The calix[4]arene-imidazolium salts 5-(3-butyl-1-imidazolylium)-25,26,27,28-tetrabenzyloxy-calix[4]arene bromide (cone) (2), and 5,11-bis(3-alkyl-1-imidazolylium)-25,26,27,28-tetrabenzyloxycalix[4]arene diiodide (cone) (R = methyl, 3a; R = n-butyl, 3b) have been synthesised. Reaction of 2 in dioxane with PdCl(2) in the presence of CsCO(3) and KBr (80 °C, 24 h) gives the carbene complex trans-[PdBr(2)(calix-monocarbene)(2)] (14), containing two N-heterocyclic carbene ligands derived from 2 (yield: 63%). Repeating the reaction in pyridine instead of dioxane gives the mixed pyridine-carbene complex trans-[PdBr(2)(calix-carbene)(pyridine)] (15) in 75% yield. Treatment of the bis-imidazolium salt 3a with [Pd(OAc)(2)] affords a chelate complex, trans-[PdI(2){calix-bis(carbene)}] (16), in which a metallo-(bis-carbene) fragment caps the upper rim of the calixarene basket. Complex 16, as well as its analogue 17, obtained from 3b, display apparent C(s)-symmetry in solution. This is not the case in the solid state, a single X-ray diffraction study carried out for 16 revealing a pinced cone structure for the calixarene skeleton, which reduces the symmetry to C(1). The chelate complex 17 shows poor activity in Suzuki-Miyaura cross-coupling of phenyl boronic acid and p-tolyl halides, an observation that suggests the presence of a strained metallocyclic unit preventing easy stereochemical rearrangement to an active species. Unlike 17, complexes 14 and 15 show good activities in cross-coupling. A comparative study using the carbene precursor 1-butyl-3-(2,6-diisopropylphenyl)imidazolium bromide (18), which is devoid of the receptor fragment, strongly suggests that the carbene ligands of 14 and 15 operate typically as bulky NHC-ligands.

International audienceBenzimidazolium salts N,N′-disubstituted with 9-alkylfluorenyl groups (3a-e, alkyl = methyl, ethyl, propyl, butyl, benzyl) have been synthesised in high yields in three steps from o-phenylenediamine. This amine was treated with fluorenone in the presence of TiCl4 and tetramethylethylenediamine (TMEDA) to form N,N′-bis(9H-fluoren-9-ylidene)benzene-1,2-diamine (1) in 91 % yield. Diamines 2a-e were then obtained in yields superior or equal to 77 % by reacting diimine 1 with the appropriate organolithium reagent. In the final step, diamines 2a-e were treated with ethylorthoformate under acidic conditions to afford benzimidazolium salts 3a-e. These were readily converted into the PEPPSI palladium complexes 4a-e (PEPPSI = pyridine-enhanced precatalyst preparation stabilisation and initiation). NMR and X-ray diffraction studies revealed that the flat fluorenylidene moiety orientates the alkyl groups towards the metal centre and because of its restricted rotational freedom makes the ligand bulkiness time independent. Thus, the metal centre is permanently confined between the two alkyl groups, and thereby forms a monoligating clamp with the carbenic centre. The CH2 groups close to the palladium ion give rise to anagostic C-H***Pd interactions. Catalytic tests revealed that the palladium complexes 4a-e are highly efficient in Suzuki-Miyaura cross-coupling reactions; their activity is equal or superior to the best PEPPSI catalysts reported to date