Organometallic Chemistry of High Valent Nickel

高价镍的有机金属化学过渡金属催化剂用于制造许多重要产品，包括救生药品、保护作物的农用化学品和电子材料。这些产品的成本和可持续性直接受到新催化剂开发的影响，这些催化剂更便宜，产生的废物更少，在更温和的条件下运行。该领域的一个特别重要的目标是取代基于稀有和昂贵的贵金属（例如钯）的催化剂，并转向来自廉价和更容易获得的金属（例如镍）的催化剂。然而，通常情况下，更理想的廉价金属具有非常不同的（通常是有问题的）特性，这使得它们难以用于这些重要的应用。在这个项目中，Sanford博士和她的研究小组正在对镍催化剂进行详细的研究。这项工作的总体目标是确定如何控制镍催化剂的性质，使它们的性能与钯类似物一样好或更好。桑福德博士还积极参与旨在增加女性在科学和工程领域参与的外展活动。例如，她正在参与一些项目，让中学年龄的女孩参与科学活动，并为科学/技术领域的职业培养多样化的研究生。在化学部化学催化项目的资助下，密歇根大学的Sanford博士正在研究高价镍中间体的基本有机金属化学[即镍（III）和镍（IV）配合物]。尽管有机金属镍（III）和镍（IV）化合物与多种重要的ni催化交叉偶联和C-H功能化反应有潜在的相关性，但它们的合成和反应性尚未得到系统的探索。目前的工作重点是利用模型系统和催化中间体在镍（III）和镍（IV）中心建立各种转化的可行性和机制。在此建立的反应性和选择性谱预计将对新的高价镍催化转化的设计和优化产生革命性的影响。桑福德博士还积极参与旨在扩大女性在K-12、本科、研究生和教师层面参与科学的推广项目。此外，她的项目是在无机和有机合成、无机反应机制、电化学和催化等跨学科领域培养一批多样化的科学家。一支训练有素和多样化的科学队伍对于21世纪创新和技术的持续进步至关重要。

Organometallic Chemistry of High Valent NickelTransition metal catalysts are used to manufacture many important products, including life-saving pharmaceuticals, crop-protecting agrochemicals, and electronic materials. The cost and sustainability of these products are directly impacted by the development of new catalysts that are less expensive, that generate less waste, and that operate under milder conditions. A particularly important goal for the field is to replace catalysts that are based on rare and expensive precious metals (e.g. palladium) and towards those derived from inexpensive and more readily available metals (e.g., nickel). Often, however, the more desirable inexpensive metals have very different (and often problematic) properties, that make them difficult to use for these important applications. In this project Dr. Sanford and her research group are conducting detailed studies of nickel catalysts. The overall goal of this work is to determine how to control the properties of nickel catalysts to enable them to perform as well or better than their palladium analogues. Dr. Sanford is also actively involved in outreach activities that seek to increase the participation of women in science and engineering. For example, she is working with programs that engage middle-school aged girls in scientific activities and that train diverse graduate students for careers in science/technology.With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Sanford of the University of Michigan is studying the fundamental organometallic chemistry of high valent nickel intermediates [i.e., nickel(III) and nickel(IV) complexes]. Despite their potential relevance to a wide variety of important Ni-catalyzed cross-coupling and C-H functionalization reactions, the synthesis and reactivity of organometallic nickel(III) and nickel(IV) compounds has not been systematically explored. The current work is focused on establishing the feasibility and mechanisms of a variety of transformations at nickel(III) and nickel(IV) centers using both model systems and catalytic intermediates. The reactivity and selectivity profiles that are being established herein are expected to have a transformative impact on the design and optimization of new high valent Ni-catalyzed transformations. Dr. Sanford is also actively engaged in outreach programs aimed at broadening participation of women in science at the K-12, undergraduate, graduate, and faculty levels. Furthermore, her project is training a diverse group of scientists in the interdisciplinary areas of inorganic and organic synthesis, inorganic reaction mechanisms, electrochemistry, and catalysis. A well-trained and diverse scientific workforce is essential for continued advances in innovation and technology in the 21st century.