CAS: Collaborative Research: Electronic Structure/Function Relationships in Base Metal Complexes Spanning the Oxo/Oxene and Imide/Nitrene Continuum

CAS：合作研究：跨越氧代/氧烯和酰亚胺/氮烯连续体的贱金属配合物中的电子结构/功能关系

• 批准号: 1954515
• 负责人: Kyle Lancaster
• 金额: $ 30万
• 依托单位: Cornell University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-07-01 至 2023-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1954515&HistoricalAwards=false
• 关键词: CAS; Collaborative; Research; Electronic; Structure

Supported by the Chemical Structure, Dynamics, and Mechanisms B program of the Chemistry Division, Professors Theodore A. Betley of Harvard University and Kyle M. Lancaster of Cornell University synthesize molecules and materials by converting inexpensive, small molecules into higher value-added, more complex molecules such as pharmaceuticals. To accomplish these transformations, the group uses metal-based catalysts to speed up reactions and to selectively produce desired products over less desirable byproducts. The knowledge gained from their catalysis reactions may contribute to achieving a sustainable chemical industry in the United States. The research team is particularly focused on designing and developing catalysts that substitute abundant, inexpensive and non-toxic metals for the precious and, in some cases, toxic metal-based catalysts used today. Professors Betley and Lancaster are involved in educational outreach activities to engage students at the pre-university, undergraduate (internal and external to the university), and graduate levels. The researchers organize and participate in interactive demonstrations for students at the K-12 level from local grade schools and high schools. In this project ,funded by the Chemical Structure, Dynamics, and Mechanisms B program of the Chemistry Division, Professors Theodore A. Betley of Harvard University and Kyle M. Lancaster of Cornell University examine electronic structure design for C-H bond functionalization. This collaboration between a synthetic inorganic chemist and inorganic spectroscopist seeks to provide new perspectives on the correlation of radical accumulation on main-group ligands towards base-metal C−H bond functionalization catalysis. Such information is critical to advancing both fundamental understanding as well as synthetic methodologies. The research involves the synthesis and characterization of novel metal-ligand multiple bonded (MLMB) systems that mimic biological monooxygenases that deliver diverse functionalities into C-H bond substrates. The ability to selectively incorporate functionality into unactivated C-H bonds represents an advance in converting inexpensive chemical feedstocks (e.g. hydrocarbons) to value-added molecules (e.g., pharmaceutical precursors). To this end, Betley and Lancaster seek to synthesize MLMB complexes featuring N- and O-bearing functionalities to examine and harness their reaction chemistry. Betley and Lancaster propose to leverage N and O K-edge XAS as means to probe the sub-octet character of coordinated N- and O-based ligand donors and to quantify metal-ligand covalency in coordination complexes. These data will be used to rationalize periodic trends in the reactivity (nucleophilic vs. electrophilic) of MLMB complexes across the late first transition series. Undergraduates, graduate students, and postdoctoral scholars from groups that are underrepresented in science are integral to carrying out the sustainability aims.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、动力学和机理B项目的支持下，西奥多A.哈佛大学的Betley和凯尔M.康奈尔大学的兰开斯特通过将廉价的小分子转化为更高附加值、更复杂的分子（如药物）来合成分子和材料。为了实现这些转化，该小组使用金属基催化剂来加速反应，并选择性地生产所需的产品，而不是不太理想的副产品。 从他们的催化反应中获得的知识可能有助于在美国实现可持续的化学工业。 该研究团队特别专注于设计和开发催化剂，以替代丰富，廉价和无毒的金属，以取代目前使用的贵金属催化剂，在某些情况下，有毒的金属催化剂。教授Betley和兰开斯特参与教育推广活动，让学生在大学预科，本科（内部和外部的大学）和研究生水平。研究人员组织并参与当地小学和高中K-12级学生的互动演示。 在这个由化学系化学结构、动力学和机理B计划资助的项目中，西奥多教授A。哈佛大学的Betley和凯尔M.康奈尔大学的兰开斯特研究了C-H键官能化的电子结构设计。合成无机化学家和无机光谱学家之间的这种合作旨在为主族配体上的自由基积累与贱金属C-H键官能化催化的相关性提供新的视角。这些信息对于推进基本理解和综合方法至关重要。该研究涉及新型金属配体多重键合（MLMB）系统的合成和表征，该系统模拟生物单加氧酶，将不同的功能传递到C-H键底物中。选择性地将官能团并入未活化的C-H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）。为此，Betley和兰开斯特寻求合成具有N-和O-承载官能团的MLMB复合物，以检查和利用它们的反应化学。Betley和兰开斯特提出利用N和O K边XAS作为手段来探测配位的N-和O-基配体供体的亚八重态特征并量化配位络合物中的金属-配体共价。这些数据将用于合理化MLMB复合物在第一次过渡系列后期的反应性（亲核与亲电）的周期性趋势。来自科学界代表性不足的群体的本科生、研究生和博士后学者是实现可持续发展目标的不可或缺的一部分。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

TEMPO coordination and reactivity in group 6; pseudo-pentagonal planar (η 2 -TEMPO) 2 CrX (X = Cl, TEMPO)

第 6 组的 TEMPO 协调性和反应性；

• DOI: 10.1039/d2cc03838b
• 发表时间: 2022
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Kayser, Ann K.;Wolczanski, Peter T.;Cundari, Thomas R.;Bollmeyer, Melissa M.;Lancaster, Kyle M.;MacMillan, Samantha N.
• 通讯作者: MacMillan, Samantha N.

An Isolable Mononuclear Palladium(I) Amido Complex

• DOI: 10.1021/jacs.1c04965
• 发表时间: 2021-07-07
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Liu, Jian;Bollmeyer, Melissa M.;Deng, Liang
• 通讯作者: Deng, Liang

Lithium superoxide encapsulated in a benzoquinone anion matrix

• DOI: 10.1073/pnas.2019392118
• 发表时间: 2021-12
• 期刊: Proceedings of the National Academy of Sciences
• 作者: Matthew J Nava;S. Zhang;Katharine S Pastore;Xiaowen Feng;K. Lancaster;D. Nocera;C. Cummins

Electronic Structure of Ru 2 6+ Complexes with Electron-Rich Anilinopyridinate Ligands

富电子苯胺基吡啶配体 Ru 2 6 配合物的电子结构

• DOI: 10.1021/acs.inorgchem.1c03346
• 发表时间: 2022
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Roy, Michael D.;Trenerry, Michael J.;Thakuri, Biswash;MacMillan, Samantha N.;Liptak, Matthew D.;Lancaster, Kyle M.;Berry, John F.
• 通讯作者: Berry, John F.