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

基本信息

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

项目摘要

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.

在化学结构和化学划分的机制B计划的支持下，Theodore A. Ity和Kyle M. Lancaster Ornell合成分子和材料通过将廉价的小分子转化为D，更复杂的分子，例如，以完成这些转化。，该小组使用基于金属的速度来加快选择性产品，从而使他们的催化中获得的知识在联合的可持续化学工业中得到了反应。目前和基于人类的催化剂的金属都使用了宇宙前的英国学生（大学内部和外部），并为K-12级的学生提供了互动式的。从当地的学院和高中。主体配体 - 金属C-H键官能化催化的新观点。模仿生物学单二酶，使c-h键的能力使anvertin g廉价的化学原料（例如碳氢化合物）到值地址分子（例如，碳氢化合物）（例如，药物的早期功能）。边缘XAS作为协调N和O的配体供体的亚octet的平均值，并量化了协调配位的金属配体协调性。在MLMB Comprexes中，第一个过渡系列中的：在科学中的ePressents是可持续性目标不可或缺的。该奖项反映了NSF的Flytututory Mission，并使用基金会的知识分子优点和更广泛的影响审查标准来通过评估来获得值得的支持。

项目成果

期刊论文数量（7）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

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
影响因子：
0
作者：
Matthew J Nava;S. Zhang;Katharine S Pastore;Xiaowen Feng;K. Lancaster;D. Nocera;C. Cummins
通讯作者：
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.