Novel Multidentate Phosphine and Phosphinite Ligands for Catalytic and Imaging Applications

膦、亚膦和亚磷酸盐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，并产生催化物种。该项目将研究一系列新的多齿膦和亚膦配体的合成，这些配体在催化和医学成像方面具有潜在的应用。最近，我们团队开发了一系列多齿膦络合物，这些络合物被发现是生物质衍生酸(如乙酰丙酸)加氢生成1，3-戊二醇和2-甲基四氢呋喃等更高价值化学品的有效催化剂。该项目将在这一初步工作的基础上，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作用的影响。此外，这种多齿配体与99mTc、188Re、68Ga和64Cu等金属的相关成像和治疗放射性视标形成高度稳定的络合物，因此这些配体在这一领域的应用也将被研究。目标：设计和合成一类新的多齿膦和亚膦配体，使之能够形成稳定的三齿和四齿配合物-系统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-用于催化氢化反应的络合物的应用，特别是用于生物质衍生的羧酸的转化-用于配体与相关的金属放射性同位素的络合用于成像应用工作计划：配体和合成：一种使用氯化膦盐生成三齿膦配体的新方法已经在我们小组内得到了良好的效果。将尝试一条类似的路线来合成新的亚磷酸盐和亚磷酸盐配体。络合合成：将研究配体与一系列合适的过渡金属前体盐的反应。形成的络合物的结构和稳定性将通过核磁共振、X射线衍射、质谱学等进行研究，特别是我们将考察形成催化剂的Ru和作为研究TC络合物的模型的Re络合物。应用：使用我们的内部高压加氢反应器，将筛选新生成的催化剂，用于一系列酸到醇的转化。我们将与伦敦国王学院的同事合作，研究放射性99mTc、68Ga和188Re的新型络合物的形成。

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.