Joffrey Wolf

Dr Agnès Labande
email: labande@lcc-toulouse.fr

Jean-Claude Daran

Rinaldo Poli

Nickel(II) Complexes with Bifunctional Phosphine-Imidazolium Ligands and their Catalytic Activity in the Kumada-Corriu Coupling Reaction

Keywords: Nickel(II), Phosphine, Imidazolium, Bifunctional Ligands, Kumada-Corriu reaction

published or not. The documents may come

Nickel(II) complexes with bifunctional phosphine-imidazolium ligands and their catalytic activity in the Kumada-Corriu coupling reaction

Introduction

The preparation of transition metal complexes of imidazolin-2-ylidenes has received an ever growing attention over the past ten years [START_REF] Bourissou | [END_REF][2][3]. Many transition metals have been used for this purpose, particularly palladium, nickel, rhodium and iridium [4][5][6][7][8][9][10][11][12], [13][14][15][16][17][18][19][20][21][22], [23][24][25][26][27][28][29][30].

The main interest of these N-heterocyclic carbene complexes, in comparison to phosphine complexes, resides in producing robust catalysts which will not undergo decomposition or deactivation. On the other hand, the incorporation of a weaker coordinating unit on the same ligand should ensure a good activity for catalytic applications.

The synthesis of complexes bearing a chelating phosphine/N-heterocyclic carbene (P-NCN) ligand has been recently described [4], [9], [23,31,32]. They are catalytically active, although no thorough study has been published yet concerning their potential in this domain.

In this paper, we describe the preparation of nickel(II) complexes bearing a chelating P-NCN ligand I. The synthesis of the phosphine-imidazolium precursor of this ligand, previously described by Nolan et al. [4] and Tsoureas et al. [9], has been improved. We also report the preparation and characterisation of two nickel(II) complexes containing the phosphine-imidazolium ligand and our attempts to characterise the species obtained by subsequent deprotonation of the imidazolium moiety. Finally, preliminary results on C-C coupling-catalysed reactions are given.

I. Ligand synthesis

The synthesis of salts of the previously reported phosphine-imidazolium cation, 1-(2diphenylphosphinoethyl)-3-mesityl-imidazolium, 1, has been improved. Indeed, the first method, described by Nolan et al., gives the desired compound in only 21% overall yield (starting from N-mesitylimidazole) (Scheme 1a) [4]. Scheme 1. Reagents and conditions: (i) 1,2-dibromoethane (4.4 eq), THF, rt, 2 d (23%); (ii) HPPh2 (1.1 eq), t-BuOK (1.05 eq), DMSO, rt, 1 h (91%). (iii) Ph2P(=O)(CH2)2Br, 150-160°C, 4-5 d (83%); (iv) HSiCl3, chlorobenzene, 120°C, 3 h (75%).

The alternative procedure, developed by Tsoureas et al., involves a phosphine oxide intermediate which is reduced under harsh conditions, and was hardly reproducible in our hands (Scheme 1b) [9]. Moreover, the latter method yields the imidazolium ligand as a mixture of chloride and bromide salts, which can prove problematic for the synthesis of metal complexes.

Our synthetic method is based on the quaternisation of N-mesitylimidazole 2 with 1bromoethanol, to give (1-hydroxyethylene-3-mesityl) imidazolium bromide 3a (90%). We then developed two different routes to obtain the title compound. The first one involves mesylation of alcohol 3a (Scheme 2). Scheme 2. Reagents and conditions: (i) 1-bromoethanol, toluene, 120 °C, 18 h (90%); (ii) NaBF4, H2O/CH2Cl2, rt, 3 d (96%); (iii) MsCl, NEt3, CH2Cl2, 0 °C, 3 h (88%); (iv) HPPh2, t-BuOK, DMSO, rt, 1 h (76%).HSiCl3, chlorobenzene, 120°C, 3 h (75%).

In a first attempt, mesylate 4 was obtained in only 13% yield. However, the presence of a bromide anion made the imidazolium salt quite soluble in water, and most of the product was lost in the aqueous phase during work-up. We thus proceeded to exchange the anion with tetrafluoroborate, leading to the salt 3b in 96% yield. Mesylation using 3b gave us compound 4 in 88% yield, then nucleophilic substitution with KPPh2 [4] produced ligand 1b in 76% yield. However, a drawback of this procedure is the fact that the tetrafluoroborate anion is partially replaced by mesylate. A second route was thus developed to avoid this problem: the imidazolium salt was obtained via bromination of alcohol 3a with PBr3 and subsequent nucleophilic substitution with KPPh2 (67% overall yield, starting from N-mesitylimidazole) (Scheme 3). The successful introduction of PPh2 on the brominated intermediate allowed us to avoid the phosphine protection/deprotection sequence described in Scheme 1 (iv), and to obtain the salt with Br -as the only anion.

Although compound 1a could be used directly for coordination studies, pure compound 1b (without mesylate contamination) was also needed in order to prepare Ni(II) complexes bearing only chloride ligands, vide infra. It was obtained in good yields from 1a (83%), following an anion exchange reaction with NaBF4.

Single crystals of compounds 1a and 1b were investigated by X-ray crystallography.

Molecule 1a (see Figure 1 Selected bond distances and angles are listed in Table 1. Such hydrogen bonding is well known from other imidazolium structures [33,34].

II. Nickel(II) complexes preparation and characterisation

Heating a sample of NiCl2 with 1b and NaCl, or NiBr2(DME) with 1a, in refluxing THF led respectively to the air stable complexes 6 (blue crystalline solid, 63% yield) and 7 (green crystalline solid, 95% yield) (Scheme 4).

N N Ph 2 P + X N Ph 2 P Ni X X X (i) or (ii) N + X = Cl, 6 X = Br, 7 X = BF 4 , 1b X = Br, 1a
Scheme 4. Reagents and conditions: (i) NiCl2, NaCl, THF, 60°C, 18 h; (ii) NiBr2(DME), THF, 75°C, 1 h. Both complexes gave X-ray quality crystals from slow evaporation of acetone solutions (see Figure 2). The metal is bonded to three halide ligands and to the phosphorus atom of the phosphine-imidazolium ligand, to give an overall neutral, zwitterionic structure. Selected bond distances and angles are listed in Table 2. the other two X-Ni-X angles. This could be attributed to the conformation adopted by the C(12) phenyl ring, which is parallel to the X(2)-Ni-X(3) wedge plane, or to the establishment of a hydrogen bonding interaction between the C(1) hydrogen atom and the halogen atom X(3). The latter is suggested by the slightly longer Ni-X(3) distance relative to Ni-X(1) and Ni-X(2) for both structures. Indeed, the X(3)-H(1) distances are 2.678 Å (X = Cl) and 2.826 Å (X = Br), which, although longer than in the free ligand 1a (vide supra), are shorter than the sum of the van der Waals radii of H and X. This does not exclude, however, the possibility of an intermolecular stacking interaction. It is important to underline that the other crystallographically characterized [NiX3L] -with X = Cl and Br show a much smaller dispersion for the Ni-X distances and X-Ni-X angles. In particular, these are symmetry Rather surprisingly, these complexes give relatively sharp 1 H NMR and 31 P resonances in MeOD, indicating diamagnetism. It would seem, therefore, that the methanol solvent has replaced the phosphine ligand in the metal coordination sphere and that the signals observed are due to the free ligand. Indeed, the observed 1 H and 31 P chemical shift(s) correspond to that of compound 1. This behaviour can be rationalized by the presence of a dynamic coordination/dissociation process, inducing broadening and shifting of the free ligand resonances as a result of the complex paramagnetism. This hypothesis is confirmed by a variable temperature 31 P NMR study of solutions obtained by dissolving complex 7 in MeOD.

imposed (C3) for [NiCl3(PPh3)] -[Ni-Cl = 2.
At lower temperatures, the signal shifts downfield and becomes sharper and more intense.

In an attempt to dihydrohalogenate complexes 6 and 7 and generate a neutral phosphinefunctionalized N-heterocyclic carbene complex of nickel(II), which would be related to the recently reported palladium(II) analogue [9], the reaction of 6 and 7 with various base/solvent systems was investigated. In a parallel fashion, we also investigated the deprotonation of compound 1a under the same conditions. We first settled our choice on strong bases like n-BuLi, LiN(SiMe3)2 or KN(SiMe3)2. Compounds 1a, 6 and 7 are all insoluble in THF, but readily dissolve when either one of these bases is added, to afford orange-brown solutions.

Our attempts to isolate a nickel complex from these solutions, however, were not successful.

The formation and stability of the putative carbenic species was therefore probed by 1 H, 13 C and 31 P NMR investigations of the reaction of 1a with KN(SiMe3)2 in THF-d8. At -10°C, the 1 H NMR spectrum clearly indicated the absence of the imidazolium proton between 10 and 11 ppm, while the 31 P NMR spectrum shows only one signal at -22.2 ppm, and the 13 C NMR spectrum shows a large upfield shift of the carbon situated between the two nitrogen atoms, from 141 to 215 ppm.

All these observations agree with the generation of a carbenic species. No degradation of the ligand occurs under these conditions. However, our attempts to crystallise the free carbene were not successful, because decomposition occurred as shown by a colour change from colourless to red at room temperature. This behaviour is quite different from that of a similar ligand, bearing a (2,6-diisopropyl)phenyl moiety instead of a mesityl, which could be crystallized under the same conditions [START_REF] Danopoulos | [END_REF]. This results suggests that the steric protection by the 2,6-isopropyl substituents plays a key role in the stabilization of the N-heterocyclic carbene at room temperature.

The 1 H and 31 1 H NMR spectra. b) 31 P spectra.

However, when the temperature reached 0°C, only one sharp signal at -20.55 ppm was left. Furthermore, no carbenic carbon resonance at 215 ppm could be seen in the 13 C NMR spectrum after leaving the sample for several days at room temperature, under argon. These results indicate the occurrence of an irreversible structural change that consumes the carbene functionality at or above 0°C, consistent with the colour change of the carbenic solution.

However, decomposition yields complex NMR spectra. The only exploitable data is the absence of signal between 10 and 11 ppm in 1 H NMR, that should correspond to the imidazolium proton.

One hypothesis is that the carbene compound dimerizes to yield an alkene derivative, as was shown to occur for analogous systems [42][43][44]. We have made no further efforts to characterize the decomposition products.

Danopoulos et al. isolated the {1-[- (diphenylphosphino)ethyl]-3-[(2,6-diisopropyl)phenyl]imidazol-2-ylidene} compound and
suggested that the presence of bulky groups on both nitrogen atoms of the heterocyclic ring is not necessary for the isolation of stable carbenes [START_REF] Danopoulos | [END_REF]. Our results, however, show that the replacement of the (2,6-diisopropyl)phenyl substituent by a mesityl group, whose steric protection is not much smaller, does not allow room temperature stability. However, the formation of the carbene by deprotonation of 1 below 0°C is indeed confirmed, thus it may be intercepted by the nickel ion to form a stable coordination compound.

In initial studies aimed at obtaining a nickel(II)-carbene complex, ligand 1a was first deprotonated using Li(NSiMe3)2 or K(NSiMe3)2 in THF at -40°C and then added to a nickel(II) precursor (NiBr2 or NiBr2(DME)). The disappearance of the imidazolium proton could be observed by 1 H NMR monitoring. However, the resulting brown-orange reaction mixture showed a complex 31 P NMR spectrum and we could not isolate and characterise the expected complex (see Scheme 5). In subsequent studies, complexes 6 and 7 were deprotonated using similar conditions (Scheme 5). A brown-orange mixture was again formed, but once again a clean product could not be obtained. These systems are able to couple aryl chlorides with aryl Grignard reagents at room temperature and in very good yields [21]. To date, no catalyst bearing a bifunctional ligand with a N-heterocyclic carbene has been tested in the Kumada-Corriu reaction. However, it is known that a proper choice of ligands can affect both oxidative addition and reductive elimination steps involved in the generally accepted mechanism, by stabilising the metal centre at different stages of the catalytic cycle.

For the above reasons, we considered that the nickel carbene-phosphine complex that is expected to form upon dehydrohalogenation of 6 or 7 may exhibit an interesting catalytic activity. Our inability to isolate this complex did not prevent us from testing 6 and 7

themselves, since they may be deprotonated to the neutral carbene complex in situ by the Grignard reagent. A first test was thus carried out with compound 7 for the reaction between phenylmagnesium chloride and iodobenzene in N,N-dimethylacetamide (the precatalyst being soluble in this solvent). The catalytic activity was poor (80% conversion, 8% yield of biphenyl after 20 h at room temperature), even lower than that of NiBr2 under identical conditions (100% conversion, 56% yield of biphenyl). Much more encouraging results were obtained, on the other hand, for the Kumada coupling of 4-chloroanisole with phenylmagnesium chloride in THF (Scheme 6). The results are summarised in Table 3. Pleasingly, when the reaction was carried out with a 3 mol% suspension of 6 in THF, without prior deprotonation of the imidazolium moiety (table 3, entry 3), a 100% conversion and a 80% yield (relative to the limiting 4-chloroanisole reagent) for the expected product 10 were obtained. Under the same conditions, Böhm et al. recovered a non negligeable amount of 4chloroanisole (entries 1 and 2) and obtained a lower proportion of 10. originates from the excess Grignard reagent.

When a base was added to pre-catalyst 6 (entry 4), a total conversion was again observed (only traces of 4-chloroanisole could be detected), but with a lower proportion of 10, and more biphenyl 12. This change in selectivity does not seem to be related to the prior addition of a base to the pre-catalyst, since similar results were obtained with 7 (entries 5 and 7), but with an inversion of the selectivity. Slightly better yields, however, were obtained with 7 compared to 6. In order to evaluate the activity of our complexes, the catalyst ratio (7, entry 6) was lowered to 2 mol%. Again, the conversion after 18h was complete, and the distribution of products was quite similar to that observed with 3 mol% catalyst. However, the amount of homocoupling product 13 raised from 1% to 7%, and the isolated yield was somewhat lower (68%). A small amount of terphenyl was observed as well, which did not occur with IMes/Ni(acac)2 or IMes/Ni(acac)2 systems [START_REF]The presence of terphenyl in the reaction mixture could be explained by the coupling of a second equivalent of Grignard on the methoxy substituent of 4-choroanisole[END_REF]. These results are equal or slightly superior to those reported by Böhm et al. for their bis-carbene nickel(II) catalytic system.

As we always observed a total conversion of the starting material after 18h, we decided to follow the conversion of 4-chloroanisole in time (typical reaction conditions of table 1, entry 5): aliquots of the reaction mixture were quenched at regular intervals and analysed by gas chromatography: we were pleased to see that the conversion was almost total after only 1h (96%, see figure 5), which suggests that the catalytic species is very active for this system.

Indeed, 75% product is formed after only 30 min, and 81% after 1h. To the best of our knowledge, no analogous monitoring experiments have been previously reported for this reaction with use of related complexes as catalysts. It is therefore impossible to make more precise comparisons of catalytic activity. It seems, however, that this system is much more active than previously appreciated and looks very promising for future catalytic applications. [21] Further studies in our laboratory will be devoted to further optimizing it.

Conclusions

In summary, we have presented the synthesis and characterisation of new nickel(II) complexes, where the metal is bonded to a phosphine ligand that contains a pendant imidazolium moiety. The deprotonation of the free ligand generates an unstable imidazolin-2ylidene (observed at low temperature by NMR). By comparison with the previously reported N-2,6-diisopropylphenyl analogue, the N-mesityl group is much poorer for sterically protecting the carbene function. The deprotonation of the coordinated ligand does not lead to isolable neutral carbene complexes. However, these precursors have shown promising results

in catalysis for the Kumada-Corriu coupling reaction, with low catalyst loadings and good yields. We are now interested in: (i) studying more thoroughly the reactivity of complexes 6 and 7 in catalysis; (ii) identify the nature of the deprotonation products of 6 and 7 and understand their catalytic role; (iii) develop related systems by ligand modification in order to improve the catalytic activity in this and other C-C coupling reactions.

Experimental

All reactions were carried out under a dry argon atmosphere using Schlenk glassware and vacuum line techniques. Solvents for synthesis were dried and degassed by standard methods before use. Elemental analyses were carried out by the "Service d'Analyse du Laboratoire de Chimie de Coordination" in Toulouse. 1 H, 13 C{ 1 H, 31 P}, 31 P{ 1 H} and 19 F NMR data were recorded on Bruker AM-250 and AV-500 spectrometers for 1 H, operating at 250 and 500

MHz respectively, on Bruker AV-500 for 13 C and 31 was slowly added to a cold CH2Cl2 solution (10 mL, 0°C) of 3a (622 mg, 2 mmol). The mixture was stirred for 15h at room temperature, diluted with CH2Cl2 (30 mL) and added to a cold saturated NaHCO3 solution (20 mL, 0°C). The organic phase was extracted and washed with cold saturated NaHCO3 solution (1 x 5 mL, 0°C). The solution was dried (MgSO4), filtered and concentrated in vacuum. A white solid was obtained. Yield: 580 mg (78%). 1 H NMR (250 MHz,CDCl3,):  = 2.07 (s, 6H), 2.33 (s, 3H), 4.03 (t, 3 J = 5.5Hz, 2H), 5.23 (t, 3 J = 5.4Hz, 2H), 7.00 (s, 2H), 7.17 (t, 3 J = 1.7Hz, 1H), 8.31 (t, 3 J = 1.7Hz, 1H), 10.09 (t, 3 J = 1.7Hz, 1H) (data consistent with those found in the litterature).

1-(2-ethylmesylate)-3-(2,4,6-trimethylphenyl)-imidazolium tetrafluoroborate 4:

NEt3 (1 mL, 6.84 mmol) was added to a cold CH2Cl2 solution (0°C,20 mL) of 3b (1.45 g, 4.56 mmol). The mixture was stirred at 0°C for 15 min, then CH3SO2Cl (0.53 mL, 6.84 mmol) was slowly added. The temperature was allowed to reach slowly 25°C over 3h and the mixture was concentrated (ca. 5 mL). Water (10 mL) was added and the mixture was stirred for 12h. The two layers were separated, the aqueous phase was extracted with CH2Cl2 (5 mL) and the combined organic extracts washed with water (5 mL). The solution was dried (MgSO4), filtered and concentrated in vacuum to give a brown wax. Yield: 1.6 g (89%

1-(2-diphenylphosphinoethyl)-3-(2,4,6-trimethylphenyl)imidazolium bromide (NCN + Br -) 1a:

KPPh2, freshly made from t-BuOK (140 mg, 1.24 mmol) and HPPh2 (0.24 mL, 1.30 mmol) in DMSO (2mL), was added to a DMSO solution (2 mL) of 5 (445 mg, 1.13 mmol). The solution was allowed to stir for 1 h at room temperature. The solvent was then removed under vacuum. Methanol (5 mL) was added to quench excess KPPh2, then removed under vacuum.

Dichloromethane (10 mL) was added and the mixture was filtered. The filtrate was concentrated (ca. 1.5 mL) and diethyl ether (20 mL) was added. The resulting precipitate was separated and the product was obtained as a white air sensitive solid. Colorless crystals were obtained by slow diffusion of diethyl ether into a CH2Cl2 solution. Yield: 540 mg (95%). 1 H NMR (500 MHz, CDCl3):  = 2.08 (s, 6H), 2.36 (s, 3H), 2.93 (t, 3 J = 6.9Hz, 2H), 4.86 (dt, 3 J = 11.9Hz, 3 J = 6.8Hz, 2H), 7.02 (s, 2H), 7.10 (t, 3 J = 1.8Hz, 1H), 7.36 (m, 6H), 7.46 (m, 4H), 7.66 (t, 3 J = 1.7Hz, 1H), 10.41 (t, 3 J = 1.4Hz, 1H); 31 [NiBr3] -(NCN + ) 7: NiBr2(DME) (309 mg, 1.00 mmol) was added to a suspension of 1a (400 mg, 0.83 mmol) in THF (5 mL). The mixture was stirred at 75°C for 1h. The precipitate was filtered, the green solid obtained was washed with THF (2 x 5 mL) and CHCl3 (2 x 10 mL).

The product was dissolved in acetone (20 mL), filtered on silica and was crystallised from acetone to give green crystals. Yield: 555 mg (95%

Typical procedures for Kumada-Corriu reactions:

Method A: 4-chloroanisole (0.12 mL, 1.0 mmol) was added to a suspension of 7 (21 mg, 0.03 mmol) in 1 mL THF. Phenylmagnesium chloride (0.75 mL, 1.5 mmol) was then added dropwise, and the reaction mixture was stirred for 18 h at room temperature. H2O was added, the solution was dried (MgSO4), filtered on a short path of silica gel and rinsed with dichloromethane. The crude mixture was analysed by gas chromatography, and then purified by column chromatography on silica gel (eluent: pentane/dichloromethane 95:5) to give 10 as a white solid (NMR data consistent with those found in the literature). Yield: 153 mg (83 %).

Method B: n-BuLi (22 L, 0.036 mmol) was added to a suspension of 7 (21 mg, 0.03 mmol) in 1 mL THF, which dissolved instantaneously to give a brown solution. 4-Chloroanisole (0.12 mL, 1.0 mmol) was added to the solution and after stirring for 5 min at room temperature, phenylmagnesium chloride (0.75 mL, 1.5 mmol) was added dropwise. The reaction mixture was stirred for 18 h at room temperature. H2O was added, the solution was dried (MgSO4), filtered on a short path of silica gel and rinsed with dichloromethane. The crude mixture was analysed by gas chromatography, and then purified by column chromatography on silica gel (eluent: pentane/dichloromethane 95:5) to give 10 as a white solid. Yield: 170 mg (92 %) (NMR data consistent with those found in the litterature).

X-ray Structure Determinations: single crystal of each compound was mounted under inert perfluoropolyether at the tip of glass fibre and cooled in the cryostream of the Oxford-Diffraction XCALIBUR CCD diffractometer. Data were collected using the monochromatic MoK radiation (= 0.71073). The structures were solved by direct methods (SIR97 [START_REF] Altomare | [END_REF])

and refined by least-squares procedures on F 2 using SHELXL-97 [62]. All H atoms attached to carbon were introduced in calculation in idealised positions and treated as riding models.

The drawing of the molecules was realised with the help of ORTEP32 [63]. Crystal data and refinement parameters are shown in

Scheme 3 .

 3 Scheme 3. Reagents and conditions: (i) 1-bromoethanol, toluene, 120 °C, 18 h (90%); (ii)

  , left) shows a hydrogen bonding interaction between the bromide anion and the acidic imidazolium proton [C(1)•••Br = 3.506(5) Å, H(1)•••Br = 2.561(1) Å].

Figure 1 .

 1 Figure 1. An ORTEP view of compounds 1a (left) and 1b (right). Ellipsoids are drawn at the

Figure 2 .

 2 Figure 2. An ORTEP view of compounds 6 (left) and 7 (right). Ellipsoids are drawn at the

Figure 3 .

 3 Figure 3. Temperature dependence of selected 1 H NMR resonances of complex 6.

  P NMR monitoring of the deprotonation product of 1a in THF-d8 demonstratesits thermal instability. The two imidazole ring proton signals in the 1 H NMR (located at 7.45 and 7.04 ppm at or below -10°C) noticeably shift upfield to 7.32 and 6.91 ppm, respectively, by the time the temperature reaches 0°C (Figure 4, a). Simultaneously, the 31 P NMR spectrum exhibits a sharp, predominant signal at -21.75 ppm and a small, broad signal at ca. -20.5 ppm (probably minor amounts of material that has already decomposed) at -10°C or below (Figure 4, b).

Figure 4 .

 4 Figure 4. NMR monitoring of the THF-d8 solution obtained from 1a and KN(SiMe3)2. a)

Figure 5 .

 5 Figure 5. Percent conversion of 4-chloroanisole 8 () vs time to give coupling product 10

Final

Final

Table 1

 1

	(a) distances	1a	1b
	P(1)-C(111)	1.825(4)	1.833(2)
	P(1)-C(121)	1.827(5)	1.832(2)
	P(1)-C(12)	1.857(4)	1.856(2)
	N(1)-C(1)	1.315(5)	1.331(2)
	N(1)-C(2)	1.389(5)	1.374(2)
	N(1)-C(11)	1.479(5)	1.477(2)
	N(2)-C(1)	1.337(5)	1.321(2)
	N(2)-C(3)	1.388(5)	1.378(2)
	N(2)-C(211)	1.448(5)	1.460(2)
	C(2)-C(3)	1.330(6)	1.340(3)
	C(11)-C(12)	1.505(6)	1.515(3)
	(b) angles	1a	1b
	C(111)-P(1)-C(121) 103.7(2)	102.60(9)
	C(111)-P(1)-C(12) 101.46(19) 99.20(10)

. Selected bond distances (Å) and angles (°) for compounds 1a and 1b. C(121)-P(1)-C(12) 101.6(2) 102.48(10) C(1)-N(1)-C(2) 109.0(3) 108.31(17) C(1)-N(1)-C(11) 125.4(3) 125.37(17)

Table 2 .

 2 Selected bond distances (Å) and angles (°) for compound 6 and 7.

	(a) distances	6	7
	Ni(1)-X(1)	2.2644(11)	2.3376(11)
	Ni(1)-X(2)	2.2197(11)	2.3072(11)
	Ni(1)-X(3)	2.2959(11)	2.3679(10)
	Ni(1)-P(1)	2.2811(11)	2.2865(17)

  Amongst them is a very efficient Pd-imidazolium chloride precatalyst described by Huang et al., though this system required the use of relatively elevated temperatures [59]. The only known examples involving nickel-N-heterocyclic carbene systems are complexes A, reported by Böhm et al. in 2000.

					N				N	+
	N N +	Br	(i)	Ph 2 P	Ni X X	N	(ii)	Ph 2 P X X Ni	X	N
	1a	PPh 2					6 or 7
	Scheme 5. Reagents and conditions: (i) KN(SiMe3)2, THF, -40°C, then NiBr2 or NiBr2(DME).
			Cl
	Ar		Ar
							Ar = 2,4,6-trimethylphenyl or
		N	N
			+	/ Ni(acac)
						2
							2,6-diisopropylphenyl
			A

(ii) n-BuLi, LiN(SiMe3)2 or KN(SiMe3)2, THF, -

III. Catalytic studies

Nickel catalysts have been proved highly effective for C-C coupling reactions between a Grignard reagent and an aryl or alkyl halide (Kumada-Corriu reaction), usually more so than their palladium analogues. Since the discovery of the metal-catalysed reaction by Kumada and Corriu in the early 1970's

[45,46]

, many ligands have been reported, especially (chelating) diphosphines

[47][48][49][50][51][52][53][54][55][56][57]

, but very few examples of metal-imidazolium salt systems have been reported. Moreover, catalytic systems involving the reaction of unactivated aryl chlorides with aryl Grignard reagents have been described only recently

[58,59]

.

Table 3 .

 3 Nickel-catalysed (NiCl3L 6 and NiBr3L 7) Kumada-Corriu reaction of 4chloroanisole (1 equiv) with phenylmagnesium chloride (1.5 equiv) at room temperature in THF (18h). All reactions were repeated to ensure a good reproducibility of the results. Yields are not optimised. c Relative to 4-chloroanisole. The relatively large amount of biphenyl 12

	Entry	Catalyst	Base	Products % distribution (GC)	Isolated yield 10 (%) c
		(mol%)		10/8/11/12/13/14
	1 a	IMes/Ni(acac)2	-	67/18/2/6/7/0	-
	2 a	IPr/Ni(acac)2	-	71/19/1/16/9/0	-
	3 b	NiCl3L 6 (3)	-	85/0/0.5/9.5/2/3	80
	4 b	NiCl3L 6 (3)	KN(SiMe3)2	75/0.3/0.5/18/4/1.3	80
	5 b	NiBr3L 7 (3)	-	74/0/4/20/1/tr.	83
	6 b	NiBr3L 7 (2)	-	66/0/4/22/7/1	68
	7 b	NiBr3L 7 (3)	n-BuLi	87/0/1/10/1.5/0.5	92

a Ref.

21. b

  P, operating at 125.8 and 202.5 Hz respectively, and on Bruker AC-200 for 19 F, operating at 188 Hz. The spectra were referenced internally using the signal from the residual protiosolvent ( 1 H) or the signals of the solvent

	1-(2-hydroxyethyl)-3-(2,4,6-trimethylphenyl)-imidazolium tetrafluoroborate 3b: NaBF4 (7.05
	g, 64.26 mmol) was added to a biphasic solution (CH2Cl2/H2O: 1/2, 60 mL) of 3a (4.0 g,
	12.85 mmol). The mixture was stirred for 3 days at room temperature (10 mL). The two layers
	were separated, the aqueous phase was extracted with CH2Cl2 (5 mL) and the combined
	organic extracts washed with water (10 mL). The solution was dried (MgSO4), filtered and
	concentrated in vacuum to give a pale orange wax. Yield: 3.95 g (97%). Mp 81-82°C.
	C14H19BF4N2O (318.12) Calcd: C 52.86, H 6.02, N 8.81%. Found: C 52.82, H 5.76, N 8.63
	%. 1 H NMR (500 MHz, CDCl3):  = 2.03 (s, 6H), 2.34 (s, 3H), 3.06 (br, 1 H), 3.96 (t, 3 J =
	4.8Hz, 2H), 4.51 (t, 3 J = 4.8Hz, 2H), 7.01 (s, 2H), 7.19 (t, 3 J = 1.6Hz, 1H), 7.78 (t, 3 J = 1.6Hz,
	1H), 8.70 (t,
	During this time a white solid precipitated in the flask. The suspension was cooled to room
	temperature, the solid was decanted off and washed with toluene (2 x 15 mL). A white solid
	was obtained. Yield: 7.4g, 90%. 1 H NMR (250 MHz,CDCl3):  = 2.07 (s, 6H), 2.33 (s, 3H),
	3.54 (br, 1 H), 4.03 (t, 3 J = 4.8Hz, 2H), 4.85 (t, 3 J = 4.9Hz, 2H), 6.99 (s, 2H), 7.16 (t, 3 J =
	1.5Hz, 1H), 7.97 (t, 3 J = 1.5Hz, 1H), 9.64 (s, 1H) (data consistent with those found in the
	litterature).

( 13 C). Mass spectra (electrospray ionisation or chemical ionisation) were obtained from acetonitrile or methanol solutions on a Nermag R10-10 instrument. GC chromatograms were recorded on a Fisons 8000 Series GC equipped with a SPB-5 capillary column and the products were identified by comparison with authentic samples. Chromatographic work was performed on Silica gel 60Å. Commercial chemicals were from Acros, Aldrich and Avocado. 1-(2-hydroxyethyl)-3-(2,4,6-trimethylphenyl)imidazolium bromide 3a: 2-Bromoethanol (2.1 mL, 29.0 mmol) was added at room temperature to a toluene solution (75 mL) of N-(2,4,6trimethylphenyl) imidazole 2 (4.92 g, 26.4 mmol). The mixture was stirred at 120°C for 18h. 3 J = 1.6Hz, 1H); 13 C NMR (125.8 MHz, CDCl3):  = 17.15, 21.09, 52.37, 60.46, 123.28, 123.95, 129.77, 130.68, 134.46, 136.85, 141.24; 19 F NMR (188 MHz, CDCl3):  = -74.79. MS (IS), m/z (%): 232, (100) [M + -BF4]; 87, (100) [M --C14H19N2O]. 1-(2-bromoethyl)-3-(2,4,6-trimethylphenyl)imidazolium bromide 5: PBr3 (0.19 mL, 2 mmol)

  MHz, CDCl3):  = 17.18, 21.12, 37.34, 49.45, 68.09, 123.63, 124.17, 129.80, 130.56, 134.56, 137.23, 141.35;

	). Mp 42-44°C.
	C15H21BF4N2O3S (396.21) Calcd: C 45.47, H 5.34, N 7.07 %. Found: C 45.36, H 4.95, N 6.84
	%. 1 H NMR (500 MHz, CDCl3):  = 2.06 (s, 6H), 2.35 (s, 3H), 3.07 (s, 3H), 4.71 (t, 3 J =
	4.3Hz, 2H), 4.82 (t, 3 J = 4.3Hz, 2H), 7.02 (s, 2H), 7.22 (s, 1H), 7.85 (s, 1H), 8.73 (s, 1H); 13 C
	NMR (125.8

19

F NMR (188 MHz, CDCl3):  = -74.22. MS (IS), m/z (%): 309.6, (100) [M + -BF4]; 87, (100) [M --C15H21N2O3S].

  P NMR (202.5 MHz, CDCl3):  = -23.29 (s) (data consistent with those found in the litterature).

	2H), 4.55 (dt, 3 J = 10.7, 3 J = 7.2Hz, 2H), 7.01 (s, 2H), 7.15 (t, 3 J = 1.8Hz, 1H), 7.36 (m, 6H), (IS), m/z (%): 399, (100) [M + -NiCl3]; 35, (100) [M --C26H28N2PNiCl2]. MS (DCI[NH3]), m/z
	7.44 (m, 4H), 7.61 (t, 3 J = 1.8Hz, 1H), 8.82 (t, 3 J = 1.8Hz, 1H); 13 C NMR (125.8 MHz, (%): 544, (3) [(M+NH3) + -Cl].
	CDCl3):  = 17.31, 21.13, 29.11, 48.09, 123.43, 123.44, 128.98, 129.44, 129.79, 130.56,
	1-(2-diphenylphosphinoethyl)-3-(2,4,6-trimethylphenyl)imidazolium 132.77, 134.44, 136.82, 141.37; 19 F NMR (188 MHz, CDCl3):  = -74.69 (s); 31 P NMR (202.5 tetrafluoroborate
	(NCN + BF4 -) 1b: MHz, CDCl3):  = -23.52 (s). MS (IS), m/z (%): 399.6, (100) [M + -BF4]; 87, (100) [M --
	Method A: KPPh2, freshly made from t-BuOK (460 mg, 4.1 mmol) and HPPh2 (0.75 mL, 4.3 C26H28N2P].
	mmol) in DMSO (5 mL), was added to a DMSO solution (3 mL) of 4 (1.55 g, 3.9 mmol). The
	solution was allowed to stir for 1 h at room temperature. The solvent was then removed under [NiCl3] -(NCN +) 6: NiCl2 (18 mg, 0.14 mmol) was added to a THF suspension (3 mL) of 1b
	vacuum. . Methanol (15 mL) was added to quench excess KPPh2, then removed under (49 mg, 0.1 mmol) [synthesised by method B]. The mixture was stirred for 18h at 60°C to
	vacuum. CH2Cl2 (10 mL) was added and the mixture was filtered. The filtrate was give a red/violet suspension. After filtration, a blue solid was obtained and washed with
	concentrated (ca. 3 mL) and diethyl ether (40 mL) was added. The resulting precipitate was CHCl3 (3 x 2 mL), dissolved in acetonitrile (2 mL), filtered and acetonitrile was removed in
	separated and the product was obtained as a white air sensitive solid. Yield: 1.42 g (75%). 1 H vacuum to give a blue solid. NaCl (30 mg, 0.5 mmol) was added to the violet solution. The
	NMR (250 MHz, CDCl3):  = 2.03 (s, 6H), 2.33 (s, 3H), 2.80 (t, 3 J = 6.9Hz, 2H), 4.64 (t, 3 J = mixture was stirred at 60°C for 1h. A blue precipitate appeared and the solution became
	6.9Hz, 2H), 6.99 (s, 2H), 7.10 (s, 1H), 7.35 (m, 6H), 7.46 (m, 4H), 7.57 (s, 1H), 9.34 (s, 1H). colorless. The suspension was filtered and washed with THF (2 x 5 mL). The product was
	19 F NMR (188 MHz,CDCl3):  = -74.70 (s); 31 P NMR (101 MHz,CDCl3):  = -20.08 (s). 1 H dissolved in acetonitrile, filtered and dried in vacuo to give a blue solid. Global yield: 35 mg
	NMR revealed a mixture of anions (MeSO3 -[ 2.61, s]/BF4 -). (63%). Blue crystals were obtained by slow diffusion of diethyl ether into an acetonitrile
	Method B: NaBF4 (530 mg, 4.75 mmol) was added to a biphasic solution (CH2Cl2/ H2O, 1/3, solution. Mp 231-233°C. C26H28Cl3N2NiP (564.55) Calcd: C 55.32, H 5.00, N 4.96%. Found:
	12 mL) of 1a (460 mg, 0.95 mmol). The mixture was stirred for 24h at room temperature then C 55.00, H 4.99, N 4.57 %. 1 H NMR (500 MHz, d3-MeOD):  = 1.94 (s, 6H), 2.23 (s, 3H),
	the two layers were separated, the aqueous phase was extracted with CH2Cl2 (5 mL) and the 2.71 (t, 3 J = 5.9Hz, 2H), 4.35 (t, 3 J = 5.8Hz, 2H), 6.99 (s, 2H), 7.26 (m, 6H), 7.35 (m, 4H),
	combined organic extracts washed with water (2 mL). The solution was dried 7.59 (t, 3 J = 1.3Hz, 1H), 7.84 (t, 3 J = 1.3Hz, 1H), 9.14 (s, 1H); 31 P NMR (202.5 MHz, d3-
	(MgSO4),filtered and concentrated (2 mL). Et2O (20 mL) was added to give a white MeOD):  = -23.25 (br); 13 C NMR (125.8 MHz, d3-MeOD):  = 15.94, 19.62, 28.27, 47-48,
	precipitate, it was separated and dried in vacuum. Colorless, air sensitive crystals were 123.06, 124.20, 128.47, 128.97, 129.19, 130.95, 132.43, 134.33, 136.42, 141.06. 1 H NMR
	obtained by slow diffusion of diethyl ether into a CH2Cl2 solution. Yield: 410 mg (88%). Mp (500 MHz, d6-(Me)2CO):  = -2.13 (br), 0.47 (br), 1.30 (s), 1.42 (br), 1.90 (s), 2.07 (br +
	109-110°C. C26H28BF4N2P (486.3) Calcd: C 64.22, H 5.80, N 5.76%. Found: C 63.73, H 6.28, Acetone), 2.12 (s), 2.90 (br), 3.76 (s), 4.07 (br), 6.16 (s), 6.33 (s), 6.57 (br), 20.80 (br). MS
	N 5.29%. 1 H NMR (500 MHz, CDCl3):  = 2.03 (s, 6H), 2.35 (s, 3H), 2.77 (t, 3 J = 7.1Hz,

Table 4 .

 4 Crystallographic data (excluding structure factors) have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 277961-277964. Copies of the data can be obtained free of charge on application to the Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK

(fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk) .

Table 4 .

 4 Crystal data and structure refinement, compounds 1a and 1b.

	Identification code	1b	1a
	Empirical formula	(C26H28N2 P)(BF4)	(C27H30Cl2N2P)Br,CH2Cl2
	Formula weight	486.28	564.31
	Temperature, K	180(2)	180(2)
	Wavelength, Å	0.71073	0.71073
	Crystal system	Triclinic	Monoclinic
	Space group	P -1	P 21/c
	a, Å	9.3799(12)	14.352(2)
	b, Å	10.8049(14)	10.7141(18)
	c, Å	14.090(2)	17.644(2)
	 	71.863(13).
	 	70.702(13)	90.289(10)
	 	74.799(11)
	Volume, Å 3	1260.5(3)	2713.1(7)
	Z	2	4
	Density (calculated), Mg/m 3	1.281	1.382
	Absorption coefficient, mm -1	0.155 mm -1	1.789
	F(000)	508	1160
	Crystal size, mm 3	0.51 x 0.14 x 0.137	0.61 x 0.55 x 0.056
	Theta range, °	2.80 to 26.37	2.84 to 26.37
	Reflections collected	9909	18657
	Independent reflections (Rint)	5159 (0.0323)	5539 (0.0734)
	Completeness, %	99.7	99.8
	Absorption correction	None	Multi-scan
	Max. and min. transmission		0.4461 and 0.2067
	Refinement method	F 2	F 2
	Data / restraints / parameters	5159 / 0 / 310	5539 / 0 / 301
	Goodness-of-fit on F 2	0.890	0.906

Table 5 .

 5 Crystal data and structure refinement, compounds 6 and 7.

	Identification code	6	7
	Empirical formula	C27 H31 Cl3 N2 Ni P, ½(C3H6O)	C26 H28 Br3 N2 Ni P
	Formula weight	593.57	697.91
	Temperature, K	180(2)	180(2)
	Wavelength, Å	0.70930	0.71073
	Crystal system	Monoclinic	Monoclinic
	Space group	P 21/n	P 21/c
	a, Å	12.1663(11)	9.2547(7)
	b, Å	9.1747(8)	13.0627(10)
	c, Å	26.402(2)	23.2366(17)
	 	102.537(7)	94.230(6)
	Volume, Å 3	2876.7(4)	2801.5(4)
	Z	4	4
	Density (calculated), Mg/m 3	1.371	1.655
	Absorption coefficient, mm -1	1.030	5.045
	F(000)	1232	1384
	Crystal size, mm 3	0.32 x 0.21 x 0.073	0.25 x 0.2 x 0.18
	Theta range, °	3.01 to 26.31	2.89 to 26.37
	Reflections collected	18520	20049
	Independent reflections (Rint)	5867 (0.0523)	5730 (0.0490)
	Completeness, %	99.8	99.8
	Absorption correction	Analytical	Analytical
	Max. and min. transmission	0.9303 and 0.7776	0.5762 and 0.4246
	Refinement method	F 2	F 2
	Data / restraints / parameters	5872 / 2 / 317	5730 / 263 / 301
	Goodness-of-fit on F 2	0.868	0.931

Acknowledgements

We are grateful to the CNRS for support of this work and the "Fonds Social Européen" for a Ph.D. fellowship to JW.