Manipulating Ligand Fields: Can 1st Row Transition Elements Behave as Their 2nd Row Congeners?

操纵配体场：第一行过渡元素可以表现得像第二行同系物一样吗？

基本信息

批准号：
1664580
负责人：
Peter Wolczanski
金额：
$ 54万
依托单位：
Cornell University
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=1664580&HistoricalAwards=false
关键词：
Manipulating Ligand Fields 1st Row

项目摘要

The Chemical Synthesis Program of the Division of Chemistry supports Prof. Peter T. Wolczanski, Chemistry Department, Cornell University, for research into imparting properties associated 2nd transition elements to 1st transition series elements. Many important commercial applications of transition metals use expensive, heavier elements that often pose significant health risks. This proposal seeks replacement compounds that contain earth abundant, less toxic, base- metals, hence first row transition metal complexes are the general focus. A significant product of this research is the human element; the generation of independent, versatile PhDs capable of adapting to a challenging market, which encompasses academic, industrial, government, and entrepreneurial occupations. The work will be disseminated through the scientific literature, in professional meetings, in the patent literature should the situation arise, and via other appropriate public forums. Iron is targeted specifically for utilization in olefin metathesis, and "redox non-innocent" (RNI) organic ligands are also featured, due to their ability to enhance chemical reactivity by giving or taking electrons from the metal. Special emphasis is given to compounds and transformations that pertain to future catalytic and environmentally friendly applications. A fundamental understanding of ionic vs. covalent character is naturally addressed via the studies of RNI, and comparisons of transition metal reactivity. The scientific product of the research is the expansion of general knowledge regarding first row transition metal electronic structure, and concomitant reactivity. A desktop methodology for determining chemical stability, which provides insight into differences between first row transition metals and their heavier congeners, is under development, thus providing an additional pedagogical product.

化学系的化学合成项目支持康奈尔大学化学系的 Peter T. Wolczanski 教授进行将第二过渡元素相关特性赋予第一过渡系列元素的研究。过渡金属的许多重要商业应用都使用昂贵的较重元素，这些元素通常会带来严重的健康风险。该提案寻求含有地球丰富、毒性较小的贱金属的替代化合物，因此第一排过渡金属配合物是普遍关注的焦点。这项研究的一个重要成果是人的因素。培养独立、多才多艺的博士，能够适应充满挑战的市场，包括学术、工业、政府和创业职业。该工作将通过科学文献、专业会议、专利文献（如果出现这种情况）以及其他适当的公共论坛进行传播。铁专门用于烯烃复分解，并且“氧化还原非无害”（RNI）有机配体也具有特色，因为它们能够通过从金属中给予或夺取电子来增强化学反应性。特别强调与未来催化和环保应用相关的化合物和转化。通过 RNI 的研究和过渡金属反应性的比较，自然可以对离子与共价特性有一个基本的了解。该研究的科学成果是扩展了有关第一行过渡金属电子结构和伴随反应性的常识。一种用于确定化学稳定性的桌面方法正在开发中，该方法可以深入了解第一排过渡金属与其较重同系物之间的差异，从而提供额外的教学产品。

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）

Dispersion forces play a role in (Me 2 IPr)Fe(NAd)R 2 (Ad = adamantyl; R = neo Pe, 1-nor) insertions and Fe–R bond dissociation enthalpies (BDEs)

色散力在 (Me 2 IPr)Fe(NAd)R 2 （Ad = 金刚烷基；R = Neo Pe, 1-nor）插入和 Fe–R 键解离焓 (BDE) 中发挥作用

DOI：
10.1039/c7dt04145d
发表时间：
2018-01
期刊：
Dalton Transactions
影响因子：
4
作者：
Cundari, Thomas R.;Jacobs, Brian P.;MacMillan, Samantha N.;Wolczanski, Peter T.
通讯作者：
Wolczanski, Peter T.

Synthesis and Characterization of 5-Coordinate Tungsten Hydride Anions: [( t Bu 3 SiNH)( t Bu 3 SiN=) 2 HWR]M

5配位氢化钨阴离子的合成与表征：[( t Bu 3 SiNH)( t Bu 3 SiN=) 2 HWR]M

DOI：
10.1002/ijch.201700042
发表时间：
2017-11
期刊：
Israel Journal of Chemistry
影响因子：
3.2
作者：
Schafer, II, Daniel F.;Wolczanski, Peter T.;Lobkovsky, Emil B.;MacMillan, Samantha N.
通讯作者：
MacMillan, Samantha N.

Rare Examples of Fe(IV) Alkyl-Imide Migratory Insertions: Impact of Fe—C Covalency in (Me 2 IPr)Fe(═NAd)R 2 (R = neo Pe, 1-nor)

Fe(IV) 烷基酰亚胺迁移插入的罕见例子： (Me 2 IPr)Fe(-NAd)R 2 (R = neo Pe, 1-nor) 中 Fe-C 共价的影响

DOI：
10.1021/jacs.7b06960
发表时间：
2017-08
期刊：
Journal of the American Chemical Society
影响因子：
15
作者：
Jacobs, Brian P.;Wolczanski, Peter T.;Jiang, Quan;Cundari, Thomas R.;MacMillan, Samantha N.
通讯作者：
MacMillan, Samantha N.

Oxidative Additions to Ti(IV) in [(dadi) 4– ]Ti IV (THF) Involve Carbon–Carbon Bond Formation and Redox-Noninnocent Behavior

[(dadi) 4â ]Ti IV (THF) 中 Ti(IV) 的氧化加成涉及碳-碳键的形成和氧化还原非无害行为

DOI：
10.1021/acs.organomet.8b00930
发表时间：
2019-03
期刊：
Organometallics
影响因子：
2.8
作者：
Heins, Spencer P.;Zhang, Bufan;MacMillan, Samantha N.;Cundari, Thomas R.;Wolczanski, Peter T.
通讯作者：
Wolczanski, Peter T.

Azaallyl-derived ring formation via redox coupling in first row transition metals

第一排过渡金属中通过氧化还原偶联形成氮杂烯丙基衍生环

DOI：
10.1016/j.poly.2018.10.070
发表时间：
2019-01
期刊：
Polyhedron
影响因子：
2.6
作者：
Hulley, Elliott B.;Heins, Spencer P.;Wolczanski, Peter T.;Lancaster, Kyle M.;Lobkovsky, Emil B.
通讯作者：
Lobkovsky, Emil B.