Novel Multidentate Phosphine and Phosphinite Ligands for Catalytic and Imaging Applications

膦、次膦酸酯和亚磷酸酯是无机化学中普遍存在的配体。它们被广泛用于螯合大量过渡金属，稳定氧化态和产生催化物质。本计画将研究一系列新的多齿膦及次膦酸配体的合成，这些配体在催化及医学影像上具有潜在的应用。最近，我们的小组已经开发了一系列多齿膦络合物，这些络合物已经被发现是用于将生物质衍生的酸（例如乙酰丙酸）氢化成更高价值的化学品（例如1，3-戊二醇和2-甲基THF）的有效催化剂。该项目将建立在这一初步工作的基础上，并研究新的螯合配体对一系列其他生物质衍生底物的催化氢化的影响。此外，已知此类多齿螯合配体可与99 mTc、188 Re、68 Ga和64 Cu等金属的相关成像和治疗放射性同位素形成高度稳定的螯合物，因此此类配体在该领域的应用也将被研究。目的：-设计和合成一类新的多齿膦和亚膦酸酯配体，其将能够形成稳定的三齿和四齿配合物-系统地研究这些配体与一系列过渡金属离子如Ru、Re和Cu的配位化学-配合物用于催化氢化反应的应用，特别是用于生物质衍生的羧酸的转化-配体用于配体与相关金属放射性同位素的配位以用于成像应用的应用。一种新的方法，使用氯化鏻盐生成三齿膦配体已被用于在我们的小组内的良好效果。一个类似的路线将尝试用于合成新的次膦酸酯和亚磷酸酯配体。配合物合成：将研究配体与一系列适当的过渡金属前体盐的反应。所形成的络合物的结构和稳定性将通过NMR、X射线衍射、质谱等进行研究。特别是我们将研究Ru形成催化剂和Re络合物作为研究Tc螯合物的模型应用：使用我们内部的高压加氢反应器，将筛选新生成的催化剂用于一系列酸到醇的转化。在与同事在国王学院伦敦，我们将调查与放射性99 mTc，68 Ga和188 Re的新螯合物的形成。

Phosphines, phosphinites and phosphites are ubiquitous ligands in inorganic chemistry. They are widely used to chelate a host of transition metals, stabilise oxidation states and generate catalytic species. This project will investigate synthesis of a range of new multidentate phosphine and phosphinite ligands that have potential applications in catalysis and for medical imaging. Recently our group has developed a range of multidentate phosphine complexes that have found to be effective catalysts for the hydrogenation of biomass derived acids, such as levulinic acid, to higher value chemicals like 1,3-pentanediol and 2-methylTHF. This project will build on this initial work and examine the effect new chelating ligands will have on the catalytic hydrogenation of a range of other biomass derived substrates. Additionally, such multidentate chelating ligands are known to form highly stable chelates with relevant imaging and therapy radioistopes of metals such as 99mTc, 188Re, 68Ga and 64Cu, hence applications of such ligands in this field will also be investigated. Objectives:- design and synthesis of a new class of multidentate phosphine and phosphinite ligands that will enable the formation of stable tri and tetradentate complexes- systematic study of the coordination chemistry of these ligands with a range of transition metal ions such as Ru, Re and Cu- application of complexes for catalytic hydrogenation reactions, specifically for the conversion of biomass derived carboxylic acids- application of ligands for the complexation of ligands with relevant metal radioisotopes for imaging applications Work-Plan: Ligand synthesis: A novel approach using phosphonium chloride salts to generate tridentate phosphine ligands has been used to good effect within our group. An analogous route will be attempted for the synthesis of new phosphinite and phosphite ligands. Complex synthesis: reaction of ligands with a range of appropriate transition metal precursor salts will be investigated. The structures and stabilities of the complexes formed will be investigated by NMR, X-ray diffraction, mass spectrometry etc. in particular we will look at Ru for the formation of catalysts and Re complexes as a model for studying Tc chelatesApplications: using our in-house high pressure hydrogenation reactor newly generated catalysts will be screened for a range of acid to alcohol transformations. In collaboration with colleagues at King's College London we will investigate the formation of novel chelates with radioactive 99mTc, 68Ga and 188Re.