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From Low to High Oxidation States - New Oxidative Routes to Lanthanide Multiple Bonds

从低氧化态到高氧化态 - 稀土多重键的新氧化路线

基本信息

批准号：
EP/L014416/1
负责人：
David Mills
金额：
$ 12.88万
依托单位：
University of Manchester
依托单位国家：
英国
项目类别：
Research Grant
财政年份：
2014
资助国家：
英国
起止时间：
2014 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=EP%2FL014416%2F1
关键词：
Low Oxidation States New Oxidative

项目摘要

The lanthanides are fourteen chemically related elements which exhibit diverse optical and magnetic properties that have facilitated their employment in a myriad of technological applications. They are defined by their highly polarised bonding, which is dominated by electrostatic attractions, and their marked tendency to exhibit the +3 oxidation state in the vast majority of their complexes.As a direct consequence of the predominantly electrostatic bonding in these systems, multiply-bonded lanthanide chemistry is underdeveloped in comparison to corresponding d-block chemistry and is limited to double bonds to carbon to date. Given the catalytic applications of d-transition metal complexes exhibiting double bonds, the development of lanthanide-multiple bond chemistry is a long-term synthetic target and it is proposed that with judiciously selected supporting ligands and synthetic routes terminal lanthanide-element double bonds with a variety of p-block elements are accessible. These complexes will exhibit properties that contrast with and complement examples from well-understood d-block chemistry.In this proposal, cerium(IV) complexes exhibiting terminal multiple bonds to nitrogen, phosphorus and chalcogens (O, S, Se, Te) are targeted. Cerium is unique amongst the lanthanides in having a readily accessible +4 oxidation state. Complexes of Ce(IV) are strong oxidising agents and this property has been utilised in synthesis with ubiquitous reagents such as ceric ammonium nitrate (CAN). Given that CAN has some selectivity and solubility issues, the Ce(IV) complexes developed herein will be investigated for their viability as alternatives to CAN in synthetic chemistry.The Ce(IV) complexes targeted in this proposal will be prepared from Ce(II) synthon precursors. Divalent lanthanide chemistry, with metals in a formal + 2 oxidation state, was previously limited to only a handful of lanthanides but recent major advances in this field have now allowed the isolation and study of divalent chemistry for all lanthanides with the exception of radioactive promethium. The Ce(II) synthons in this proposal will be interesting complexes in their own right with distinctive and unique oxidation potentials. Therefore they will be investigated as alternatives to the widely-used one electron reducing agent samarium(II) diiodide in synthesis. It is important to expand this area in order to realise new synthetic methodologies.All complexes prepared herein will be analysed by advanced analytical and computational techniques. This will give fundamental insight into terminal cerium multiple bonds and although the properties of these complexes cannot be accurately predicted, they promise to be highly reactive and interesting. The target Ce(IV) complexes will exhibit enhanced reactivity in comparison to their early d-transition metal counterparts as they will additionally be strong oxidising agents. Detailed analysis will determine if these complexes hold promise in materials chemistry and catalysis, as archetypal Ce(IV) complexes have previously shown.It is expected that results generated from these studies will be worthy of publication in leading international journals such as Science, Nature Publishing Group, Journal of the American Chemical Society and Angewandte Chemie. These fundamental studies will not just be confined to textbook examples because results from this research will have implications for physics, engineering and materials science.The award of this grant will give the principal investigator the means to train post-graduate and -doctoral workers with the rare ability to handle highly air sensitive f-element complexes, recently highlighted as a major skills shortage by government and the nuclear and fine chemical industries. This research will be communicated to the public by outreach activities as its benefit to society and the environment are favourable for the public perception of science.

镧系元素是14种化学相关的元素，它们表现出不同的光学和磁性，这些特性促进了它们在无数技术应用中的应用。它们被定义为高度极化的键合，这是由静电吸引力为主，和他们的显着趋势，表现出+3氧化态在绝大多数他们的complex.As一个直接后果，占主导地位的静电键合在这些系统中，多重键合镧系元素化学是欠发达相比，相应的d-块化学，并限于双键碳的日期。考虑到d-过渡金属络合物表现出双键的催化应用，镧系元素多重键化学的发展是一个长期的合成目标，并且提出了通过明智地选择支持配体和合成路线，可以获得具有各种p-区元素的末端镧系元素双键。这些配合物将表现出的性质，对比和补充的例子，从众所周知的d-块chemical.In这个建议，铈（IV）配合物显示终端多重键的氮，磷和硫族元素（O，S，Se，Te）的目标。铈在镧系元素中是独特的，具有容易获得的+4氧化态。Ce（IV）的络合物是强氧化剂，并且这种性质已被用于与普遍存在的试剂如硝酸铈铵（CAN）的合成中。鉴于CAN具有一些选择性和溶解性问题，本文开发的Ce（IV）络合物将被研究其作为CAN在合成化学中的替代物的可行性。二价镧系元素化学，金属在形式上的+2氧化态，以前仅限于少数镧系元素，但最近在这一领域的重大进展，现在允许分离和研究的二价化学的所有镧系元素，放射性的promethium除外。在这个建议中的Ce（II）离子将是有趣的配合物在自己的权利与独特的和独特的氧化电位。因此，它们将被研究作为合成中广泛使用的单电子还原剂二碘化钐（II）的替代品。为了实现新的合成方法，扩大这一领域是很重要的。本文制备的所有配合物将通过先进的分析和计算技术进行分析。这将给终端铈多重键的基本见解，虽然这些配合物的性质不能准确预测，他们承诺是高度反应性和有趣的。目标Ce（IV）络合物与它们的早期d-过渡金属对应物相比将表现出增强的反应性，因为它们另外是强氧化剂。详细的分析将确定这些配合物是否在材料化学和催化方面具有希望，正如原型Ce（IV）配合物先前所显示的那样。预计这些研究产生的结果将值得在国际领先期刊上发表，如Science，Nature Publishing Group，Journal of the American Chemical Society和Angewandte Chemie。这些基础研究将不仅仅局限于教科书上的例子，因为这项研究的结果将对物理学、工程学和材料科学产生影响。该基金的授予将使首席研究员能够培养研究生和博士生工作人员，使他们具有处理高度空气敏感的f元素复合物的罕见能力，最近，政府和核工业及精细化学工业强调，这是一个主要的技能短缺问题。这项研究将通过外联活动向公众宣传，因为它对社会和环境的好处有利于公众对科学的看法。

项目成果

期刊论文数量（10）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Functionalized Tris(anilido)triazacyclononanes as Hexadentate Ligands for the Encapsulation of U(III), U(IV) and La(III) Cations

功能化三(苯胺基)三氮杂环壬烷作为六齿配体用于封装 U(III)、U(IV) 和 La(III) 阳离子

DOI：
10.3390/inorganics9120086
发表时间：
2021
期刊：
Inorganics
影响因子：
2.9
作者：
Formanuik A
通讯作者：
Formanuik A

Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy

DOI：
10.1038/nchem.2692
发表时间：
2017-06-01
期刊：
NATURE CHEMISTRY
影响因子：
21.8
作者：
Formanuik, Alasdair;Ariciu, Ana-Maria;Mills, David P.
通讯作者：
Mills, David P.

[U(III) {N(SiMe2 tBu)2 }3 ]: a structurally authenticated trigonal planar actinide complex.

DOI：
10.1002/chem.201404864
发表时间：
2014-11-03
期刊：
CHEMISTRY-A EUROPEAN JOURNAL
影响因子：
4.3
作者：
Goodwin, Conrad A. P.;Tuna, Floriana;McInnes, Eric J. L.;Liddle, Stephen T.;McMaster, Jonathan;Vitorica-Yrezabal, Inigo J.;Mills, David P.
通讯作者：
Mills, David P.

Homoleptic Trigonal Planar Lanthanide Complexes Stabilized by Superbulky Silylamide Ligands