CAS: Collaborative Research: Electronic Structure/Function Relationships Underpinning Atom Transfer Reactivity

CAS：合作研究：支撑原子转移反应性的电子结构/功能关系

• 批准号: 2247818
• 负责人: Kyle Lancaster
• 金额: $ 36.64万
• 依托单位: Cornell University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2023
• 资助国家: 美国
• 起止时间: 2023-07-15 至 2026-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2247818&HistoricalAwards=false
• 关键词: CAS; Collaborative; Research; Electronic; Structure

With the support of the Chemical Structure, Dynamics & Mechanisms-B Program of the Chemistry Division, Professors Theodore Betley of the Department of Chemistry and Chemical Biology at Harvard University and Kyle Lancaster of the Department of Chemistry and Chemical Biology at Cornell are investigating the electronic structure of radicaloid ligand transition metal complexes. This collaborative project seeks to synthesize and characterize novel metal-ligand multiple bond (MLMB) systems that can deliver diverse functionalities into carbon hydrogen bond substrates. The ability to selectively incorporate functionality into unactivated carbon hydrogen bonds represents a significant advance in converting inexpensive chemical feedstocks (e.g. hydrocarbons) to value-added molecules (e.g., pharmaceutical precursors). The joint project will leverage the combined expertise of the Lancaster group to perform inorganic spectroscopy and the Betley group’s expertise in synthesis to explore periodic trends in the electronic structure and reactivity of mono- and trinuclear transition metal complexes bearing nitrenoid and nitrido ligands. The project lies at the interface of inorganic and organometallic chemistry and is therefore well suited to the education of scientists at all levels. These groups organize and participate in interactive demonstrations for students at the K-12 level from local grade schools and high schools. Here the students are invited to participate in a series of experiments and observe chemical phenomena at their laboratories. The overarching goals of the project are to probe how metal-ligand compositions and their changing oxidation levels alter the resultant physical properties and reactivity for these coordination complexes. To this end, they seek to synthesize mono- and trinuclear complexes featuring nitrenoid and nitrido functionalities to examine and harness their reaction chemistry. Thus, they aim to address the following questions: (1) How are molecular redox processes distributed along the primary redox pair in MLMB associations? (2) How do molecular redox changes of MLMBs alter oxidative group transfer processes? (3) For cluster-bound imido/nitrido complexes, how is the redox load localized? (4) For cluster-bound functionalities, can ligand hole character accumulate under oxidative processes? The target open-shell units will be designed to support a breadth of molecular oxidation states, altering the electronic structure of the MLMB or cooperatively bound moiety. They will leverage N K-edge XAS as means to probe the sub-octet character of coordinated N-donors and to quantify M–N covalency in coordination complexes. These data will be used to rationalize periodic trends in the reactivity (nucleophilic vs. electrophilic) of MLMB and cluster-based complexes across the late first transition series.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学结构、动力学机制-B计划的支持下，哈佛大学化学与化学生物学系的西奥多·贝特利教授和康奈尔大学化学与化学生物学系的凯尔·兰开斯特教授正在研究类自由基配体过渡金属配合物的电子结构。该合作项目旨在合成和表征新型金属配体多重键（MLMB）系统，该系统可以将不同的功能传递到碳氢键底物中。选择性地将官能团结合到未活性碳氢键中的能力代表了将廉价的化学原料（例如烃）转化为增值分子（例如，药物前体）。该联合项目将利用兰开斯特集团的综合专业知识进行无机光谱学和Betley集团的专业知识在合成中探索周期性趋势的电子结构和反应性的单核和三核过渡金属配合物轴承nitrenoid和nitrido配体。该项目位于无机和有机金属化学的界面，因此非常适合各级科学家的教育。这些团体为当地小学和高中的K-12级学生组织和参加互动示范。在这里，学生们被邀请参加一系列实验，并在他们的实验室观察化学现象。该项目的首要目标是探索金属配体组合物及其氧化水平的变化如何改变这些配位络合物的物理性质和反应性。为此，他们试图合成具有类氮和次氮官能团的单核和三核配合物，以检查和利用它们的反应化学。因此，他们的目标是解决以下问题：（1）分子氧化还原过程如何分布沿着MLMB协会的主要氧化还原对？(2)MLMBs的分子氧化还原变化如何改变氧化基团转移过程？(3)对于团簇结合的亚氨基/氮化物复合物，氧化还原负载如何定位？(4)对于团簇结合的官能团，在氧化过程中配体空穴特征是否会积累？目标开壳单元将被设计为支持分子氧化态的宽度，改变MLMB或协同结合部分的电子结构。他们将利用N-K边XAS作为手段来探测配位的N-供体的亚八位组特征并量化配位络合物中的M-N共价性。这些数据将用于合理化MLMB和基于簇的复合物的反应性（亲核与亲电）的周期性趋势在后期的第一个transition series.This award reflects NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。

项目成果

Tellurolate: an effective Te-atom transfer reagent to prepare the triad of group 5 metal bis(tellurides).

• DOI: 10.1039/d3sc03470d
• 发表时间: 2023-11-08
• 期刊: CHEMICAL SCIENCE
• 影响因子: 8.4
• 作者: Senthil, Shuruthi;Kwon, Seongyeon;Kong, Richard Y.;MacMillan, Samantha N.;Zatsepin, Pavel;Gau, Michael R.;Carroll, Patrick J.;Baik, Mu-Hyun;Lancaster, Kyle M.;Mindiola, Daniel J.
• 通讯作者: Mindiola, Daniel J.