NJC

Published on 03 May 2016. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2016 15:27:32.

View Article Online

PAPER View Journal

Mono- and bis-N-heterocyclic carbene complexes

of tantalum and niobium with high oxidation states†
Cite this: DOI: 10.1039/c6nj00223d
ZhenHong Wei,* Wenbiao Zhang, Guangming Luo, Feng Xu, YingXuan Mei and
Hu Cai*

Reactions of two free N-heterocyclic carbenes (NHCs) 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr)

Received (in Montpellier, France)
22nd January 2016,
Accepted 2nd May 2016
DOI: 10.1039/c6nj00223d
www.rsc.org/njc
and 1,3-dimesitylimidazol-2-yliden (IMes) with group VB transition metals MCl5 at low temperature gave
a mono-NHC complex [(IPr)TaCl5] (1) and two bis-NHCs [(IMes)2MCl4][MCl6] (M = Ta, 2; =Nb, 3).
Crystallographic studies revealed that the substitution effect plays an important role in the construction of
these two different types of NHC complexes. Although mono-NHC complex 1 has been theoretically
analyzed by F. Marchetti, complexes 2 and 3 represented the first examples of the structurally characterized
bis-NHCs Ta(V) and Nb(V) complexes. In addition, complexes 1–3 showed catalytic efficiency in the
cycloaddition between CO2 and propylene oxide to synthesize cyclic carbonates under mild conditions.

Introduction
In the past few decades, N-heterocyclic carbenes (NHCs) have
attracted intense interest because of their unique structural
and chemical properties.1–4 Compared with traditional ligands
containing N, P, and O coordinated atoms,5 NHCs present
interesting properties such as strong s donor ability, structural
diversity, electronic effects and steric effects.6 Therefore, NHCs
have been widely used in organic synthesis, organometallic
chemistry, coordination chemistry and other research fields,7–9
since the first synthesis of a stable NHC in 1991 by Arduengo.10
In recent years, NHC metal complexes containing late transition
metals with low and medium valences have been primarily investi-
gated.11–15 Conversely, the early-transition-metal NHC complexes
have yet to be explored to the same depth,16–22 particularly, group
VB NHC metal complexes with high oxidation states are scarce.23,24
For example, the first vanadium NHC complex was obtained by the
reaction of free carbene IMes with trichloro–oxo–vanadium VOCl3 in
2003.25 Compared with vanadium NHC complexes,26 NHC com-
plexes containing Nb or Ta are rarely reported owing to the fact that
they have few d electrons, strong oxophilic properties and extreme
moisture sensitivity. Until now only Fryzuk27,28 and Hollis23 have
reported chelating pincer NHC–Ta complexes, and Marchetti
has reported mono-NHC Ta and Nb complexes.29,30
On the other hand, NHC metal complexes have shown catalytic
activity because they can achieve greater selectivity and more
efficient reactivity than either component individually.28,31–33
For example, in 1995 Herrmann reported a Pd metal NHC
complex showing effective catalysis in the Heck reaction,34 and
in 2010 Scheidt et al. reported the combination of Lewis base
(NHCs) and Lewis acid (Mg2+ and Li+) catalyzed [3+2] annulation
with high stereoselectivity.35,36 However, the use of NHCs with
early metals,35,37,38 in particular with group 5 metals, for the
catalytic reactions was rarely reported.39,40 On the basis of the
above, the field of VB metal complexes ligated by NHC ligands
requires in-depth research studies.
In this paper, two free NHCs 1,3-bis(2,6-diisopropylphenyl)-
imidazol-2-ylidene (IPr) and 1,3-dimesitylimidazol-2-yliden
(IMes) were reacted with MCl5 to give a neutral NHC complex
[(IPr)TaCl5] (1) and two ionic NHC complexes [(IMes)2MCl4][MCl6]
(2, 3) (M = Ta, Nb), in which complex 1 has been DFT calculated
by Marchetti in 2016.30 But, to our knowledge, complexes 2 and
3 are the first crystallographically characterized Ta(V), Nb(V)
NHC complexes coordinated by two NHC ligands. All these
complexes exhibited catalytic activity in the cycloaddition reaction
between CO2 and propylene oxide to synthesize cyclic carbonates.
Herein we report the synthesis, structures and catalytic activity
of complexes 1–3.

College of Chemistry, Nanchang University, Nanchang, 330031, China.

E-mail: weizh@ncu.edu.cn, caihu@ncu.edu.cn
† Electronic supplementary information (ESI) available: Fig. S1–S6 show the NMR
Experimental
spectra of the products; Fig. S7 shows the UV-vis spectra of the products; Fig. S8 Materials and methods
and S9 show the DFT-calculated structure of complex 1, while Tables S1 and S2
contain the relevant bonding parameters of complexes 1–3. CCDC 850308 (1),
All manipulations were performed under an atmosphere of
1413433 (2) and 1413429 (3). For ESI and crystallographic data in CIF or other dry oxygen-free argon or nitrogen by means of standard Schlenk
electronic format see DOI: 10.1039/c6nj00223d or glove box techniques. Toluene and THF were purified by

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016 New J. Chem.

Paper
distillation from potassium/benzophenone ketyl and stored
under N2. CH2Cl2 was distilled over CaH2 and stored with
activated 4 Å molecular sieves under N2. Deuterium reagents were
Published on 03 May 2016. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2016 15:27:32.
purchased from Cambridge Isotopes and dried over activated 4 Å
molecular sieves and stored under N2. Tantalum pentachloride and
niobium pentachloride were purchased from Alfa Aesar and freshly
sublimed prior to use. CO2 (purity Z99.999%) was dried over
anhydrous CaCl2 and activated 4 Å molecular sieves. NMR-scale
reactions were conducted in Teflon-valve-sealed J. Young-type NMR
tubes. 1H NMR and 13C NMR spectra were recorded on a DD2
400MR (Agilent) or a Bruker 600 Avance III spectrometer with TMS
as internal standard. Elemental analysis was performed in the
Analytical Laboratory of Shanghai Institute of Organic Chemistry.
The free NHCs 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene
(IPr) and 1,3-dimesitylimidazol-2-yliden (IMes) were prepared
according to the literature procedures.41,42
Syntheses
[(IPr)TaCl5] (1). To a solution of IPr (0.78 g, 2 mmol) in cold
toluene (20 mL, 40 1C) was added TaCl5 (0.72 g, 2 mmol). The
reaction mixture was kept stirring overnight at 0 1C to give a
yellow solid, which was filtered, washed three times with
toluene and dried under reduced pressure. Recrystallization
of the crude residue in CH2Cl2 (15 mL) gave yellow crystals.
Yield: 1.12 g, 75%. Anal. calcd for C27H37Cl5N2Ta (%): C, 43.37;
H, 4.99; N, 3.75. Found (%): C, 43.47; H, 4.99; N 3.76. 1H NMR
(600 MHz, CD2Cl2): d 1.12 (d, 12H, J = 6.7, CH3), 1.37 (d, 12H,
J = 6.9, CH3), 2.76 (m, 4H, J = 13.6, 6.8, CHMe2), 7.21 (s, 2H,
NCHQ), 7.30 (d, 4H, J = 7.8, m-C6H3) 7.49 (t, 2H, J = 7.8, p-C6H3);
13
C{1H} NMR (150 MHz, CD2Cl2): d 22.95, 25.94 (s, CH3),
29.24 (s, CHMe2), 124.45 (s, NCHQ), 126.08 (s, m-C6H3),
131.06 (s, p-C6H3), 136.99 (s, o-C6H3), 146.36 (s, ipso-C6H3),
190.57 (s, NCN).
[(IMes)2TaCl4][TaCl6]
4CH2Cl2 (2). To a solution of IMes (0.30 g,
1 mmol) in cold toluene (20 mL, 60 1C) was added TaCl5 (0.36 g,
1 mmol). The reaction temperature was increased to 5 1C and the
reaction mixture was kept stirring overnight to give a yellow
precipitate, which was filtered, washed with toluene and recrystal-
lized in CH2Cl2 to give yellow crystals in two days. Yield: 0.46 g, 70%.
Anal. calcd for C42H48Cl10N4Ta2 (%): C, 38.06; H, 3.65; N, 4.23.
Found (%): C, 38.10, H; 3.79; N, 4.22. 1H NMR (400 MHz,
CD2Cl2): d 7.16 (s, 4H, NCHQ), 6.94 (s, 8H, m-C6H2), 2.33
(s, 12H, p-CH3), 1.97 (s, 24H, o-CH3). 13C NMR (101 MHz,
CD2Cl2): d 141.0 (N-C6H2), 135.8 (p-C6H2), 134.9 (m-C6H2),
129.7 (o-C6H2), 125.3 (NCHQ), 21.3 (p-CH3), 18.5 (o-CH3).
[(IMes)2NbCl4][NbCl6]
4CH2Cl2 (3). The red crystals of 3 were
obtained using similar procedures to synthesise 2 starting from
IMes (0.30 g, 1 mmol) and NbCl5 (0.27 g, 1 mmol). Yield: 0.38 g,
67%. Anal. calcd for C42H48Cl10N4Nb2 (%): C, 43.90; H, 4.21;
N, 4.88. Found (%): C, 43.90; H, 4.06; N, 4.77. 1H NMR (400 MHz,
CD2Cl2): d 7.16 (s, 4H, m-C6H2), 6.95 (s, 8H, NCHQ), 2.34 (s, 12H,
p-CH3), 2.01 (s, 24H, o-CH3). 13C NMR (101 MHz, CD2Cl2): d 141.1
(N-C6H2), 136.0 (p-C6H2), 134.7 (m-C6H2), 129.7 (o-C6H2), 125.2
(NCHQ), 21.3 (p-CH3), 18.6 (o-CH3).
X-ray crystallography. X-ray diffraction data for single crystals
of 1–3 were collected on a Bruker Smart CCD diffractometer with
New J. Chem. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016
View Article Online
NJC
graphite-monochromated Mo Ka radiation (0.71073 Å). The
structures were solved by the direct methods in the SHELXS
program and refined on F2 in SHELXL.43 In the structure of
complex 3, four chlorine atoms, in which two atoms are coordi-
nated to Nb metal and the remaining two atoms are bonded to
the C atom of one CH2Cl2 solvated molecule, were severely
disordered, and split into two fragments with occupancy factors
of 0.52/0.48. In crystals 1–3, all non-hydrogen atoms were
modeled anisotropically, and all hydrogen atoms were placed
in idealized positions and treated as riding atoms. Details of the
data collection and refinement are given in Table 1. CCDC
850308 (1), 1413433 (2), and 1413429 (3).
Typical procedures for the synthesis of propylene carbonate.
A Schlenk tube was charged with the catalyst (0.1 mmol),
1,2-propylene oxide (1 mmol), CH2Cl2 (2 mL) and 1 MPa CO2.
After being stirred for 10 h at 20 1C, the reaction mixture was
subjected to NMR detection. 1H NMR (600 MHz, CD2Cl2): d 4.83
(m, J = 7.4, 6.3 Hz, 1H, CH), 4.53 (dd, J = 8.4, 7.7 Hz, 1H, CH2),
4.00 (dd, J = 8.4, 7.3 Hz, 1H, CH2), 1.44 (d, J = 6.3 Hz, 3H, CH3).
Results and discussion
Synthesis and characterization
Reactions of free NHC IPr and IMes with tantalum pentachloride
and niobium pentachloride led to many precipitates, which were
recrystallized from CH2Cl2 to give complexes 1–3, respectively,
Scheme 1. All the complexes were characterized by NMR technology,
elemental analysis and X-ray crystallography. It is to be noted that
complexes 1–3 were obtained by the same reactions between free
carbenes (IPr and IMes) and MCl5 (M = Ta, Nb) with equimolar
ratios, but the isopropyl group was bulkier than the methyl group,
leading to complex 1 being constructed with only one NHC ligand,
while 2 and 3 have two NHC ligands. Furthermore, complex 3 is an
ionic bis(IMes) complex obtained by the reaction of one equivalent
of NbCl5 with IMes. This is all the more surprising since a similar
reaction was reported to give the mono-adduct [(IMes)NbCl5] by
Marchetti et al.29 While it could well be possible that the two
different compounds be obtained under the reverse feeding orders.
Complexes 1–3 are unstable in air, but can be kept under an argon
atmosphere for over one week without decomposition at room
temperature in the solid state.
From the NMR spectra, it can be seen that the chemical
shifts in the two kinds of complexes were close to each other,
which was ascribed to their similar structures, Fig. S1–S4 (ESI†).
In the 1H NMR spectra of 1–3, the peaks at high field were
ascribed to the shifts of protons in the alkyl groups of isopropyl
and methyl, and the peaks at low field belonged to the shifts
of protons in the aromatic rings of benzene and imidazole. In
the 13C NMR spectra, the chemical shift of carbenic carbon in
complexes 1–3 was not observed, which was consistent with the
vanadium NHC complex reported by Abernethy in 2003.25
Structural analysis
Complex 1 crystallizes in the monoclinic system with a space
group of P21/n and the asymmetric units contain a neutral
 View Article Online

NJC Paper

Table 1 Crystallographic data for complexes 1–3

Compounds 1 2 3
Chemical formula C27H36Cl5N2Ta C46H56Cl18N4Ta2 C46H56Cl18N4Nb2
Published on 03 May 2016. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2016 15:27:32.

Fw 746.78 1664.95 1488.87

Crystal system Monoclinic Triclinic Triclinic
Space group P21/n P1% P1%
a (Å) 10.4051(18) 13.870(2) 13.8499(10)
b (Å) 17.875(3) 15.029(2) 15.0205(10)
c (Å) 17.596(3) 17.015(3) 16.9789(11)
a (1) 90 66.680(2) 66.765(3)
b (1) 104.341(2) 86.872(2) 86.819(4)
g (1) 90 71.673(2) 71.851(3)
V (Å3) 3170.72(187) 9131(3) 3075.0(4)
Z 4 2 2
Dcalc (g cm 3) 1.564 1.794 1.608
F(000) 1480 1624 1496
m (Mo Ka, mm 1) 3.906 4.364 1.191
Total no. of reflns. 22 657 21 775 47 265
ymax 25.5 25 27.88
No. of unique reflns. 5840 [Rint = 0.0399] 10 779 [Rint = 0.0435] 14275 [Rint = 0.0380]
No. of observed refns. 5906 10 860 11 414
No. of variables 316 643 671
R1, wR2 (obsd data) 0.0377, 0.0980 0.0454, 0.1064 0.0600, 0.1252
R1, wR2 (all data) 0.0568, 0.1053 0.0584, 0.1165 0.0802, 0.1417
GOF, S 1.069 1.080 1.072

Scheme 1 The synthesis routes for NHC–Ta and –Nb complexes 1–3.

[(IPr)TaCl5] molecule. The metal center in 1 chose a slightly
distorted octahedral geometry coordinated by five chlorine
atoms and a carbene C atom, in which the NHC served as a
monodentate ligand and occupied the axial position with the
maximum angles +Cl(2)–Ta(1)–C(15) = 179.32(12)1, almost
near 1801, Fig. 1. The steric effect of bulky IPr-groups on the
NHC unit is evident in that the imidazole ring was not coplanar
to benzene rings. In complex 1, the Ta(1)–C(15) carbene bond
length of 2.373(5) Å is little shorter than that in the analogous
bromide complex [(IPr)TaBr5] (2.383(10) Å),30 indicating that
the metal–carbene bond distance slightly decreases upon
decreasing the size of the halide ligands. The Ta–Cl(2) bond
length of 2.3557(16) Å in the axial direction is longer than the
other four, which is caused by the trans influence of the NHC
ligand. The DFT calculations proved that two out of four
equatorial chlorides may interact with the vacant p orbital of
carbene with C–Cl(3) = 3.156 Å and C–Cl(4) = 3.1889 Å, which
are within the sum of the van der Waals radii of the respective
atoms [sum = 3.45 Å]44 (see the ESI†).
Fig. 1 The structures of complex 1, hydrogen atoms were omitted for clarity.
Selected bonds (Å) and angles (1): Ta(1)–Cl(1) = 2.2989(16), Ta(1)–Cl(5) =
2.3023(15), Ta(1)–Cl(4) = 2.3259(19), Ta(1)–Cl(2) = 2.3557(16), Ta(1)–Cl(3) =
2.3220(18), Ta(1)–C(15) = 2.373(5), Cl(2)–Ta(1)–C(15) = 179.32(12).
The structures of complexes 2 and 3 are similar except for
the metal centers, Fig. 2. Both complexes crystallize in the
triclinic system with a space group of P1% and the asymmetric
units contain one [(IMes)2MCl4]+ cation, two half [MCl6] anions,
and four CH2Cl2 solvated molecules (M = Ta, or Nb). In
both complexes, the metal centers chose a distorted octahedral
geometry, in which the four chlorine atoms are located at the
equatorial position and the two carbenic carbon atoms are
located at the axial position with the C–M–C bond angles at
176.0(2)1 in 2 and 174.70(13)1 in 3. While in anionic [MCl6] , the
metal centers adopted a regular octahedron, which were proved
by +Cl(9)#–Ta(3)–Cl(9) = 180.000(1)1 in 2; +Cl(9)#–Nb(2)–Cl(9) =
180.00(6)1 in 3. The corresponding M–C and M–Cl bond lengths
in complexes 2 and 3 are similar due to lanthanide contraction.
Compared with complex 1, the average M–C and M–Cl bond

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016 New J. Chem.

Paper
Published on 03 May 2016. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2016 15:27:32.
Fig. 2 The cationic structures of complexes 2 and 3, anions [MCl6] and
hydrogen atoms were omitted for clarity. Selected bonds (Å) and angles (1)
for 2: Ta(1)–Cl(1) = 2.2837(19), Ta(1)–Cl(2) = 2.3056(18), Ta(1)–Cl(3) =
2.2985(18), Ta(1)–Cl(4) = 2.2811(19), Ta(1)–C(10) = 2.346(6), Ta(1)–
C(31) = 2.346(6), C(31)–Ta(1)–C(10) = 176.0(2); for 3: Nb(1)–Cl(1) =
2.277(7), Nb(1)–Cl(2) = 2.3107(11), Nb(1)–Cl(3) = 2.278(11), Nb(1)–Cl(4) =
2.2952(12), Nb(1)–C(10) = 2.352(4), Nb(1)–C(33) = 2.356(4), C(10)–Nb(1)–
C(33) = 174.70(13).
lengths in complexes 2 and 3 were slightly shorter, which was
due to the fact that complex 1 was constructed with one NHC
ligand and complexes 2 and 3 were bis-NHC complexes. Besides,
similar to complex 1, there are interactions between carbene C
and the four equatorial Cl atoms in complexes 2 and 3.
The formation of cyclic carbonates
CO2 is a main greenhouse gas, but also a cheap, nontoxic, and
abundant C1 building block. Many homogeneous and hetero-
geneous catalysts have been intensively developed for the inser-
tion of CO2 into the C–O bond of epoxide molecules to form
cyclic carbonates.45–48 For example, (Salen)Co(II) complexes,49
Schiff base complexes of M(III), where M = Cr, Co, or Al,50 and
expensive transition metal complexes51 have been shown to be
effective in this reaction. But in general these reported catalytic
reactions were performed under severe conditions at a high
temperature of above 80 1C, a high CO2 pressure of above
3 MPa, or in the presence of co-catalysts.52
While in our case, synthesis of cyclic carbonates by the reaction
of CO2 with 1,2-propylene oxide catalysed by complexes 1–3 was
carried out under mild conditions at a temperature of 20 1C and a
CO2 pressure of 1 MPa without co-catalysts as shown in Scheme 2.
New J. Chem. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016
View Article Online
NJC
Scheme 2 The catalytic reaction of CO2 with 1,2-propylene oxide to
produce cyclic carbonates using complexes 1–3 under mild conditions.
Table 2 Catalytic cyclization of 1,2-propylene oxide with CO2 by com-
plexes 1–3
Entrya Catalyst Conversionb (%) Yield (%) Selectivity (%)
1 1 499 91 95
2 2 46 29 63
3 3 499 16 16
4 TaCl5 0 Trace —
5 NbCl5 0 Trace —
6 IPr 0 Trace —
7 IMe 0 Trace —
a
Reaction conditions: 20 1C, 1 MPa CO2, 10 h, 10 mol% catalyst.
b
Conversion rates were determined by comparing the ratio of the
product to the substrate in the reaction mixture through 1H NMR
spectroscopy.
1
H NMR spectroscopic monitoring revealed the final results,
which are listed in Table 2. It can be seen that complexes 1–3
have substantial differences in their catalytic performance.
Compared to complexes 2 and 3 (entries 2 and 3), complex 1
showed the best performance in both the conversion rate
(499%) and selectivity (95%) (entry 1). It is interesting to note
that complex 3 also exhibited high catalytic efficiency with almost
100% conversion of 1,2-propylene oxide, where 16% was converted
into propylene carbonate and the remaining 84% was converted
into poly(propylenecarbonate) (entry 3). At last, neither Lewis acids
MCl5 (M = Ta, Nb) nor Lewis bases IPr and IMe showed catalytic
activity in the cycloaddition reaction (entries 4–7).
A general mechanism could be proposed for the cyclization
reaction, as shown in Scheme 3. In the initial step, 1,2-propylene
oxide was inserted into the Ta–C bond of the NHC complex to
give a free NHC ligand and the [TaCl5(OC3H6)] intermediate in
which the oxygen atom of the epoxide binds to the metal centre
as the sixth coordination. In the second step the free carbene
attacked the carbon atom with fewer electrons and the oxirane
ring is opened to produce a negatively charged oxide (O ). In
the third step, the ring opening accompanies concertedly the
binding of CO2 to the carbon atom of the epoxide. The binding
leads to the breaking-up of one of the CQO bonds to generate
the second negatively charged oxide (O ). In the last step, the
oxygen atoms coordinated to the metal centre subsequently
bind to the carbon connected to the carbenic carbon in head to
tail mode to cleave the product and close the catalytic cycle.
The proposed mechanism starting from the reaction of NHC
with epoxide and not with CO2 was proved by two experiments
performed in J. Young-type NMR tubes. Firstly, the reactions of
[IPrTaCl5] with CO2 did not give any signals of new products,
Fig. S5 (ESI†). In contrast, the reaction of [IPrTaCl5] with
1,2-propylene oxide led to new products, which can be observed
in 1H NMR spectra, Fig. S6 (ESI†).

NJC
Published on 03 May 2016. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2016 15:27:32.
Scheme 3 The possible mechanism of the cyclization reaction.
Conclusions
In summary, the reactions of two free N-heterocyclic car-
benes 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr)
and 1,3-dimesitylimidazol-2-yliden (IMes) with group VB metals
MCl5 gave a neutral complex [(IPr)TaCl5] (1) and two ionic
complexes [(IMes)2MCl4][MCl6] (2, 3) (M = Ta, Nb). All these
complexes showed catalytic efficiency in the cycloaddition
reaction between CO2 and 1,2-propylene oxide. Crystallographic
studies revealed that the substituted groups in NHCs played
a role in the construction of these two different types of NHC
complexes. Combination of the exceptional electronic and steric
stabilization provided by NHCs with the intrinsically reactive
VB metal center is likely to allow the stabilization of unusual
structural motifs, which will be the source of high catalytic
activity of this family of NHC metal compounds.
Acknowledgements
The authors thank the NSF of China (No. 20871064 and 21171073)
for financial support.
References
1 S. P. Nolan, Acc. Chem. Res., 2011, 44, 91–100.
2 P. L. Arnold and I. J. Casely, Chem. Rev., 2009, 109,
3599–3611.
3 F. E. Hahn and M. C. Jahnke, Angew. Chem., Int. Ed., 2008,
47, 3122–3172.
4 W. J. Sommer and M. Weck, Coord. Chem. Rev., 2007, 251,
860–873.
5 F. Marchetti and G. Pampaloni, Chem. Commun., 2012, 48,
635–653.
6 J. E. Thomson, C. D. Campbell, C. Concellon, N. Duguet,
K. Rix, A. M. Z. Slawin and A. D. Smith, J. Org. Chem., 2008,
73, 2784–2791.
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016
View Article Online
Paper
7 J. Li, C. Sehulzke, S. Merkel, H. W. Roesky, P. P. Samuel,
A. Doering and D. Stalke, Z. Anorg. Allg. Chem., 2010, 636,
511–514.
8 D. Zhang, H. Aihara, T. Watanabe, T. Matsuo and
H. Kawaguchi, J. Organomet. Chem., 2007, 692, 234–242.
9 S. P. Downing, S. C. Guadano, D. Pugh, A. A. Danopoulos,
R. M. Bellabarba, M. Hanton, D. Smith and R. P. Tooze,
Organometallics, 2007, 26, 3762–3770.
10 A. J. Arduengo, R. L. Harlow and M. Kline, J. Am. Chem. Soc.,
1991, 113, 361–363.
11 W. A. Herrmann, T. Weskamp and V. P. W. Bohm, in
Adv. Organomet. Chem., ed. R. West and A. F. Hill, 2001,
vol. 48, pp. 1–69.
12 D. J. Nelson, Eur. J. Inorg. Chem., 2015, 2012–2027.
13 M. Hernandez-Juarez, J. Lopez-Serrano, P. Lara, J. P. Morales-
Ceron, M. Vaquero, E. Alvarez, V. Salazar and A. Suarez,
Chem. – Eur. J., 2015, 21, 7540–7555.
14 L. Zhang, Y. Liu and L. Deng, J. Am. Chem. Soc., 2014, 136,
15525–15528.
15 K. Liu, M. T. Hovey and K. A. Scheidt, Chem. Sci., 2014, 5,
4026–4031.
16 N. Zhao, G. Hou, X. Deng, G. Zi and M. D. Walter, Dalton
Trans., 2014, 43, 8261–8272.
17 J. Cho, T. K. Hollis, E. J. Valente and J. M. Trate,
J. Organomet. Chem., 2011, 696, 373–377.
18 C. Lorber and L. Vendier, Dalton Trans., 2009, 6972–6984.
19 G. B. Nikiforov, H. W. Roesky, P. G. Jones, J. Magull,
A. Ringe and R. B. Oswald, Inorg. Chem., 2008, 47,
2171–2179.
20 I. S. Edworthy, A. J. Blake, C. Wilson and P. L. Arnold,
Organometallics, 2007, 26, 3684–3689.
21 D. Pugh, J. A. Wright, S. Freeman and A. A. Danopoulos,
Dalton Trans., 2006, 775–782.
22 L. P. Spencer, S. Winston and M. D. Fryzuk, Organometallics,
2004, 23, 3372–3374.
23 T. R. Helgert, T. K. Hollis, A. G. Oliver, H. U. Valle, Y. Wu
and C. E. Webster, Organometallics, 2014, 33, 952–958.
24 M. Aresta, A. Dibenedetto, L. Gianfrate and C. Pastore,
J. Mol. Catal. A: Chem., 2003, 204, 245–252.
25 C. D. Abernethy, G. M. Codd, M. D. Spicer and M. K. Taylor,
J. Am. Chem. Soc., 2003, 125, 1128–1129.
26 S. Bellemin-Laponnaz, R. Welter, L. Brelot and S. Dagorne,
J. Organomet. Chem., 2009, 694, 604–606.
27 L. P. Spencer, C. Beddie, M. B. Hall and M. D. Fryzuk, J. Am.
Chem. Soc., 2006, 128, 12531–12543.
28 S. Dagorne, S. Bellemin-Laponnaz and C. Romain, Organo-
metallics, 2013, 32, 2736–2743.
29 M. Bortoluzzi, E. Ferretti, F. Marchetti, G. Pampaloni and
S. Zacchini, Chem. Commun., 2014, 50, 4472–4474.
30 M. Bortoluzzi, E. Ferretti, F. Marchetti, G. Pampaloni and
S. Zacchini, Dalton Trans., 2016, 45, 6939–6948.
31 T. R. Helgert, T. K. Hollis and E. J. Valente, Organometallics,
2012, 31, 3002–3009.
32 R. J. Rubio, G. T. S. Andavan, E. B. Bauer, T. K. Hollis, J. Cho,
F. S. Tham and B. Donnadieu, J. Organomet. Chem., 2005,
690, 5353–5364.
New J. Chem.

Paper
33 H. A. Duong, T. N. Tekavec, A. M. Arif and J. Louie, Chem.
Commun., 2004, 112–113.
34 W. A. Herrmann, M. Elison, J. Fischer, C. Kocher and
Published on 03 May 2016. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 20/05/2016 15:27:32.
G. R. J. Artus, Angew. Chem., Int. Ed., 1995, 34, 2371–2374.
35 D. T. Cohen and K. A. Scheidt, Chem. Sci., 2012, 3, 53–57.
36 D. E. A. Raup, B. Cardinal-David, D. Holte and K. A. Scheidt,
Nat. Chem., 2010, 2, 766–771.
37 S. A. Mungur, A. J. Blake, C. Wilson, J. McMaster and
P. L. Arnold, Organometallics, 2006, 25, 1861–1867.
38 L. P. Spencer and M. D. Fryzuk, J. Organomet. Chem., 2005,
690, 5788–5803.
39 M. A. Rankin and C. C. Cummins, J. Am. Chem. Soc., 2010,
132, 10021–10023.
40 G. S. McGrady, A. Haaland, H. P. Verne, H. V. Volden,
A. J. Downs, D. Shorokhov, G. Eickerling and W. Scherer,
Chem. – Eur. J., 2005, 11, 4921–4934.
41 X. Bantreil and S. P. Nolan, Nat. Protoc., 2011, 6, 69–77.
42 A. J. Arduengo, R. Krafczyk, R. Schmutzler, H. A. Craig,
J. R. Goerlich, W. J. Marshall and M. Unverzagt, Tetrahedron,
1999, 55, 14523–14534.
New J. Chem. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016
View Article Online
NJC
43 G. M. Sheldrick, Acta Crystallogr., Sect. C: Struct. Chem.,
2015, 71, 3–8.
44 P. Shukla, J. A. Johnson, D. Vidovic, A. H. Cowley and
C. D. Abernethy, Chem. Commun., 2004, 360–361.
45 B.-H. Xu, J.-Q. Wang, J. Sun, Y. Huang, J.-P. Zhang, X.-P. Zhang
and S.-J. Zhang, Green Chem., 2015, 17, 108–122.
46 A. Pinaka and G. C. Vougioukalakis, Coord. Chem. Rev.,
2015, 288, 69–97.
47 C. Martin, G. Fiorani and A. W. Kleij, ACS Catal., 2015, 5,
1353–1370.
48 M. Aresta, A. Dibenedetto and A. Angelini, Chem. Rev., 2014,
114, 1709–1742.
49 D. J. Darensbourg and A. I. Moncada, Macromolecules, 2009,
42, 4063–4070.
50 G. W. Coates and D. R. Moore, Angew. Chem., Int. Ed., 2004,
43, 6618–6639.
51 Z. Bu, Z. Wang, L. Yang and S. Cao, Appl. Organomet. Chem.,
2010, 24, 813–816.
52 D. J. Darensbourg and A. I. Moncada, Inorg. Chem., 2008, 47,
10000–10008.