Modulating the reactivity of uranyl by manipulating the O=U=O bond angle in uranyl ansa-type cyclopentadienyl complexes

通过操纵双氧铀酰型环戊二烯基配合物中的 O=U=O 键角来调节双铀酰的反应性

• 批准号: 2657739
• 金额: --
• 依托单位: University of Manchester
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2021
• 资助国家: 英国
• 起止时间: 2021 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2657739
• 关键词: Modulating; reactivity; uranyl; manipulating; O=U=O

The actinide elements display some of the most diverse chemistry encountered anywhere in the Periodic Table, with the key nuclear fuel cycle elements (U, Np and Pu) being the most complex. In aerobic conditions, the +VI (U) and +V (Np) oxidation states dominates and these formdioxo actinyl ions AnO22+ with linear O=An=O bonds. While these have well known andextensive coordination chemistry, there are some remarkable features that have been recentlydiscovered challenging the traditional view and understanding of the thermodynamic stability andkinetic inertness of the actinyl unit (here, uranyl). The redox chemistry of the actinides is also complex;uranyl(V) ions are susceptible to disproportionation and these reactions involve activation of the uranyl bond and oxygen atom transfer reactions, yet the mechanisms for such processes remain unclear. This project aims to probe the bonding in the uranyl cation by employing strongly sigma donating and geometrically constrained ansa-type cyclopentadienyl ligands to influence the reactivity of the uranyl unit. This will alter its electronic structure and reactivity, where we will probe its redox chemistry by luminescence spectroscopy in particular, including oxygen atom transfer reactions, to understand redox processes that occur in nuclear recycle and disposal scenarios.Specific aims are to:- Synthesise a new family of uranyl(VI) complexes coordinated to ansa-Cp type ligands from high valent oxo precursors.- Probe of the electronic structure by optical/ vibrational spectroscopies and DFT calculations.- Investigate the reactivity of the ansa-Cp uranyl complexes for oxygen atom transfer reactions with O atom transfer reagents.- Investigate the photophysics of the ansa-Cp uranyl complexes using UV and visible light using transient absorption and ultrafast emission spectroscopies.- Investigate synthetic routes to uranyl(V) derivatives.

actinide元素显示了元素周期表中任何地方遇到的一些最多样化的化学反应，关键的核燃料循环元素（U，NP和PU）是最复杂的。在有氧条件下， +vi（u）和 +V（NP）氧化状态占主导地位，而这些形式的dioxo stricinyl离子ano22 +具有线性O = AN = O键。尽管这些具有众所周知且扩展的协调化学性质，但最近发现了一些显着的特征，挑战了阳式素基单元的热力学稳定性和运动惰性的传统观点和理解（在这里，铀酰）。肌动剂的氧化还原化学也很复杂；铀酰（V）离子易于占比例，这些反应涉及激活铀酰键和氧原子转移反应，但此类过程的机制尚不清楚。该项目的目的是通过强烈的捐赠和几何限制的ANSA型环戊二烯基配体来探测铀酰阳离子中的键，以影响铀酰基单元的反应性。这将改变其电子结构和反应性，在此将通过发光光谱探测其氧化还原化学，包括氧原子转移反应，以了解核回收和处置场景中发生的氧化还原过程。特定的目的是： - 与脉冲（vi）相吻合的新家族均与Ansa-cp liigands complecters合成，以下是Ansa-cp liigands-ligands-ligands compliens-cp liigands complects-cp liigands complects-cp liigands complecters-ligands complient sa-cp liigands complecters comploce。通过光学/振动光谱和DFT计算通过电子结构。-研究ANSA-CP铀酰复合物与O原子转移试剂的氧原子转移反应的反应性。-使用瞬时吸收和超出型群体进行旋转型群体，研究ANSA-CP铀酰络合物的光生理。