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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.

在这个由化学系化学合成计划资助的项目中，宾夕法尼亚大学的Eric Schelter教授和他的研究小组正在制备铈元素的化合物。铈是稀土元素中的一员，具有独特的性质。稀土化合物形成的双键和三键具有极强的反应活性。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。这些物种的反应性有望使没有其他金属的独特化学物质成为可能，有助于发现新的潜在增值化学品，包括染料，药物和聚合物。含铈（+4）配体多重键的新配合物的发现拓展了稀土元素的基础化学。在反应性研究中发现的新有机化合物会产生社会效益。通过面向包括少数民族学生在内的小学生和高中生的外联方案传播成果。代表性不足的群体，包括妇女和代表性不足的少数民族本科生和研究生，受益于该项目的支持。本项目的重点是合成和反应性研究的配合物轴承稀土金属配体多重键，即那些铈（IV）。达到四价状态的铈的能力，预计将使反应性氧代，亚氨基，膦和其他配合物的分离，并使其反应性的研究。还合成了相关的5 f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。相关的电子结构的研究进行光谱与密度泛函理论。通过小分子活化研究识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）

Multiple Bonding in Lanthanides and Actinides: Direct Comparison of Covalency in Thorium(IV)- and Cerium(IV)-Imido Complexes

DOI：
10.1021/jacs.9b04061
发表时间：
2019-06-12
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
影响因子：
15
作者：
Cheisson, Thibault;Kersey, Kyle D.;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

DOI：
10.1016/j.jorganchem.2017.10.017
发表时间：
2018
期刊：
Journal of Organometallic Chemistry
影响因子：
2.3
作者：
Solola, Lukman A.;Carroll, Patrick J.;Schelter, Eric J.
通讯作者：
Schelter, Eric J.

Silyl Transfer Pathway to a Ce(IV) Imido Complex

DOI：
10.1021/acs.organomet.8b00366
发表时间：
2018-12-10
期刊：
ORGANOMETALLICS
影响因子：
2.8
作者：
Cheisson, Thibault;Solola, Lukman A.;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
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
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.