RUI: Harnessing the redox chemistry of silver: fundamental studies of oxidation chemistry at dinuclear silver catalysts

RUI：利用银的氧化还原化学：双核银催化剂氧化化学的基础研究

• 批准号: 1956197
• 负责人: Michael Campbell
• 金额: $ 24.95万
• 依托单位: Barnard College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1956197&HistoricalAwards=false
• 关键词: RUI; Harnessing; redox; chemistry; silver

With support from the Chemical Catalysis Program in the Division of Chemistry of the National Science Foundation, Professor Michael Campbell at Barnard College is exploring routes to new kinds of silver-based catalysts. Catalysts speed up chemical reactions and often contribute to producing specific, desired products. The potential of silver-based catalysts has been largely overlooked because little is known about how silver behaves during the steps required for key catalytic processes. In order to accomplish these goals, Professor Campbell is designing new structures that will induce novel behavior of silver-based catalysts. In some cases, multiple silver ions appear to cooperate in chemical reactions, but the products are too fragile to be of practical value. By systematically changing in the structure of the silver compounds, a new generation of rugged, useful catalysts may be produced. The grant also supports the training of undergraduate students for careers in science, with specific emphasis on developing skills in the laboratory and in scientific communication. A particular emphasis is placed on increasing the participation of women and other underrepresented groups in scientific research. The grant is also supporting a science literacy campaign involving the broader community of students at Barnard College.With support from the Chemical Catalysis Program in the Division of Chemistry of the National Science Foundation, Professor Michael Campbell at Barnard College is exploring routes to new kinds of silver-based catalysts. Despite silver’s relatively high abundance and lower cost compared to other late transition metals, homogeneous redox catalysis with silver is underdeveloped. This is fundamentally due to a lack of chemical design principles for controlling reactivity. To date there has been little data on oxidized silver complexes that are relevant to catalysis. Professor Campbell is systematically exploring the redox chemistry of dinuclear silver complexes, with a focus on the role of silver–silver interactions in facilitating redox processes. The results of these studies are used to inform catalyst design for nitrene transfer and other group transfer reactions that furnish valuable products from hydrocarbon substrates. By focusing on redox catalysis with silver, this research ultimately aims to develop synthetically useful reactivity than can supplant more commonly used rare-metal catalysts such as rhodium and iridium. The Campbell group at Barnard College trains undergraduate students for future careers in science. As a liberal arts college for women, Barnard is particularly effective in promoting the participation of women and other underrepresented groups in science.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.

在国家科学基金会化学部化学催化计划的支持下，巴纳德学院的迈克尔坎贝尔教授正在探索新型银基催化剂的途径。 催化剂加速化学反应，通常有助于生产特定的所需产品。基于银的催化剂的潜力在很大程度上被忽视，因为人们对银在关键催化过程所需的步骤中的行为知之甚少。为了实现这些目标，坎贝尔教授正在设计新的结构，以诱导银基催化剂的新行为。在某些情况下，多个银离子似乎在化学反应中合作，但产物太脆弱而没有实用价值。通过系统地改变银化合物的结构，可以生产新一代坚固的有用催化剂。 该补助金还支持本科生的科学职业培训，特别强调培养实验室和科学交流方面的技能。 特别强调增加妇女和其他代表性不足的群体对科学研究的参与。这笔赠款还用于支持一项涉及巴纳德学院更广泛学生社区的科学扫盲运动。在国家科学基金会化学部化学催化计划的支持下，巴纳德学院的迈克尔坎贝尔教授正在探索新型银基催化剂的途径。 尽管与其它后过渡金属相比，银具有相对高的丰度和较低的成本，但利用银的均相氧化还原催化尚不发达。这从根本上是由于缺乏控制反应性的化学设计原则。 迄今为止，几乎没有与催化有关的氧化银络合物的数据。坎贝尔教授正在系统地探索双核银络合物的氧化还原化学，重点是银-银相互作用在促进氧化还原过程中的作用。这些研究的结果被用来通知氮烯转移和其他基团转移反应，从烃类底物提供有价值的产品的催化剂设计。通过关注银的氧化还原催化，本研究的最终目的是开发合成有用的反应性，而不是取代更常用的稀有金属催化剂，如铑和铱。巴纳德学院的坎贝尔小组为未来的科学职业培训本科生。 作为一所女子文理学院，巴纳德在促进妇女和其他代表性不足的群体参与科学方面特别有效。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值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

Visible Light Absorption and Long-Lived Excited States in Dinuclear Silver(I) Complexes with Redox-Active Ligands

具有氧化还原活性配体的双核银 (I) 配合物的可见光吸收和长寿命激发态

• DOI: 10.1021/acs.inorgchem.0c02938
• 发表时间: 2020
• 期刊: Inorganic Chemistry
• 影响因子: 4.6
• 作者: Shields, Dylan J.;Elkoush, Tasneem;Miura-Stempel, Emily;Mak, Choi L.;Niu, Guang-Hao;Gudmundsdottir, Anna D.;Campbell, Michael G.
• 通讯作者: Campbell, Michael G.