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.

在化学合成计划中，蒙大拿州大学的Dong Wang博士正在研究生成能够将惰性碳氢化合物转换为其功能化衍生物的新方法。这种转化是涉及燃料，化学物质，药品，临床试剂和农业化学物质的几个过程的关键步骤，但是，这种重要转化的基本化学仍在开发。在这个项目中，Wang博士及其小组计划根据后期的首轮过渡金属和一个新颖的Tridentate配体平台开发新的建筑群，直到最近才发现。预计这些金属络合物将是强大的氧化物，以激活碳氢化合物底物中的惰性碳 - 氢键并在其上安装所需的官能团。基于初步结果，预计该项目将在这些复合物的结构，光谱特性和氧化反应率之间建立关键关系，并将揭示进一步开发该系统到催化碳氢化合物功能化方法。此外，该项目将通过建立“生物无机化学合作伙伴关系（PIBC）计划”，为蒙大拿州高中和美国原住民部落大学的学生和老师提供良好的培训场所。 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惰性脂肪族碳 - 氢键。这种转化是许多生物学和合成过程中的关键步骤，并且非常需要使用土壤丰富的第一行过渡金属试剂的研究。在这个项目中，Wang博士及其小组提出的提议，要开发具有异常，正式+4氧化状态的新型高价值后期过渡金属配合物，并能够使用刚性，三叉戟，Dianionic N3配体平台激活强饱和的C – H键。这项研究基于他们最近发表的有关生成和表征真正的fide Co（IV）二链络合物的工作，既足以通过X射线晶体学表征来表征，又足够反应，足以清除较强的C – H键。与堪萨斯大学的杰克逊集团合作，Wang集团旨在开发更具反应性的高价值后期过渡金属络合物，并通过计算指导的N3配体，协调阴离子和金属中心的识别的计算指导的，合理的修改来系统地研究其结构反应关系。预计这项研究将产生结果，可以提高高价值化学方面的基本知识，以实现首轮晚期过渡金属络合物，并阐明了该系统的未来开发到催化C – H债券功能化方法。这项奖项反映了NSF的法定任务，并通过该基金会的知识优点和广泛的影响来评估NSF的法定任务。