Palladium nanoparticles stabilised by tris(3-sulfophenyl)phosphine trisodium salt in neat glycerol have been synthesised and fully characterised, starting from both Pd(II) and Pd(0) species. The versatility of this innovative catalytic colloidal solution has been proved by its efficient application in C À X bond formation processes (X = C, N, P, S) and C À C multiple bond hydrogenation reactions. The catalytic glycerol phase could be recycled more than ten times, preserving its activity and selectivity. The scope of each of these processes has demonstrated the power of the as-prepared catalyst, isolating the corresponding expected products in yields higher than 90%. The dual catalytic behaviour of this glycerol phase, associated to the metallic nanocatalysts used in wet medium (molecular-and surface-like behaviour), has allowed attractive applications in onepot multi-step transformations catalysed by palladium, such as C À C coupling followed by hydrogenation, without isolation of intermediates using only one catalytic precursor.

A new series of 2,4,6‐triaryl‐λ5‐phosphinines have been synthesized that contain different substituents both on the carbon backbone and the phosphorus atom of the six‐membered heterocycle. Their optical and redox properties were studied in detail, supported by in‐depth theoretical calculations. The modularity of the synthetic strategy allowed the establishment of structure–property relationships for this class of compounds and an OLED based on a blue phosphinine emitter could be developed for the first time.

This Minireview considers the foremost reported works involving glycerol as a solvent in the synthesis of organometallic complexes and metallic nanoparticles. This analysis highlights their catalytic applications. A special emphasis is devoted to the ability of glycerol to immobilize nanometric species, which, in turn, enables an efficient recycling of the catalytic phase to give metal-free organic products.

Well‐defined and small copper(I) oxide nanoparticles stabilised by poly(vinylpyrrolidone) in neat glycerol have been synthesised under a dihydrogen atmosphere. The as‐prepared material has been successfully applied in Cheteroatom couplings and azide–alkyne cycloadditions to give the desired products selectively with isolated yields higher than 90 %. Different amines have been used in the CN couplings, which include aqueous ammonia, that led to the synthesis of anilines. Mono‐1,4‐disubstituted triazoles and also bis‐ and tris(triazoles) have been obtained by the regioselective Cu‐catalysed Huisgen reaction, which comprises the synthesis of dissymmetrical substituted bis(triazoles). The catalytic glycerol phase could be recycled at least ten times and keeps its activity and selectivity. Moreover this versatile catalyst allowed tandem cycloaddition/CN coupling processes to give the corresponding polyfunctional products in a high global yield without the isolation of intermediates.