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

区域选择性反Markovnikov加成直接生成末端烯烃，一步制得一次加成产物(醇、胺、酯等)是催化有机合成的主要挑战之一，具有最大的经济效益和绿色效益。这项建议的目的是研究多金属氧酸盐稳定的贵金属纳米团簇作为多相催化剂，用于末端烯烃与水的区域选择性亲核加成得到伯醇。该建议建立在最近发现的金属纳米团簇的稳定和多金属氧酸盐(POM)增强其催化性能的基础上。由POM稳定的后过渡金属纳米颗粒组成的新型固体多功能催化剂具有抗马尔科夫尼科夫烯烃水合反应的潜力，这意味着这些催化剂可以激活C=C双键进行区域选择性亲核加成。我们组建了一支强大的学术-工业团队来开展这项研究：总的来说，我们在多金属氧酸盐化学、催化、有机合成和反应工程方面拥有丰富的经验。拟议方案包括研究上述纳米簇在非均相液/固体系中用于末端烯烃水合反应的区域选择性催化作用。除了这项工作外，还将对催化剂进行仔细的表征，并考察其在反应条件下的稳定性。为了从机理上了解烯烃在金属中心上的吸附，将进行详细的研究。这项提议如果成功，将产生重大的学术和工业影响，提供关于POM稳定金属纳米颗粒的原理和金属催化的区域选择性加成C=C键的机理的知识，以及显著改进区域选择性烯烃水合的工艺。这一研究结果将有助于开发其他重要类型的烯烃区域选择性功能化催化剂，如胺化、酯化和醚化。作为项目合作伙伴，ICI Quest International将为这项研究提供持续的产业视角，以及商业开发的途径。

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.