Nothing to sm(Ir)k at : Under appropriate reaction conditions, iridium hydride catalysts promote the isomerization of primary allylic alcohols. The best catalysts, like (R)‐ 1 (P green, O red, N blue, Ir yellow), deliver the desired chiral aldehydes with excellent enantioselectivity and good yields. Mechanistic hypotheses have been developed on the basis of preliminary investigations.
Self‐sorting dynamic library : The effector‐induced modulation of the shape and constitution of the members of a constitutional dynamic network (see scheme) allows for the regulation of the interconnected constituents and for the control of an emergent function, here the generation of an optical output which originates from a charge‐transfer interaction.
A simple addition with a large impact : Addition of aromatic amines such as phenanthroline and 4‐DMAP (4‐dimethylaminopyridine) increases copper(I)‐catalyzed azide alkyne cycloaddition (CuAAC) catalytic activity of [CuCl(SIMes)] at a large range of temperatures in such a way that efficient catalysis can safely take place in hydro‐alcoholic solvents (see scheme).
Don't cry! The attachment of ferrocene moieties on the surface of carbon nano‐onions influences the electrochemical properties of these moieties and the photophysical properties of the carbon nano‐onions (see figure). Quantum chemical calculations confirm that the spectral properties of carbon nano‐onions depend on their size and the degree of functionalisation.
Phosphine‐assisted C? H activation of the methyl group of 2‐methylimidazolium compounds led to a series of iridium, rhodium, and palladium complexes of 2‐methyleneimidazolines. Experimental results confirmed that the product of methyl C? H activation is the kinetic product, whereas the aryl C? H activation product is the thermodynamic product (see scheme).
Phosphorus meets carbohydrates : Dimethyl phosphite reacts with ceric(IV) ammonium nitrate (CAN) to give phosphonyl radicals that add to glycals 1 . The derivatives 2 were isolated in high yields and during a subsequent Horner–Emmons reaction underwent an interesting elimination to give 3,6‐dihydro‐2H‐pyrans 3 . The short sequence with simple precursors is applicable to the transformation of hexoses, pentoses, and disaccharides. Bn=benzyl.
Buckybowls : The adsorption of penta‐tert‐butylcorannulene, a molecule with fivefold symmetry, on Cu(111), a surface with threefold symmetry, is investigated by scanning tunneling microscopy complemented by structure calculations. The symmetry mismatch is resolved by the formation of threefold‐symmetric subunits consisting of three molecules, which combine with single molecules to form a nearly perfect filling of the plane (see picture).
Osmabenzenes can be easily synthesized from two η2‐coordinated olefin osmacycles in the presence of benzonitrile by means of facile hydrogen‐transfer conversions (see graphic). Mechanisms for the formation of osmabenzenes are proposed based on DFT calculations.
Tin knows its oniums! An unusual nitride tetrastannylene and a stannylenated ammonium ion stabilized by a samarium tetradiazaphospholido counterion are the first examples of a tris(organostannylenyl)amine derivative and a divalent tin coordinate onium ion that incorporates 1,2,4‐diazaphospholide ligand (see figure).
Reacting in the 'Ni'ck of time : The title reaction is realized by using an isolated NiII complex ( 1 ). The catalysis tolerates a wide range of important functional groups that are often incompatible with Grignard reagents in cross‐coupling reactions.
