Expanding the Metal-Ligand Multiple Bond Chemistry of the Late Metals

在化学部化学合成计划的资助下，加州圣巴巴拉大学的特雷弗·海顿博士正在开发合成某些金属与氮、氧和硫原子之间的双键和三键（“M=E”键）的新方法。这些新键具有高度反应性，因此，它们与工业上有用的化学品（如带有碳-碳双键和三键的化学品、一氧化氮和一氧化碳）发生了前所未有的化学反应。然而，由于这些分子和键的反应性很强，科学家们还没有完全理解如何选择性地制造它们，而不产生大量不需要的副产物。在这个项目中，Hayton博士正在开发新的化学策略，以限制副反应并仅形成所需的M=E键。通过这种高水平的控制，可以系统地探索这些键的反应性，为新的催化转化打开大门。Hayton博士通过SoCal Organometallics（SCOM）会议积极参与妇女和代表性不足群体的指导。通过组织和参加这次年会，海顿博士为学生提供了演讲和交流的机会。在SoCal Organometallics的工业参与也为这些学生提供了接触潜在雇主的机会。Hayton博士正在开发“还原脱保护”方法，用于合成后期金属配体多重键，如铜和锌的末端硫代络合物，镍的末端氧代络合物和第10族金属的末端氮代络合物。还原性脱保护涉及从硫族元素或氮族元素原子还原性去除保护基团，从而暴露潜在的M=E键。目标配合物使他们能够量化M=E键内的π键的程度，因为它们从Fe到Zn遍历周期表，使化学家更好地理解“氧代墙”的概念。此外，与烯烃，炔烃，NO和CO的反应性研究揭示了前所未有的小分子转化，为这些工业相关底物的新催化反应性打开了大门。该研究为本科生和研究生提供了空气敏感金属络合物合成和表征方面的优秀培训，为他们在学术界，工业界或国家实验室系统的职业生涯做好准备。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

With funding from the Chemical Synthesis Program of the Chemistry Division, Dr. Trevor Hayton of the University of California Santa Barbara is developing new methods for the synthesis of double and triple bonds ("M=E" bonds) between certain metals and nitrogen, oxygen, and sulfur atoms. These new bonds are highly reactive and, consequently, they undergo unprecedented reaction chemistry with industrially useful chemicals, such as those that bear carbon-carbon double and triple bonds, nitric oxide, and carbon monoxide. However, because these molecules and bonds are so reactive, scientists do not fully understand how to make them selectively without making a large number of unwanted side products. In this project, Dr. Hayton is developing new chemical strategies to limit side reactions and form only the desired M=E bonds. With this high level of control, the reactivity of these bonds can be explored in a systematic way, opening the door to new catalytic transformations. Dr. Hayton is actively engaged in the mentoring of women and under-represented groups via the SoCal Organometallics (SCOM) meeting. By organizing and participating in this annual meeting, Dr. Hayton provides students with presentation and networking opportunities. Industry involvement at SoCal Organometallics also provides these students with access to potential employers.Dr. Hayton is developing the "Reductive Deprotection" methodology for the synthesis of late metal-ligand multiple bonds, such as terminal sulfido complexes of copper and zinc, terminal oxo complexes of nickel, and terminal nitrido complexes of group 10 metals. Reductive deprotection involves the reductive removal of a protecting group from a chalcogen or pnictogen atom, unmasking a latent M=E bond. The target complexes allow them to quantify the extent of pi-bonding within the M=E linkage as they traverse the periodic table from Fe to Zn, giving chemists a better understanding of the "oxo wall" concept. Additionally, reactivity studies with alkenes, alkynes, NO, and CO reveal unprecedented small molecule transformations, opening the door to new catalytic reactivity with these industrially relevant substrates. This research provides excellent training to undergraduate and graduate students in the synthesis and characterization of air sensitive metal complexes, preparing them for careers in academia, industry, or the national laboratory system.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.