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Abnormal Carbene Review
Abnormal Carbene Review
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Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 597
2. Overview of metal NHC chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.1. Synthetic strategies to NHC metal complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.1.1. Lappert method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.1.2. Proton abstraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.1.3. Transmetallation from silver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.1.4. In situ deprotonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.1.5. Oxidative addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.1.6. Direct metallation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.1.7. Thermal elimination of H–X from the C2 position . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
2.2. General reactivity of the NHC backbone CH groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 598
3. Syntheses and structures of abnormally bound NHC complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
3.1. Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
3.2. Ruthenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
3.3. Osmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
3.4. Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
3.5. Rhodium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
3.6. Iridium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 600
3.7. Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3.8. Palladium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
3.9. Platinum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
3.10. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
3.11. Silver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
3.12. Gold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
3.13. Yttrium and samarium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
4. Factors affecting abnormal binding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
4.1. Steric factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
4.2. Electronic effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
4.3. Thermodynamic considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
4.4. Kinetic factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
4.5. Choice of anion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
4.6. Blocking groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 606
4.7. Choice of base . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
5. Analysis of abnormal carbene prevalence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
Appendix A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
∗ Corresponding author. Tel.: +44 115 951 3437; fax: +44 115 951 3563.
E-mail address: polly.Arnold@nottingham.ac.uk (P.L. Arnold).
0010-8545/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ccr.2006.08.006
P.L. Arnold, S. Pearson / Coordination Chemistry Reviews 251 (2007) 596–609 597
Abstract
Metal NHC complexes have been known for over 50 years, but only during the last 15 have they been studied as potential catalysts.
N-heterocyclic carbene (NHC) complexes are often more straightforward to make than the phosphine analogues with which they are often
compared, are generally more stable, less odorous and on many occasions have been shown to be anywhere between 100 and 1000 times more
effective.
For a decade it was assumed that NHCs always interacted with metal atoms in the same way. However, examples have now been found that
exhibit unusual binding behaviour. It is important to understand why such abnormal binding occurs and what effects this could have on the catalytic
properties of NHC complexes.
Fig. 1. Synthesis of a palladium(II) NHC precatalyst (1.0.1) LHS, and a ruthenium(II) precatalyst, (1.0.2) RHS, for Heck and alkene metathesis reactions, respectively.
598 P.L. Arnold, S. Pearson / Coordination Chemistry Reviews 251 (2007) 596–609
3.1. Iron
(3.2)
case of (3.6.3d) (R = Me) both isomers are formed in a ratio of The imidazolium salts (3.6.9) also react with IrH5 (PPh3 )2 ,
ca. 55:45 abnormal:normal (3.6.4d:3.6.5d). The ratio was deter- like their methylene-linked analogues (3.6.3) [15]. Under iden-
mined by integration of the NMR spectra of the mixtures, since tical reaction conditions the products are the abnormal NHC
the similar solubilities of the compounds prevented their sepa- complexes (3.6.10). The reaction of the bulky (3.6.9a) is sub-
ration. stantially slower and does not result in full conversion to
Given these syntheses, work was undertaken to prepare ana- (3.6.10a), Eq. (3.4). After recrystallisation, (3.6.10b–d) were
logues where the abnormal NHC was monodentate, to determine obtained as colourless, high-melting (>200 ◦ C) solids. Most
if chelation is necessary for C5 binding [11]. The simple imi- notably for R = Me, the compound (3.6.11d) was not seen; unlike
dazolium salts (3.6.6a and b) were reacted with pyridine and its methylene-linked analogue, only the abnormal NHC was
IrH5 (PPh3 )2 under the same conditions to give a good yield observed:
(3.4)
of (3.6.7a and b), Eq. (3.3). The C5-bound NHC complexes If the C4 and C5 positions are blocked to prevent abnormal
have the least sterically hindered of the three imidazole carbon binding, the C2 bound complex can form under conditions that
atoms selectively bound to iridium. Although compound (3.6.7) would normally result in the abnormal carbene. The reaction of
is less stable than the tethered analogue (3.6.4), chelation is not IrH5 (PPh3 )2 with the benzimidazolium salt (3.6.12), under the
required for abnormal binding to occur:
(3.3)
(3.5)
(3.7)
zannelated NHC complex of Ir, Fig. 5 [17]. This ensures that The reaction was repeated under various conditions, as
only the C2-bound carbene complexes are generated. summarised in Table 1. The structure of (3.8.1) and (3.8.2)
were deduce confirmed by single crystal X-ray diffrac-
3.7. Nickel tion.
The effect of adding a base to the reaction mixture gives
[Ni(1,5-COD)2 ] was reacted with an excess of 1,3-bis- clues to the mechanistic details. The mechanism has not been
tert-butylimidazol-2-ylidene in THF in a sealed Schlenk tube unambiguously established, but it appears that the formation
P.L. Arnold, S. Pearson / Coordination Chemistry Reviews 251 (2007) 596–609 603
Scheme 5. Oxidative addition to a Pt(0) centre at C4 and C5 in imidazolium salts, nbe = norbornene.
3.11. Silver
We have been studying the lanthanide chemistry of NHCs, Fig. 9. Thermal ellipsoid drawing of the molecular structure of complex (3.13.2).
using N-alkyl functionalized amido, and alkoxide substituents Hydrogen atoms, tert-butyl and trimethylsilyl methyl groups, and solvent
to stabilize -bound complexes such as (3.13.1) in Scheme 7 molecules are omitted for clarity, thermal ellipsoids at 50% probability.
[23]. Trivalent f-element cations have recently begun to show a
rich small molecule activation chemistry when substituted 6- strongly paramagnetic metals may allow access to carbene-
heterecycles such as pyrroles and aromatic solvents are used bridged bimetallic lanthanide complexes, which have previously
to stabilize low-oxidation state and unusual f-block complexes been predicted to display unusual magnetic behaviour.
[24].
Treatment of the colorless amido carbene complex Y(L)N2 4. Factors affecting abnormal binding
(3.13.1), with potassium naphthalenide in a DME/diethyl
The factors discussed below are mainly for the formation of
ether mixture at −78 ◦ C affords a dark red solution upon
NHC Ir(III) complexes from iridium hydrides, since this is the
warming to room temperature, from which a colorless
most studied system where abnormal binding occurs. The other
crystalline solid (3.13.2) can be isolated in good yield,
examples of abnormal binding are still mostly attributed to steric
Scheme 7. Complex (3.13.2) is characterized as the bimetal-
factors and the use of blocking groups during the syntheses.
lic dimer [N2 Y(L)K(DME)]2 [25]. To the best of our knowl-
edge, this is the first instance of a negatively charged, 4.1. Steric factors
carbon–bridged NHC complex. The 13 C NMR resonances
for C2 and C4 are observed at 199.2 and 167.5 ppm, In the abnormal NHC complexes of Fe, Cu, Ir and Pd, forma-
respectively, in (3.13.2). These compare with a shift of tion of the abnormal carbene is favoured as it lowers the steric
185.8 ppm for the C2 carbene carbon in (3.13.1), and strain at the metal centre. By varying the size of the N-functional
208.4 ppm for the potassium–NHC complex [KOCMe2 CH2 (1- groups on the NHC and the length of any tether, it is possible to
C{NCHCHNPri })] [26]. The 1 JYC coupling constant of 62 Hz control whether abnormal binding will occur or not [15].
is also the largest reported to date, and in line with those Many analogies have been made between tertiary phosphines
observed for the 2-metallated thiophene and furan, and terphenyl and NHCs due to their similar bulk and -donor properties.
complexes Y(C5 Me5 )2 (2-SC4 H3 )(THF)n (E = S, n = 1, E = O, Molecular modelling studies have shown that the sterically very
n = 2) and Y(η5 :η1 -C5 Me4 SiMe2 NCMe3 )2 (2-SC4 H3 )(THF), bulky phosphine ligand Pt Bu3 is closest to IPr (N,N -bis(2,6-di-
and Y(dmp)Cl2 (THF)3 (dmp = 2,6-dimesitylphenyl) [27]. iso-propylphenyl)imidazolium). PPh3 is best compared to ICy
The solid state structure, Fig. 9, is dimeric: the Y–C4 distance (N,N -bis(cyclo-hexyl)imidazolium.
of 2.447(2) Å in (3.13.2) is significantly shorter than the Y-C2 It Bu (N,N -bis(tert-butyl)imidazolium) and IAd (N,N -
distance in (3.13.1) of 2.501(5) Å, and is at the short end of the bis(adamantyl)imidazolium) are much bulkier than Pt Bu3 ,
Y–C single -bond range [28]. The NHC is bound normally, via although the cone angle is less symmetrical [29]. This wider
C2 to K, with a very short K–C2 distance of 2.954(2) Å. range of available sizes should allow for better tuning of
The anionic nature of this bridging carbene opens up the pos- NHC–metal complexes in catalysis.
sibility of quenching the deprotonated NHC group with other
electrophiles and metal cations. A simple test reaction between 4.2. Electronic effects
complex (3.13.2) and Me3 SiCl in d8 -THF affords Y(L )N2
(3.13.3) in quantitative yield, and KCl, in which the NHC has The idea that NHC ligands should be considered as simple -
reverted to C2-binding at the metal centre. donors and poor -acceptors is still under debate, although the
The deprotonation of the backbone is also effective for largest estimate of the contribution to the metal carbene bond
the Sm(III) analogue of (3.13.1); work with this and other provided by backbonding is about 20% [2,22].
606 P.L. Arnold, S. Pearson / Coordination Chemistry Reviews 251 (2007) 596–609
4.3. Thermodynamic considerations The use of abnormally bound NHC silver complexes for
transmetallation greatly increases the chance of being able to
Density functional theory calculations have predicted that design abnormally bound complexes of metals such as Pd, Au,
the free abnormal carbene should lie about 84 kJ mol−1 higher in Rh, Ir, and Cu. Work by Crabtree and coworkers has shown that
energy than the free normal C2 carbene [15]. Given the observa- blocking the C2 position with a bulky group such as i Pr or Ph is
tions surrounding the formation of abnormal carbene complexes necessary to prevent silver cleaving the C–R group (thus forcing
from iridium hydrides this suggests therefore that the reaction silver to bind via C4/C5), Eq. (4.1) and Table 3 [31]:
is kinetic in nature. Until a system can be found in which the
binding mode can be reversibly changed, from C2 to C4(5) and
vice versa, the thermodynamics cannot be determined.
Fig. 10. Results of structural search. The number of structurally characterised NHC complexes that exhibit normal binding for the elements Fe–Au.
blocking groups such as benzene can be used to encourage the lysts derived from these metal carbene adducts are all genuinely
formation of the desired complex. C2-bound, both before, and during the catalytic chemistry.
The generic structure used for searches are shown in Fig. 11.
4.7. Choice of base
6. Conclusion
Studies of the structure of NHC–palladium complexes have
revealed that the metallation site on the imidazolium salt is stro-
The number of papers on NHCs published each year is
ngly influenced by the presence of base (Table 1) [20]. This has
increasing rapidly (last year ∼150 papers were published). This
implications for the formation of NHC–metal catalysts in situ.
review has shown that abnormal binding accounts for approxi-
The basic/acidic nature of the system will dictate if the abnormal
mately 2% of structurally characterised NHC–metal complexes.
or normal complex forms, and thus the catalytic activity of the
Given these factors it is likely that more examples of abnormal
reaction (abnormally bound have been shown to have different
binding will be discovered, which, we hope, will give access
catalytic activities to normally bound NHCs, vide supra).
to more asymmetric, and/or better catalysts, and other hetero-
bimetallic complexes with perhaps interesting magnetic or elec-
5. Analysis of abnormal carbene prevalence tronic properties. To date, the targeted synthesis of abnormally
bound NHC complexes should be most effective via transmet-
A structural database search was conducted to get an approx- allation syntheses, the use of blocking groups, and from metal
imate measure of the relative abundance of abnormal NHC hydride reagents.
complexes in the second half of the d-block, Fig. 10. It is notable The formation of abnormally bound indium complexes from
that iridium has the greatest prevalence of abnormally bound iridium hydrides at the moment are most prevalent. There are
carbene chemistry in a relatively small number of complexes. A a vast number of metal hydrides; extension of this abnormal
high number of ruthenium and palladium complexes have been chemistry to other metals through hydride complexes would be
reported, although the structurally characterised carbene com- interesting.
plexes are most numerous for rhodium and palladium. It remains Many of the other examples of abnormal binding appear to
unclear as to whether the large number of homogeneous cata- be a result of steric factors. Understanding why abnormal bind-
ing occurs is fundamental, since this alternative binding mode
further extends the versatility of NHCs as ligands.
NMR spectroscopy is a key tool for characterising the bind-
ing mode of NHC complexes. Identifying the structure of NHC
complexes with paramagnetic metals takes much longer since
the NMR spectra are strongly shifted, and often broadened to
baseline, particularly for the 3d and 4f metals. Perhaps the sim-
Fig. 11. Structural searches used (M = metal, Fe–Au; R = carbon containing ple ring deuteriation chemistry of the NHCs described in Section
group). The use of the program ConQuest to search the Cambridge structural
2 may allow 2 H NMR spectroscopy to be used as a screening
database for (5.2.1) and (5.2.2) returned 642 normal and 4 abnormal structures,
respectively [34] but we have also included some recently reported examples, yet method for abnormal binding, as the deuterium NMR spectrum
to appear in the database [35]. A SciFinder Scholar search for structure (5.1.1) of a paramagnetic complex can often prove easy to interpret in
returned more than 4000 structures up to 2005 [21]. place of the 1 H NMR spectrum [36].
608 P.L. Arnold, S. Pearson / Coordination Chemistry Reviews 251 (2007) 596–609
[12] R. Castarlenas, M.A. Esteruelas, E. Onate, Organometallics 24 (2005) W.J. Evans, J. Organomet. Chem. 652 (2002) 61;
4343. S. Gambarotta, J. Scott, Angew. Chem. Int. Ed. 43 (2004) 5298;
[13] H.V. Huynh, C. Holtgrewe, T. Pape, L.L. Koh, E. Hahn, Organometallics Z.M. Hou, Y.G. Zhang, O. Tardif, Y. Wakatsuki, J. Am. Chem. Soc. 123
25 (2006) 245. (2001) 9216.
[14] M. Alcarazo, S.J. Roseblade, A.R. Cowley, R. Fernandez, J.M. Brown, J.M. [25] P.L. Arnold, S.T. Liddle, Organometallics 25 (2006) 1485.
Lassaletta, J. Am. Chem. Soc. 127 (2005) 3290; [26] P.L. Arnold, M. Rodden, C. Wilson, Chem. Commun. (2005) 1743.
A.R. Chianese, A. Kovacevic, B.M. Zeglis, J.W. Faller, R.H. Crabtree, [27] S. Amdt, A. Trifonov, T.P. Spaniol, J. Okuda, M. Kitamura, T. Takahashi,
Organometallics 23 (2004) 2461. J. Organomet. Chem. 647 (2002) 158;
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