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

对末端烯烃进行区域选择性反马氏加成，以在一步中直接产生初级加成产物（醇、胺、酯等）。是具有最大经济效益和绿色效益的催化有机合成中的主要挑战之一。这个建议的目的是调查纳米簇的贵金属稳定的聚氧乙烯酸盐作为非均相催化剂的区域选择性亲核加成水的末端烯烃，以获得伯醇。该提案建立在最近发现的金属纳米团簇的稳定性和通过聚氧乙烯酸盐（POM）增强其催化性能的基础上。包含由POM稳定的后过渡金属的纳米颗粒的新型固体多功能催化剂显示出烯烃的反马尔可夫尼科夫水合的潜力，这意味着这些催化剂可以活化C = C双键朝向区域选择性亲核加成。我们已经组建了一支强大的学术-工业团队来开展这项研究：我们在聚氧乙烯酸酯化学，催化，有机合成和反应工程方面拥有丰富的经验。拟议的方案包括区域选择性催化上述纳米团簇的非均相液体/固体体系中的末端烯烃的水合作用的调查。这项工作将通过仔细表征催化剂和研究其在反应条件下的稳定性来补充。将进行烯烃在金属中心上的吸附的详细研究，以获得机理上的理解。该提案如果成功，将产生重大的学术和工业影响，提供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到C = C键的机制的知识，以及烯烃区域选择性水合的显著工艺改进。本研究的结果将是有用的催化剂的发展，其他重要类型的区域选择性功能化的烯烃，如胺化，酯化和醚化。作为项目合作伙伴，ICI Quest International将为研究提供持续的工业视角，以及商业开发路线。

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.