Metal nanoclusters stabilised by polyoxometalates as novel catalysts for regioselective functionalisation of olefins

Regioselective anti-Markovnikov addition to terminal olefins to yield directly, in one step the primary addition products (alcohols, amines, esters, etc.) is one of the major challenges in catalytic organic synthesis which offers the greatest economic reward and green benefits. The aim of this proposal is to investigate nanoclusters of noble metals stabilised by polyoxometalates as heterogeneous catalysts for regioselective nucleophilic addition of water to terminal olefins to obtain primary alcohols. The proposal builds upon the recent discovery of stabilisation of metal nanoclusters and enhancement of their catalytic properties by polyoxometalates (POM). Novel solid multifunctional catalysts comprising nanoparticles of the late transition metals stabilised by POM show the potential for anti-Markovnikov hydration of olefins, which implies that these catalysts can activate the C=C double bond towards regioselective nucleophilic addition. We have assembled a strong academic-industrial team to carry out this research: collectively we have extensive experience in polyoxometalate chemistry, catalysis, organic synthesis and reaction engineering. The proposed programme includes the investigation of regioselective catalysis by the aforementioned nanoclusters for the hydration of terminal olefins in heterogeneous liquid/solid systems. This work will be complemented by a careful characterisation of the catalysts and by investigation of their stability under reaction conditions. A detailed study of adsorption of olefins on metal centres will be carried out in order to obtain mechanistic understanding. The proposal, if successful, will make a major academic and industrial impact providing knowledge of the principles of stabilisation of metal nanoparticles by POM and of the mechanism of metal-catalysed regioselective addition to the C=C bond, as well as dramatic process improvements for the regioselective hydration of olefins. The outcome of this study will be useful for the development of catalysts for other important types of regioselective functionalisation of olefins such as amination, esterification and etherification. As the project partner ICI Quest International will provide a continual industrial perspective on the research, as well as the route for commercial exploitation.