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.

在化学部门的化学结构，动力学和机制-B计划的支持下，哈佛大学化学与化学生物学系西奥多·贝特利（Theodore Betley）和康奈尔大学化学和化学生物学系的凯尔·兰卡斯特（Kyle Lancaster）正在研究自由基配体过渡金属复合物的电子结构。该协作项目旨在综合和表征新型的金属配体多键（MLMB）系统，该系统可以将潜水功能传递到碳氢键底物中。选择性地将功能合并到未活化的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）的重大进步。该联合项目将利用兰开斯特组的联合专业知识来执行无机光谱法和贝特利集团在合成方面的专业知识，以探索单核和三核过渡金属络合物的周期性趋势以及带有硝酸盐和氮气配体的单核过渡金属络合物。该项目位于无机和有机化学的界面，因此非常适合各个级别的科学家的教育。这些小组在当地小学和高中的K-12级学生组织并参加了互动演示。在这里，邀请学生参加一系列实验，并在实验室观察化学现象。该项目的总体目标是探测金属 - 配体组成及其变化的氧化物水平如何改变所得的物理特性和这些配位复合物的反应性。为此，他们试图合成具有硝酸和硝基氮功能的单核和三核配合物，以检查和利用其反应化学。他们的目的是解决以下问题：（1）分子氧化还原过程如何沿MLMB关联中的主要氧化还原对分布？ （2）MLMB的分子氧化还原变化如何改变氧化物组转移过程？ （3）对于结合群集的imido/nitrido复合物，氧化还原负载如何定位？ （4）对于结合簇的功能，配体孔特性丙烯酸可以在氧化物过程中吗？目标开放壳单元将旨在支持广泛的氧化物状态，从而改变MLMB或合作结合的部分的电子结构。他们将利用n k边缘XAS作为探测协调的N符号的亚周期特征的手段，并量化配位复合物中的M – N共价。这些数据将用于使MLMB和基于集群的复合物在第一个过渡晚期序列中合理化定期趋势（亲核与亲电的趋势）。该奖项反映了NSF的法定任务，并已通过评估基金会的知识绩效和更广泛的影响来审查审查标准。

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.