Articles in 2015

Proton-coupled electron transfer (PCET) of metal hydrides, in which electrons and protons go to or from different molecular sites, are key steps in catalytic reactions involving solar fuels. Using [(Cp)W(CO)₃H] as a model compound, it is now shown that this PCET reaction can occur in a concerted fashion, suggesting a possible low-barrier pathway to catalysis.

Bringing porphyrins in contact with well-defined interfaces generates a rich playground of chemical behaviour and properties for exploration and exploitation. This Review examines our current understanding of surface-confined tetrapyrroles and their embedding in nanoarchitectures - discussing both the structural and functional attributes, and methods by which to manipulate their intramolecular and organizational features.

Organic molecular crystals with guest-occupied cavities are often observed, but the cavities tend to collapse when the guests are removed. Now, the porous domain of a crystalline solvate has been stabilized by formation of a cocrystal with a second molecule whose size and shape matches those of the unstable voids.

In vitro assembly of out-of-equilibrium enzymatic reaction networks has proved challenging, limiting the development of autonomous synthetic systems. Now, a methodology has been developed to construct an enzymatic reaction network producing oscillations of active trypsin. The modular approach allows amplification or analog-to-digital conversion of the oscillations, and control over a self-assembly process.

A highly enantio- and diastereoselective route to complex indanes via a 5-endo-trig Michael reaction catalysed by a chiral ammonium salt is described. The preference for this formally disfavoured cyclization over a formally favoured alternative shows that geometric and stereoelectronic constraints may not be decisive in the observed outcome of irreversible ring closing reactions.

The synthetic challenge of constructing arrays of contiguous, chlorinated stereogenic centres in natural products, like the chlorosulfolipids, has sparked recent interest in new methods for stereocontrolled chlorination. Now the first catalytic, syn-stereospecific dichlorination of alkenes, employing a redox-active main group element as a group transfer catalyst is described.

Porous-alumina filter discs typically used to prepare graphene-oxide films are found to corrode during filtration and release aluminium ions that crosslink the negatively charged sheets and make the films insoluble in water. In contrast, aluminium-free graphene-oxide films are significantly weaker and readily disintegrate in water.