hexafluoro-
phosphate counterpart by salt metathesis reaction using KPF6.
Further, Ag(I)- and Hg(II)-complexes (8a and 8b) of salt 7 were syn-
thesized by in situ deprotonation method as shown in Scheme 3.
3.2. Spectral characterization
The IR spectra of 1b and 3b show a medium intensity band at
around 1610 cm1, which is assigned to the m(C@N) of both
imidazole moieties. However, in the spectra of the complexes
6a–c, the band due to m(C@N) is almost shifted up to 20 cm1, sug-
gesting its involvement in the coordination [17,18]. The appear-
ance of the imidazolium proton at C20 in the 1H NMR spectra in
the range d 8.9–9.3 is indicative for the formation of imidazolium
salts 2b, 3b and 4b. Similarly, the correlating carbon resonated in
the range d 130–136 in the 13C NMR spectra of the respective salts.
A small down filed shift of the signal for C20 was observed in the
case of 2b, resulting in a characteristic signal around d 136, as it
undergoes measured hydrolysis in the solvent. The resonance of
204 A.W. Salman et al. / Polyhedron 49 (2013) 200–206

Scheme 3. Synthesis of imidazolium salt 7 and silver(I)/mercury(II) complexes 8a and 8b.

the imidazolium NH for all 1H-azolium salts was found in the
range d 6.2–7.1 in the respective 1H NMR spectra. Apart from these
significant signals, the NMR spectra of all the compounds con-
tained signals which were consistent with the proposed structures.
However, all our attempts to isolate the 2-ethylcyano salt 2b gave
negative results as it underwent measured elimination to produce
3b, and a highly volatile acrylonitrile formation upon dehydration
of 3-hydroxyproionitrile and other cyanoethylated byproducts. So,
we were not able to isolate any of the byproducts occurring from
possible dipolar cycloaddition reaction. Very similar examples
are also available in the literature, where the isolation of the
similar byproducts is not possible when a 2-ethylcyano group is
employed in forming the imidazolium/benzimidazolium salts
[15,19].
On the other hand, IR spectrum of the salt 7 shows two medium
intensity sharp bands at 2236 and 1617 cm1, ascribed to the
stretching vibrations of nitrile (C„N) and imine (C@N) functional-
ities, respectively. In the complex spectra, band due to nitrile vibra-
tions remains unaltered, indicating its non-involvement in the
coordination. However, vibrations due to imidazole core were
shifted towards higher energy region by 56 cm1, indicating the
formation of desired C-N module in the complexes. The 1H NMR
spectrum of imidazolium salt 7 shows two distinguished singlets
at d 9.31 and 5.47 indicates the presence of NCHN and benzylic
protons (CH2), respectively. The multiplets in the range d 7.61–
7.89 are due to the resonance of aromatic protons. In the 13C
NMR spectrum, the chemical shift value of C-2 carbon was ob-
served at most downfield shift of d 136.75. Aromatic, nitrile and
benzylic carbon resonances were observed at around d 118.31–
135.76, 111.93 and 51.3, respectively. Further, the successful for-
mation of Ag(I) and Hg(II)–carbene complexes 8a and 8b is indi-
cated by the disappearance of the acidic C2 proton characteristic
of imidazolium salt in the 1H NMR spectra of complexes. In addi-
tion, in the 13C NMR spectra of the complexes, the characteristic
carbene carbon value at d 180.58 and 167.71 is consequently
observed for 8a and 8b, respectively. These observations collec-
tively confirm the formation of desired Ag(I)– and Hg(II)–NHC
complexes.
variety of tertiary nitrogen-containing systems subsequent to
dequaternarization. Similar observations were recorded with the
1H-azolium salts 3b and 4b when they were subjected to metalla-
tion with Ag2O. Also, we confirmed the formation dequarternaiza-
tion of 1H-azolium salts 3b and 4b when treated with Ag2O or
Hg(OAc)2. Actually, we were expected Ag(I)–NHC complexes from
3a/b, but eventually, 1a2H2O and 1b resulted along with the for-
mation of AgBr followed by the dequaternarization of the salts.
This pathway of dequaternarization proceeds with formation of a
hydroxide intermediate salt and AgBr. Additionally, the transi-
tional hydroxide salt undergoes dehydration to form the respective
aryl–alkyl bridged imidazoles. In order to avoid this deactivation
process, 3b was treated with excess Ag2O at a higher temperature.
As opposed to the formation of 1b, silver(I)-coordination com-
plexes 6a and b were formed. Yet another route was used to give
the silver(I)/mercury(II)–NHC complexes by converting 3b into
hexafluorophosphate counterpart 4b. However, no silver(I)/mer-
cury(II)–NHC complexes were formed, instead following the for-
mation of the same silver(I)- and mercury(II)-coordination
complexes tag along the Hofmann-type elimination reaction. In
6a–c, the bis-imidazoles are in cis-conformation and each is at-
tached to two silver/mercury atoms via a nitrogen atom of each
imidazolyl groups. All analytical and spectral data of the complexes
6a–c were in well agreement with the similar reported compounds

3.3. Hofmann-type elimination studies

In a wide variety of quaternary ammonium and azolium salts,

the formally tolerable dequaternarization following treatment
with basic Ag2O became faster due to the formation of a hydroxide
intermediate salt [20]. Further, this salt undergoes dehydration to
form amines or 1H-azoles. This phenomenon is called ‘Hofmann
elimination’, and it is the principle cause for the formation of a
Fig. 1. Crystal structure of 1a2H2O with two lattice held water molecules, drawn at
50% probability displacement ellipsoids. Selected bond distances (Å) and angles (°):
C1–H1 = 0.95 and angles (°): N2–C4–C5 = 112.32 (13).
 A.W. Salman et al. / Polyhedron 49 (2013) 200–206
[13,14]. Unlike 2-cyanoethyl substituted imidazolium salts, bis-
benzonitrile-substituted salt 7 was stable to air and moisture and
does not undergo the formation of 1H-imidazolium salt. Addition-
ally, stable Ag(I)– and Hg(II)–NHC complexes were prepared by the
reaction of Ag2O and Hg(OAc)2 with salt 7, respectively.
3.4. Crystal structures
Crystals suitable for single crystal X-ray diffraction studies were
obtained by slow evaporation of the salt/complex solution in ace-
tonitrile. In order to make easier the comparison, crystal structures
of 1a2H2O and 3a are also given as Figs. 1 and 2, respectively.
Crystal structures, selected bond lengths and angles of 1a2H2O,
3a, 3b and 8a are shown in Figs. 3 and 4, respectively. The crystal
refinement data for 3b and 8a are listed in Table 1. The imidazoli-
um salt 3b crystallizes in monoclinic space group P2(1)/c, and pos-
ses a three-dimensional network through hydrogen bonding. An
asymmetric unit of the salt 3b consist an imidazolium cation and
two bromide anions along with one water molecule. Both the imid-
azole rings in 3b are lies in planes with obtuse angles of around
112° with respect to the aryl–alkyl spacers and are oriented oppo-
site to each other in order to impart a boat-like shape. The internal
Fig. 2. Crystal structure of imidazolium salt 3a with two counter bromide ions,
drawn at 50% probability displacement ellipsoids. Selected bond distances (Å):
N1B–H1NB = 0.75(3), N4B–H2NB = 0.82(3) and angles (°): N3B–C11B–
C10B = 110.36(16), N2B–C4B–C5B = 112.70(16), C14B–N4B–H2NB = 121(2), C1B–
N1B–H1NB = 118(2).
Fig. 3. Crystal structure of imidazolium salt 3b with two independent bromide
anions, showing 50% probability displacement ellipsoids. Selected bond distances
(Å) and angles (°): N2–H1N2 = 0.86 (3), N4–H1N4 = 0.78 (2), and angles (°): N3–C4–
C5 = 112.08 (11), N1–C11–C7 = 112.97 (11), C14–N2–H1N2 = 123.3 (19), C13–N2–
H1N2 = 127 (2), C1–N4–H1N4 = 125.3 (16), C2–N4–H1N4 = 125.6 (16).
205
Fig. 4. Crystal structure of 8a with two independent water molecules, showing 50%
probability displacement ellipsoids. Selected bond distances (Å) and angles (°): C1–
Ag1 = 2.074(5), C20–Ag1 = 2.077(6), N1–C1 = 1.350(8), N2–C1 = 1.347(7), N3–
C20 = 1.363(7), N4–C20 = 1.342(8), C11–N5 = 1.141(11). C1–Ag1–C20 = 179.4(2),
N1–C1–N2 = 103.7(5), N3–C20–N4 = 103.8(5), C9–C11–N5 = 179.3(10).
ring angles of imidazole (N–C–N) at the carbene center are N2–
C14–N1 = 108.16(13) and N4–C1–N3 = 108.31(12), these values
are also well within the range for dibromide salt 3a, neutral bis-
imidazole derivative 1a2H2O, and other related bis-imidazolium
and benzimidazolium salts [21–26].
 with one Ag
Complex 8a crystallizes in a triclinic space group P1
complex cation and one hexafluorophosphate anion occupying an
asymmetric unit. The Ag(I) exist in a linear coordination geometry
with the bond angle 179.4(2)° (C1–Ag1–C20) perpendicular to the
ac plane, formed by two carbene carbon atoms of the central imid-
azole ring. Planes of central imidazole rings are perpendicular to
each other, forming an X-shaped complex molecule. The fluoride
ions of the general-position hexafluorophosphate anion are disor-
dered over two sets of sites. The internal ring angles of imidazole
(N–C–N) at the carbene center are 103.7(5)° and 103.8(5)° for
N1–C1–N2 and N3–C20–N4, respectively which are in agreement
with the previous reports [27,28]. This considerable decrease in
the internal ring angles of imidazole rings is originated from the
formation of new Ag–C bond from carbene carbon atoms. In the ex-
tended structure, the complex cations are connected with hexa-
fluorophosphate anions into three-dimensional networks by two
types of intermolecular C–H  F and C„N  H hydrogen bonds
with the bond distances 2.546 and 3.257 Å, respectively.
4. Conclusions
The results illustrated herein represent a new way to prepare
1H-azolium salts, which readily undergo Hofmann-type elimina-
tion when treated with Ag2O or Hg(OAc)2 in a quantitative ratio.
These are also the first examples of aryl–alkyl bridged 1H-imida-
zoles (3a/b) determined by X-ray crystallographic analyses formed
via Hofmann-type elimination reaction. However, the silver(I) (6a/
b) and mercury(II) coordination complex (6c) were obtained when
Ag2O and Hg(OAc)2 is used in excess, respectively. Counterions
have been switched to hexafluorophosphates to check the forma-
tion of Ag(I)/Hg(II)–NHC complexes when 3b is treated with basic
metal sources. However, this method also follows the bromide
pathway to form coordination compounds followed by the Hof-
mann-type elimination. To compare the extent of Hofmann-type
elimination, an aromatic nitrile-substituted imidazolium salt and
its Ag(I) and Hg(II) complexes were prepared. Conversely, these
206 A.W. Salman et al. / Polyhedron 49 (2013) 200–206

Table 1
Crystal data and structure refinement parameters for compounds 3b and 8a.

12H2O 3a 3b 8a
Formula C14H18N4O2 C14 H16 Br2 N4 C17H24Br2N4O C38H28AgN8F6P
Formula weight 274.32 400.13 460.22 849.52
Crystal system triclinic monoclinic monoclinic triclinic
Space group P1 P2(1)/C P2(1)/C P1
Unit cell dimensions
a (Å) 8.07770(10) 15.4206(5) 8.6968(2) 8.1353(10)
b (Å) 8.7249(2) 13.8314(4) 23.3183(6) 13.3832(15)
c (Å) 10.8716(2) 16.7964(6) 10.0722(3) 17.530(2)
a (°) 80.7030(10) 90.00 90.00 75.716(3)
b (°) 69.8770(10) 120.924(2) 108.1170(10) 82.018(2)
c (°) 84.5800(10) 90.00 90.00 88.328(2)
V (Å3) 709.35(2) 3073.23(17) 1941.32(9) 1831.7(4)
Z 2 8 4 2
Dcalc (gm/cm3) 1.284 1.730 1.575 1.540
Absorption coefficient (mm1) 0.089 5.271 4.187 0.665
F(0 0 0) 292 1584 928 856
Crystal size (mm) 0.38  0.18  0.05 0.33  0.18  0.08 0.43  0.33  0.24 0.13  0.15  0.57
T (K) 293 293 293 293
Radiation (Å) MoKa 0.71073 MoKa 0.71073 MoKa 0.71073 MoKa 0.71073
h Minimum, maximum (°) 2.37, 30.07 2.83, 31.82 2.30, 35.39 1.2, 28.5
Dataset 11:11, 12:12, 15:15 22:22, 19:19, 24:24 14:14, 39:36, 17:17 10: 0; 17:17; 12: 3
Total; unique data 15 093 41 091 41 549 9110
Rint 0.0817 0.0369 0.0601 0.00
Nref, Npar 4137, 197 10 421, 377 10 185, 236 9110, 517
R, wR2, S 0.0349, 0.1608, 1.100 0.0443, 0.0715, 1.059 0.0332, 0.0863, 1.031 0.0786, 0.2700, 1.11

compounds found to be stable and forms NHC complexes without
showing Hofmann-type elimination reaction. Further, work in or-
der to stabilize the 1H-imidazolium salts so as to prepare a wide
variety of coordination and NHC complexes with different aryl–
alkyl spacers is underway.
Acknowledgments
R.A.H. thanks Universiti Sains Malaysia (USM) for the Short
term Grant (203/PKIMIA/6311123) and the Research University
(RU) Grant 1001/PKIMIA/811217. A.W.S. and Z.Z.H thank USM for
the RU Grants 1001/PKIMIA/843090 and 1001/PKIMIA/834086.
Appendix A. Supplementary material
CCDC 849996, 849997, 849998, and 862525 contain the supple-
mentary crystallographic data for complexes 1a2H2O, 3a, 3b, and
8a, respectively. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/
10.1016/j.poly.2012.09.020.
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