Summary Calcium salts consisting of Ca2+ weakly coordinated by carborate counterions have been prepared through anhydrous and aqueous methods. The Ca2+ center is sufficiently Lewis acidic to weakly coordinate olefins, alkynes and aromatics, and catalyze the hydrosilylation of 1-hexene and several…
Abstract The first soluble and stable Mg2+ dication stabilized only by weakly coordinating and chemically robust carborate anions [HexCB11Cl11]− is described. Mg[HexCB11Cl11]2 (1), prepared by reaction of Mg(nBu)2 with 2 equiv of [Ph3C][HexCB11Cl11], consists, in the solid state, of a central Mg2+…
Abstract The present study details the synthesis and characterization of a robust, monomeric Al–H aluminate supported by a tridentate tris-phenolate ligand, isolated as [2][Li(THF)4] and [2][N(nBu)4] salts, which were then exploited as CO2 hydroboration catalysts. As initial reactivity studies, it…
Abstract This work details the synthesis and characterization of low-coordinate Zn(II)-based organocations [(NHC)Zn(R)]+ incorporating extremely bulky NHCs [ITr] and [IAd] ([ITr] = ([ITr] = [(HCNCPh3)2C:]; [IAd] = [(HCNAd)2C:], Ad = adamantyl)). Their structural features and particularities are…
Abstract he present report describes the first use of unprotected and “free” N-heterocyclic carbenes (NHCs), such as IMes, IPr and air-stable Cl-IPr carbenes, as single component initiators for the alternating ring-opening co-polymerization (ROCOP) of cyclic anhydrides (phthalic anhydride, PA;…
Abstract We herein report the first use of thiosquaramides as polymerization catalysts, which are shown to be effective for the controlled ROP of lactide in the presence of an alcohol source and NEt3. Comparison of their catalytic performances with the less acidic squaramides are also discussed.…
Abstract The present study details the synthesis and characterization of novel Zn(II)-based organocations of the type [IPr*-Zn-R]+ (IPr* = 1,3-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]-1,3-dihydro-2H-imidazol-2-ylidene; R = alkyl, aryl) and their use in styrene, alkyne, and carbonyl…
Summary A salt compound containing a formal Zn2+ dication only stabilized by weakly coordinated carborate anions was first structurally characterized and shown to be soluble in low polarity solvents. Based on its reactivity with alkene, alkyne and in hydrosilylation catalysis, it is a strong Lewis…
Summary π‐Acids catalysts: Some NHC‐Zn+, NHC‐Al+, as well as other zinc and aluminium cations derived from simple halide salts have been tested as π‐acids in various reactions. Some of these species proved to be excellent catalysts, competing with noble metal complexes.
