Synthesis, Characterization and Reactivity Studies of Cerium Metal-Ligand Multiple Bonds

金属铈-配体多重键的合成、表征及反应性研究

基本信息

批准号：
1664928
负责人：
Eric Schelter
金额：
$ 40.5万
依托单位：
University of Pennsylvania
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2017
资助国家：
美国
起止时间：
2017-08-01 至 2020-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1664928&HistoricalAwards=false
关键词：
Synthesis Characterization Reactivity Studies Cerium

项目摘要

In this project funded by the Chemical Synthesis program of the Chemistry Division Professor Eric Schelter and his research group at the University of Pennsylvania is preparing compounds of the element cerium. Cerium is a member of the rare earth elements, which possess distinctive properties. Compounds of rare earths form double and triple bonds that are extremely reactive. The goal of this project is to develop synthetic cerium chemistry that will be used to understand the unique reactivity of cerium-ligand multiple bonds. The reactivity of such species is expected to enable unique chemistry found with no other metals, contributing to the discovery of new, potentially value-added chemicals including dyes, pharmaceuticals and polymers. The discovery of new complexes bearing cerium(+4)-ligand multiple bonds expands fundamental chemistry of the rare earth elements. Societal benefits are accrued from new organic compounds identified in reactivity studies. Results are communicated through outreach programs for grade- and high school students including minority students. Underrepresented groups including women and underrepresented minority undergraduates and graduate students benefit from support of the project. This project focuses on synthesis and reactivity studies of complexes bearing rare earth metal-ligand multiple bonds, namely those of Ce(IV). The ability to attain the tetravalent state for cerium is expected to enable isolation of reactive oxo-, imido-, phosphinidine and other complexes and enable studies of their reactivity. Analogous compounds of the related 5f congeners uranium and thorium are also synthesized to understand the reactivity and bonding patterns through comparison. Studies of the associated electronic structures are performed using spectroscopy together with density functional theory. Reactivity patterns, discerned through small molecule activation studies, are established the unique nucleophilic/electrophilic characteristics.

在这个由宾夕法尼亚大学化学系化学合成项目资助的项目中，埃里克·谢尔特教授和他的研究小组正在制备元素铈的化合物。铈是稀土元素的一员，具有独特的性质。稀土化合物形成极其活泼的双键和三键。该项目的目标是开发合成铈化学，用于了解铈配体多重键的独特反应性。这些物质的反应性有望实现其他金属所没有的独特化学反应，从而有助于发现新的、具有潜在附加值的化学品，包括染料、药物和聚合物。带有铈(+4)-配体多重键的新配合物的发现扩展了稀土元素的基础化学。社会效益是从反应性研究中发现的新有机化合物中获得的。结果通过针对小学和高中学生（包括少数族裔学生）的外展计划进行传达。包括女性和少数族裔本科生和研究生在内的代表性不足的群体受益于该项目的支持。该项目重点关注稀土金属-配体多重键配合物（即 Ce(IV) 配合物）的合成和反应性研究。铈达到四价状态的能力有望实现活性氧代、亚氨基、膦胺和其他络合物的分离，并能够研究它们的反应性。还合成了相关 5f 同系物铀和钍的类似化合物，以通过比较了解反应性和成键模式。使用光谱学和密度泛函理论对相关电子结构进行研究。通过小分子活化研究辨别的反应模式建立了独特的亲核/亲电特性。

项目成果

期刊论文数量（9）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

13 C NMR Shifts as an Indicator of U–C Bond Covalency in Uranium(VI) Acetylide Complexes: An Experimental and Computational Study

13 C NMR 位移作为铀 (VI) 乙炔络合物中 U–C 键共价的指标：实验和计算研究

DOI：
10.1021/acs.inorgchem.8b03175
发表时间：
2019-03
期刊：
Inorganic Chemistry
影响因子：
4.6
作者：
Mullane, Kimberly C.;Hrobárik, Peter;Cheisson, Thibault;Manor, Brian C.;Carroll, Patrick J.;Schelter, Eric J.
通讯作者：
Schelter, Eric J.

An investigation of the binding of ( S )-monothioBINOLate to rare earth metal cations

(S)-monothioBINOLate 与稀土金属阳离子结合的研究

DOI：
10.1080/10426507.2019.1602773
发表时间：
2019-04
期刊：
and Silicon and the Related Elements
影响因子：
0
作者：
Panetti, Grace B.;Varela, Elena J.;Gau, Michael R.;Schelter, Eric J.;Walsh, Patrick J.
通讯作者：
Walsh, Patrick J.

Exploration of the Solid- and Solution-State Structures and Electrochemical Properties of Ce IV (atrane) Complexes

Ce IV（阿特拉烷）配合物的固态和溶液态结构及电化学性质的探索

DOI：
10.1021/acs.inorgchem.8b00712
发表时间：
2018-08
期刊：
Inorganic Chemistry
影响因子：
4.6
作者：
Solola, Lukman A.;Cheisson, Thibault;Yang, Qiaomu;Carroll, Patrick J.;Schelter, Eric J.
通讯作者：
Schelter, Eric J.

C–H Bond Addition across a Transient Uranium–Nitrido Moiety and Formation of a Parent Uranium Imido Complex

瞬态铀亚氮基团上的 C–H 键加成以及母体铀亚氨基配合物的形成

DOI：
10.1021/jacs.8b06090
发表时间：
2018-08
期刊：
Journal of the American Chemical Society
影响因子：
15
作者：
Mullane, Kimberly C.;Ryu, Ho;Cheisson, Thibault;Grant, Lauren N.;Park, Ji Young;Manor, Brian C.;Carroll, Patrick J.;Baik, Mu;Mindiola, Daniel J.;Schelter, Eric J.
通讯作者：
Schelter, Eric J.

Cationic cerium(IV) complexes with multiple open coordination sites

具有多个开放配位位点的阳离子铈(IV)配合物