SusChEM: Redox Non-Innocence in N- and C-donor Chelate Complexes of 1st Row Transition Elements: Radical Character in Chemistry

SusChEM：第一行过渡元素的 N 和 C 供体螯合物中的氧化还原非纯真：化学中的自由基特征

• 批准号: 1402149
• 负责人: Peter Wolczanski
• 金额: $ 60万
• 依托单位: Cornell University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-08-01 至 2017-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1402149&HistoricalAwards=false
• 关键词: SusChEM; Redox; Non; Innocence; donor

This project, funded by the NSF Chemical Synthesis Program in the Division of Chemistry, supports the research of Professor Peter T. Wolczanski of Cornell University to explore the design and synthesis of first row transition metal complexes containing ligands that expand the chemistry of the metal, primarily through oxidation and reduction processes. The coordinating ligands feature nitrogen (N)- and carbon (C)-donors with multiredox capability, that is they are "redox non-innocent" (RNI) by virtue of giving or taking electrons from the metal, thereby increasing the metal's reactivity. The Wolczanski group employs many first row transition metals such as iron and chromium, making complexes that are uniquely reactive and more environmentally-friendly and sustainable than current precious metal complexes. Professor Wolczanski and his group are active in the local community, actively planning and participating in multi-week after-school experiments for the Chemistry Club at Caroline Elementary School in Ithaca, New York. This research project focuses on experimental studies that seek to: expand the scope of first row transition metal complexes that express redox non-innocence, increase the field strengths about first row transition metals via chelation and metal-carbon bonds, prepare new species capable of unique carbon-carbon bond-forming processes, and generate metal-carbon clusters based on dicarbides. Redox non-innocent (RNI) ligands "electronically buffer" transition metal centers and expand their ability to conduct redox events inherent to bond-making and bond-breaking reactions. This research project focuses on the application of N-donor chelates to the chemistry of first row transition metal complexes, with an emphasis on stabilizing metal-nitrogen and -carbon multiple bonds while rendering them reactive. Operational, functionality tolerant, first row olefin metathesis catalysts are a critical target. The preparation of nitrogen and carbon-based chelates possessing the strong fields are necessary to transform first row transition metal complexes into those capable of second or third row reactivity. Studies also focus on C-C bond-making, featuring metal-stabilized carbanions that possess radical character. Radical hydrocarbon bond activations have led to ligand design features for hydrogen-atom abstraction and C-C couplings; these bond-making processes are scrutinized with regard to scope and the potential for catalysis. Graduate and undergraduate researchers are actively involved in both the experimental and theoretical aspects of the project. The students receive training in several characterizational techniques including Electron Paramagnetic Resonance and Mossbauer spectroscopies as well as magnetometry and electronic structure calculations.

该项目由NSF化学合成计划在化学部门资助，支持康奈尔大学的Peter T. Wolczanski教授的研究，以探索主要通过氧化和还原过程来扩展金属化学的第一行过渡金属络合物的设计和合成，这些金属络合物的设计和合成。配位配体具有氮（N）和具有多氧化氧化氧化的碳（c） - 碳（C） - 即通过从金属中给出或取电子物质，从而提高了金属的反应性。 Wolczanski集团采用了许多第一行过渡金属，例如铁和铬，与当前的贵重金属配合物相比，它们具有独特的反应性和更环保和可持续性的络合物。 Wolczanski教授及其小组活跃于当地社区，积极计划并参加了纽约卡罗琳小学的化学俱乐部的多周课后实验。该研究项目的重点是试图：扩大表达氧化还原非幼体的第一排过渡金属配合物的范围，通过螯合和金属碳键提高野外过渡金属的现场强度，为基于二甲氧甲基于Dicarbides产生独特的碳碳碳键形成过程的新物种，从而提高了第一行过渡金属的田间强度。 氧化还原（RNI）配体“电子缓冲液”过渡金属中心，并扩大了进行粘合和断开键反应固有的氧化还原事件的能力。该研究项目的重点是将N-主螯合剂应用于第一行过渡金属复合物的化学性质，重点是稳定金属氮和碳多键，同时使它们具有反应性。操作，功能耐受性，第一行烯烃的分解催化剂是关键目标。 具有强场的氮和基于碳的螯合物的制备对于将第一排过渡金属配合物转变为能够进行第二行反应性的氮气。 研究还侧重于C-C结合，具有具有激进特征的金属稳定的碳纤维。自由基碳氢化合物的活化导致了氢原子抽象和C-C耦合的配体设计特征。这些结合过程在范围和催化潜力方面进行了审查。 研究生和本科研究人员积极参与项目的实验和理论方面。 学生接受了几种特征技术的培训，包括电子顺磁共振和莫斯鲍尔光谱以及磁力测定法和电子结构计算。