Nanoengineering heterogeneous catalysts for the selective hydrogenation of key agrochemical derivatives

Rapidly rising world populations have sparked growing concerns over global food production to meet this increasing demand. Figures released by The World Bank suggest that a 50 % increase in worldwide cereal production is required by 2030. Primary amines are important intermediates in the synthesis of a wide variety of fine chemicals utilised within the agrochemical industry, and hence new 'greener' routes to their low cost manufacture from sustainable resources would permit significantly enhanced crop yields. Early synthetic pathways to primary amines employed stoichiometric (and often toxic) reagents via multi-step protocols, resulting in a large number of by-products and correspondingly high Environmental factors of 50-100 (compared with 1-5 for typical bulk chemicals syntheses). Alternative catalytic routes to primary amines have proven fruitful, however new issues relating to selectivity and deactivation have slowed commercialisation. The potential of heterogeneous catalysts for nitrile hydrogenation to amines has been demonstrated in a simplified reaction framework under benign conditions, but further work is required to improve the atom economy and energy efficiency through developing fundamental insight into nature of the active species and origin of on-stream deactivation. Supported palladium nanoparticles have been investigated for the hydrogenation of crotononitrile to butylamine (Figure 1) under favourable conditions, and the impact of reaction temperature, hydrogen pressure, support and loading upon activity and selectivity to C=C versus CºN activation assessed.

Octahedral molybdenum cluster complexes with aromatic sulfonate ligands

This article describes the synthesis, structures and systematic study of the spectroscopic and redox properties of a series of octahedral molybdenum metal cluster complexes with aromatic sulfonate ligands (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] (where X- is Cl-, Br- or I-; OTs- is p-toluenesulfonate and PhSO3 - is benzenesulfonate). All the complexes demonstrated photoluminescence in the red region and an ability to generate singlet oxygen. Notably, the highest quantum yields (>0.6) and narrowest emission bands were found for complexes with a {Mo6I8}4+ cluster core. Moreover, cyclic voltammetric studies revealed that (nBu4N)2[{Mo6X8}(OTs)6] and (nBu4N)2[{Mo6X8}(PhSO3)6] confer enhanced stability towards electrochemical oxidation relative to corresponding starting complexes (nBu4N)2[{Mo6X8}X6].