High-Valent Non-Oxo-Metal Complexes of Late Transition Metals For sp3 C–H Bond Activation

用于 sp3 C–H 键活化的后过渡金属高价非氧代金属配合物

• 批准号: 2102339
• 负责人: Dong Wang
• 金额: $ 47.5万
• 依托单位: University of Montana
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-07-01 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2102339&HistoricalAwards=false
• 关键词: Valent; Non; Oxo; Metal; Complexes

With the support of the Chemical Synthesis program in the Division of Chemistry, Dr. Dong Wang of the University of Montana is studying new methodologies to generate transition metal complexes that are capable of converting inert hydrocarbons to their functionalized derivatives. This transformation is a key step in several processes involved in the production of fuels, chemicals, pharmaceuticals, clinical reagents, and agrochemicals, however, the underlying chemistry of this important transformation is still being developed. In this project, Dr. Wang and his group plan to develop new complexes based on late first-row transition metals and a novel tridentate ligand platform discovered only recently. These metal complexes are expected to be strong oxidants to activate inert carbon-hydrogen bonds in hydrocarbon substrates and install desired functional groups on them. Based on preliminary results, it is expected that this project will establish key relationships between the structures, spectroscopic properties and oxidative reactivities of these complexes, and will shed light on further developing this system to a catalytic hydrocarbon functionalization method. Further, this project will provide a solid training ground to educate Montana high school and Native American tribal college students and teachers in the field of bioinorganic chemistry by establishing a “Partnership in Bioinorganic Chemistry (PIBC)” program. This program includes three interactive training and outreach components with scientific evaluation and assessment protocols, and is expected to advance science, technology, engineering, and mathematics (STEM) education within the local and Native American communities.With the support of the Chemical Synthesis program in the Division of Chemistry, Dr. Dong Wang of the University of Montana is studying high-valent non-oxo-metal complexes of first-row late transition metals for the activation and functionalization of inert aliphatic carbon-hydrogen bonds. This transformation is a key step in many biological and synthetic processes, and studies that utilize earth-abundant first-row transition metal reagents are highly desirable. In this project, Dr. Wang and his group propose to develop novel high-valent late transition metal complexes having unusual, formal +4 oxidation states and capable of activating strong saturated C–H bonds using a rigid, tridentate, dianionic N3 ligand platform. This research builds on their recently published work on generating and characterizing a bona fide Co(IV)-dinitrate complex that is both stable enough for characterization by X-ray crystallography and reactive enough to cleave strong C–H bonds. In collaboration with the Jackson group at the University of Kansas, the Wang group aims to develop more reactive high-valent late transition metal complexes and systematically investigate their structure-reactivity relationship through computationally guided, rational modifications of the N3 ligand, coordinating anions, and the identity of the metal center. This research is expected to produce results that advance fundamental knowledge in high-valent chemistry for first-row late transition metal complexes, and shed light on future development of this system to a catalytic C–H bond functionalization method.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.

在化学综合计划中的支持下，蒙大拿大学的Dong Wang博士正在研究新方法，以生成能够将惰性碳氢化合物转换为其功能化衍生物的过渡金属复合物。在该项目中，该项目仍在开发燃料，临床试剂和农业化学方面的严重性过程 - 直到最近才发现这些金属配合物的新型三叉戟配体平台有望在碳氢化合物基板中激活惰性碳 - 氢键，并基于初步结果安装所需的功能组。项目将建立关键关系结构，并将该系统开发为催化碳氢化合物功能化方法。化学（PIBC）“该计划将培训和外展成分与Scientific评估和评估评估评估。T协议，并被启动为进步的科学，技术，工程和数学（STEM）当地和美国原住民社区。蒙大拿州大学的综合计划，蒙大拿大学的董王正在研究第一行晚期塔塔尔人的高价值非氧化 - 金属配合物，用于NERT ANERT ANERT ANERT ANERT ANERT ANERT ANERT算体碳 - 氢键在许多生物学和合成过程中迈出的关键步骤，以及利用地球丰富的第一行过渡金属试剂的研究是具有异常，正式+4氧化状态的compplexes，并且能够使用Arigid，Trentate，Trentate，Dianionic，Dianionic，Dianicic，Dianicic，diaionication，diaionication，diaionication，能够激活强的饱和C-H键。 N3配体平台。晚期通过计算指导的结构相对关系，3个配体的原理，协调阴离子和金属中心的身份。方法。该奖项反映了NSF的遗迹，它值得使用Toundation的智力MERIT和更广泛的影响审查标准进行支持。