UNIQUE ADVANTAGES OF ORGANOMETALLIC SUPPORTING LIGANDS FOR METAL COMPLEXES

金属配合物有机金属支持配体的独特优势

• 批准号: 1362999
• 负责人: Paula Diaconescu
• 金额: $ 39万
• 依托单位: University of California-Los Angeles
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-08-01 至 2017-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1362999&HistoricalAwards=false
• 关键词: UNIQUE; ADVANTAGES; ORGANOMETALLIC; SUPPORTING; LIGANDS

Innocent ligands, such as phosphines and cyclopentadienyl derivatives, impart electronic and steric properties once coordinated to the metal center but the ligands themselves are not modified during the course of a chemical transformation. In contrast, non-innocent ligands cooperate with the metal during its reactions. The distinction between these two classes of ligands is becoming blurry and the research team led by Professor Paula Diaconescu at the University of California-Los Angeles seeks to identify and exploit the effect of non-innocent ligands on reactivity, particularly carbon-hydrogen (C-H) bond activation, aromaticity, single molecular magnets and metal-metal interactions. The experimental research team at UCLA collaborates with theoretical and computational scientists at other universities forming an interdisciplinary group focused on tuning the reactivity of the synthesized metal complexes, observing their resultant reactivity patterns, and incorporating unreactive molecules into value-added compounds. The diverse work environment allows for the integration of women and underrepresented minority students while expanding the representation from different ethnic and cultural backgrounds in the scientific enterprise. Professor Diaconescu collaborates with a number of high school students, enabling them to learn advanced experimental techniques as well as to gain an understanding of molecular and materials synthesis and catalysis. Professor Diaconescu continues to work with the California NanoSystems Institute, particularly the High School Nanoscience Program, in partnership with the Los Angeles Unified School District.This award from the NSF Chemical Synthesis Program supports the research efforts of Professor Paula Diaconescu at the University of California-Los Angeles, in examining the role of ancillary groups as they participate in reactions at rare earth metal centers. The research group is focused on ferrocene-based chelating ligands because they possess unique electronic characteristics that make them especially versatile in supporting the reactivity of the metal centers, especially in relation to (1) the reductive cleavage of C-H/C-fluorine (F) bonds by rare earth metals, (2) aromaticity in arene-bridged rare-earth complexes, (3) inverse sandwiches of arene-bridged paramagnetic lanthanides, and (4) the importance of organometallic supporting ligands.

无辜的配位体，如膦和膦衍生物，一旦与金属中心配位，就赋予电子和空间性质，但配位体本身在化学转化过程中不会被修饰。 相反，非无辜配体在其反应期间与金属合作。这两类配体之间的区别越来越模糊，由加州大学洛杉矶分校的Paula Diaconescu教授领导的研究小组试图识别和利用非无辜配体对反应性的影响，特别是碳氢（C-H）键活化，芳香性，单分子磁体和金属-金属相互作用。加州大学洛杉矶分校的实验研究团队与其他大学的理论和计算科学家合作，形成了一个跨学科小组，专注于调整合成金属络合物的反应性，观察其反应性模式，并将非反应性分子纳入增值化合物。多样化的工作环境允许妇女和代表性不足的少数民族学生的融合，同时扩大来自不同种族和文化背景的科学企业的代表性。 Diaconescu教授与许多高中生合作，使他们能够学习先进的实验技术，并了解分子和材料合成和催化。Diaconescu教授继续与加州纳米系统研究所合作，特别是高中纳米科学计划，与洛杉矶联合学区合作。NSF化学合成计划的这一奖项支持了加州大学洛杉矶分校的Paula Diaconescu教授的研究工作，研究了辅助基团在稀土金属中心参与反应时的作用。 该研究小组专注于基于二茂铁的螯合配体，因为它们具有独特的电子特性，使得它们在支持金属中心的反应性方面特别通用，特别是与（1）稀土金属对C-H/C-氟（F）键的还原裂解，（2）芳烃桥接稀土络合物中的芳香性，（3）芳烃桥接顺磁性镧系元素的反三明治，（4）有机金属支撑配体的重要性。