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

在化学系化学合成计划的资助下，加州大学圣巴巴拉分校的特雷弗·海顿博士正在开发新的方法来合成某些金属与氮、氧和硫原子之间的双键和三键(M=E键)。这些新的键是高度活性的，因此，它们与工业上有用的化学品经历了前所未有的反应化学反应，例如那些带有碳-碳双键和三键、一氧化氮和一氧化碳的化学品。然而，由于这些分子和键是如此活跃，科学家们并不完全了解如何在不产生大量不需要的副产品的情况下选择性地制造它们。在这个项目中，海顿博士正在开发新的化学策略，以限制副反应，只形成所需的M=E键。有了这种高水平的控制，这些键的反应性可以系统地探索，为新的催化转化打开了大门。海顿博士通过南加州有机金属学会(SCOM)会议，积极参与指导妇女和代表不足的群体。通过组织和参加这次年度会议，海顿博士为学生提供了演讲和交流的机会。SoCal有机金属公司的行业参与也为这些学生提供了接触潜在雇主的机会。海顿正在为合成晚期金属-配体多键，如铜和锌的末端硫化物络合物，镍的末端氧配合物，以及第10族金属的末端硝基络合物，正在开发“还原去保护”方法。还原去保护包括从硫族或pNictogen原子上还原移除保护基团，揭示潜在的M=E键。目标络合物使它们能够在遍历元素周期表中从Fe到Zn的过程中量化M=E键中的pi-键的程度，使化学家更好地理解“氧代墙”的概念。此外，对烯烃、炔烃、NO和CO的反应性研究揭示了前所未有的小分子转化，为与这些工业相关底物进行新的催化反应打开了大门。这项研究为本科生和研究生提供了合成和表征空气敏感金属络合物的优秀培训，为他们在学术界、工业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优势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.