Electronic origin of negative thermal expansion in VOPO.

Negative volume expansion between 620 and 800 K in VOPO is discovered to be of electronic origin due to the charge ordering transition at 605 K. Domain reorientation and coexistence of the low and high temperature phases close to the transition are observed in X-ray diffraction data from single crystals grown by chemical vapour transport.

Mechanochemical dehydrocoupling of dimethylamine borane and hydrogenation reactions using Wilkinson's catalyst.

Mechanochemistry enabled the selective synthesis of the recherché orange polymorph of Wilkinson's catalyst [RhCl(PPh3)3]. The mechanochemically prepared Rh-complex catalysed the solvent-free dehydrogenation of Me2NH·BH3 in a ball mill. The in situ-generated hydrogen (H2) could be utilised for Rh-catalysed hydrogenation reactions by ball milling.