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？

• 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

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Peter T. Wolczanski，康奈尔大学化学系，研究赋予第二过渡元素与第一过渡系列元素相关的性质。过渡金属的许多重要商业应用使用昂贵的重元素，这些元素通常会造成重大的健康风险。该建议寻求含有地球丰富的、毒性较小的贱金属的替代化合物，因此第一行过渡金属络合物是一般的焦点。这项研究的一个重要成果是人的因素;能够适应充满挑战的市场，其中包括学术，工业，政府和创业职业的独立，多才多艺的博士的一代。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。 铁是专门用于烯烃复分解的目标，“氧化还原非无辜”（RNI）有机配体也是其特征，因为它们能够通过从金属中给予或获取电子来增强化学反应性。特别强调的是与未来的催化和环境友好型应用有关的化合物和转化。通过RNI的研究和过渡金属反应性的比较，自然地解决了对离子与共价特性的基本理解。这项研究的科学成果是扩展了关于第一行过渡金属电子结构和伴随反应性的一般知识。目前正在开发一种确定化学稳定性的桌面方法，以深入了解第一行过渡金属及其较重同系物之间的差异，从而提供一种额外的教学产品。

项目成果

Unrealized concepts of masked alkylidenes in (PNP)FeXY systems and alternative approaches to LnXmFe(IV)=CHR

• DOI: 10.1016/j.poly.2020.114460
• 发表时间: 2020-05
• 期刊: Polyhedron
• 影响因子: 2.6
• 作者: Gregory M. George;P. T. Wolczanski;S. MacMillan;T. Cundari

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
• 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.

Activation of Carbon–Hydrogen Bonds via 1,2-RH-Addition/-Elimination to Early Transition Metal Imides

通过早期过渡金属酰亚胺的 1,2-RH 加成/消除来活化碳氢键

• DOI: 10.1021/acs.organomet.7b00753
• 发表时间: 2018
• 期刊: Organometallics
• 影响因子: 2.8
• 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
• 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.