CAREER: Multimetallic Architectures for Dioxygen Chemistry with First-Row Transition Metals

职业：第一行过渡金属的双氧化学多金属结构

• 批准号: 1151918
• 负责人: Theodor Agapie
• 金额: $ 55万
• 依托单位: California Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-07-01 至 2017-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1151918&HistoricalAwards=false
• 关键词: CAREER; Multimetallic; Architectures; Dioxygen; Chemistry

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Theodor Agapie of the Division of Chemistry and Chemical Engineering at California Institute of Technology will synthesize multinuclear metal complexes and study their ability to form and break O-O bonds. Since biological and heterogeneous catalysts perform dioxygen chemistry at multimetallic sites, the synthesis of small-molecule structural and functional synthetic models will afford a better understanding of cluster chemistry broadly relevant to catalysis. Detailed studies of the effect of cluster structure on physical and chemical properties, and oxygen reactivity will be performed. These studies are focused on earth abundant first-row transition metals, with the long-term goal of developing practical and inexpensive catalysts for oxygen chemistry. The educational components of this project integrate aspects of chemistry related to energy and catalysis researched in the laboratory and reach high school students and teachers from the Los Angeles area, and undergraduates and graduate students.The present studies are significant in understanding biological and heterogeneous reaction mechanisms and have potential applications in energy storage in chemical bonds and functionalization of organic molecules. These areas are of broad importance to society in the context of carbon-neutral energy conversion to fuels and synthesis of pharmaceuticals. Professor Agapie will establish teacher-research group partnerships and summer workshops with a special focus on students from groups underrepresented in sciences. Undergraduate and graduate students involved in the research efforts will be trained in synthetic chemistry and will develop a culture of contributing to their scientific and non-scientific communities that is expected to last well beyond their formative years.

在这个由化学系化学合成计划资助的项目中，加州理工学院化学与化学工程系的Theodor Agapie教授将合成多核金属配合物，并研究其形成和断裂O-O键的能力。由于生物和非均相催化剂在多金属位点进行双氧化学，因此小分子结构和功能合成模型的合成将更好地理解与催化广泛相关的簇化学。详细研究团簇结构对物理和化学性质以及氧反应性的影响。这些研究集中在地球上丰富的第一行过渡金属，长期目标是开发实用和廉价的氧化学催化剂。该项目的教育部分整合了实验室研究的与能量和催化相关的化学方面，并覆盖了来自洛杉矶地区的高中学生和教师，以及本科生和研究生。目前的研究对于理解生物和非均相反应机制具有重要意义，并在化学键的能量存储和有机分子的功能化方面具有潜在的应用。这些领域在将碳中和能源转化为燃料和合成药物方面对社会具有广泛的重要性。Agapie教授将建立教师-研究小组伙伴关系和夏季讲习班，特别关注来自科学领域代表性不足的群体的学生。 参与研究工作的本科生和研究生将接受合成化学方面的培训，并将培养一种为他们的科学和非科学社区做出贡献的文化，这种文化预计将远远超过他们的成长期。

项目成果

Dipalladium(I) terphenyl diphosphine complexes as models for two-site adsorption and activation of organic molecules.

• DOI: 10.1021/ja406696k
• 发表时间: 2013-10-23
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Lin S;Herbert DE;Velian A;Day MW;Agapie T
• 通讯作者: Agapie T

Molybdenum catalyzed ammonia borane dehydrogenation: oxidation state specific mechanisms.

• DOI: 10.1021/ja5059923
• 发表时间: 2014-08-13
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Buss, Joshua A.;Edouard, Guy A.;Cheng, Christine;Shi, Jade;Agapie, Theodor
• 通讯作者: Agapie, Theodor

Arene non-innocence in dinuclear complexes of Fe, Co, and Ni supported by a para-terphenyl diphosphine

• DOI: 10.1039/c4cc00838c
• 发表时间: 2014-01-01
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Horak, Kyle T.;Velian, Alexandra;Agapie, Theodor
• 通讯作者: Agapie, Theodor

Trinuclear Nickel Complexes with Metal-Arene Interactions Supported by Tris- and Bis(phosphinoaryl)benzene Frameworks.

• DOI: 10.1021/om400976x
• 发表时间: 2013-12-09
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Suseno S;Horak KT;Day MW;Agapie T
• 通讯作者: Agapie T

Terminal Molybdenum Phosphides with d Electrons: Radical Character Promotes Coupling Chemistry

• DOI: 10.1002/anie.201707921
• 发表时间: 2017-11-13
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Buss, Joshua A.;Oyala, Paul H.;Agapie, Theodor
• 通讯作者: Agapie, Theodor