Non-Innocent Main Group Centers for Targeted Multi-Electron Transformations

目标多电子转变的非无辜主族中心

• 批准号: 1900651
• 负责人: Gabriel Menard
• 金额: $ 45万
• 依托单位: University of California-Santa Barbara
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-07-15 至 2022-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1900651&HistoricalAwards=false
• 关键词: Non; Innocent; Main; Group; Centers

Catalysts are species that improve the speed, the energy consumption, and/or the efficiency of chemical reactions; they are essential for industrial chemistry and for biological processes. The design of new catalysts is an important area of research as there is continual need for them in order to develop more efficient chemical processes. A special class of catalysts are those that can facilitate a flow of electrons to perform multi-electron chemical transformations. Professor Gabriel Menard, Chemistry Department, University of California - Santa Barbara, is supported by the Chemical Synthesis Program of the Chemistry Division to develop new catalysts for multi-electronic processes. These catalysts are based on inexpensive, abundant metals that are able to transfer electrons to and activate a non-metal center. This is nearly opposite the usual design in which the electron transfer goes from a non-metal to activate a metal center. These new catalysts open new processes to everyday goods and utilize common, inexpensive starting materials. Students from underrepresented groups are engaged in this research and Professor Menard seeks to increase broader scientific literacy by hosting a free, monthly "Science Pub Night" event, where scientists present their research to the public in an open and accessible way.This project investigates how tethering multi-metallic redox-active platforms to group 13 or group 15 centers facilitate multi-electron transformations at the main-group site. A goal is to develop main-group catalysts for multi-electron processes. By coordinating vanadium to various ligands, complexes with a variety of redox properties are obtained. These are attached to group 13 or 15 centers to generate species that contain up to three vanadium moieties attached to a main-group atom. The compounds are characterized by the usual chemical and spectroscopic techniques, with particular attention being paid to the electrochemical and magnetic properties. The presence of several vanadium atoms provides the ability for cooperative, multi-electron redox chemistry at the main group unit. This reactivity is probed in atom or group transfer chemistry and for the activation of water, ammonia, and hydrogen. This research provides excellent training to undergraduate and graduate students in the synthesis and characterization of typically air sensitive molecules. This prepares them for careers in academia, industry, or national laboratories.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.

催化剂是一种可以提高化学反应速度、能量消耗和/或效率的物种；它们对于工业化学和生物过程是必不可少的。新催化剂的设计是一个重要的研究领域，因为为了开发更有效的化学过程，对它们的需求一直存在。一类特殊的催化剂是那些可以促进电子流动以执行多电子化学转化的催化剂。加州大学圣巴巴拉分校化学系加布里埃尔·梅纳德教授在化学部化学合成计划的支持下，为多电子过程开发新的催化剂。这些催化剂基于廉价、丰富的金属，这些金属能够将电子转移到非金属中心并激活它们。这几乎与通常的设计相反，在这种设计中，电子从非金属转移到激活金属中心。这些新催化剂为日常用品开辟了新的工艺，并利用了普通、廉价的原料。来自代表性不足群体的学生参与了这项研究，梅纳德教授试图通过每月举办一次免费的“科学酒吧之夜”活动来提高更广泛的科学素养，在那里，科学家们以一种开放和可访问的方式向公众展示他们的研究。这个项目调查了将多金属氧化还原活性平台连接到第13族或第15族中心如何促进主族中心的多电子转换。一个目标是开发用于多电子过程的主基催化剂。通过将钒配位到不同的配体上，得到了具有各种氧化还原性质的配合物。它们被连接到第13或15族中心，以生成含有最多三个连接到主族原子的钒部分的物种。用常规的化学和光谱技术对化合物进行了表征，特别注意了其电化学性质和磁学性质。几个钒原子的存在提供了在主要基团单元进行合作的多电子氧化还原化学的能力。这种反应性在原子或基团转移化学以及水、氨和氢的活化中得到了探讨。这项研究为本科生和研究生提供了典型的空气敏感分子的合成和表征方面的优秀培训。这为他们在学术界、工业界或国家实验室的职业生涯做好了准备。这一奖项反映了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。

项目成果

Facile proton-coupled electron transfer enabled by coordination-induced E–H bond weakening to boron

通过配位诱导 E-H 键弱化至硼，实现轻松的质子耦合电子转移

• DOI: 10.1039/d1cc02832d
• 发表时间: 2021
• 期刊: Chemical Communications
• 影响因子: 4.9
• 作者: Wong, Anthony;Chakraborty, Arunavo;Bawari, Deependra;Wu, Guang;Dobrovetsky, Roman;Ménard, Gabriel
• 通讯作者: Ménard, Gabriel

Redox-Controlled Reactivity at Boron: Parallels to Frustrated Lewis/Radical Pair Chemistry

硼的氧化还原控制反应性：与受挫的路易斯/自由基对化学相似

• DOI: 10.1021/acs.inorgchem.0c01464
• 发表时间: 2020
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Wong, Anthony;Chu, Jiaxiang;Wu, Guang;Telser, Joshua;Dobrovetsky, Roman;Ménard, Gabriel
• 通讯作者: Ménard, Gabriel

Unusual C–H Bond Activation and C(sp 3 )–C(sp 3 ) Bond Formation at an Fe(II) Bis(amide) Carbene Complex

Fe(II) 双(酰胺)卡宾配合物中异常的 C–H 键激活和 C(sp 3 )–C(sp 3 ) 键形成

• DOI: 10.1021/acs.organomet.9b00674
• 发表时间: 2020
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Wong, Anthony;Guevara, Kevin;Wu, Guang;Ménard, Gabriel
• 通讯作者: Ménard, Gabriel