RUI: Synthesis and Reactivity of Coordinatively Unsaturated Zwitterionic Half-Sandwich Group VIII Metal Complexes

RUI：配位不饱和两性离子半夹心第VIII族金属配合物的合成和反应活性

• 批准号: 1011800
• 负责人: Paul Fischer
• 金额: $ 18.7万
• 依托单位: Macalester College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-07-15 至 2014-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1011800&HistoricalAwards=false
• 关键词: RUI; Synthesis; Reactivity; Coordinatively; Unsaturated

This research award in the Chemical Synthesis (SYN) program in the Division of Chemistry at NSF supports work by Professor Paul J. Fischer at Macalester College to synthesize and probe the reactivity of neutral half-sandwich organometallic complexes that feature a formal +1 charge on a group VIII metal (M = Fe, Ru, Os) and a formal -1 charge on a B atom within the ligand backbone. Related positively charged group VIII complexes are intermediates in metal-catalyzed organic transformations; this project probes how reactivity can be tuned by employing neutral complexes with an internal charge separation. The extent of electronic stabilization afforded by this M-B intramolecular charge separation will be probed via investigating syntheses of neutral complexes with unknown cationic analogues. This project trains Macalester College chemistry majors in chemical synthesis by teaching these students an array of critical skills for the synthesis and characterization of organic and inorganic compounds. Students will emerge from their research experiences with the laboratory skills and maturation as experimentalists to engage all aspects of graduate level synthetic research projects.The impact of an intramolecular charge separation on organometallic complex reactivity informs catalyst design strategies; complexes synthesized via this study will be excellent candidates for cross-coupling, atom transfer radical addition, and atom transfer radical cyclization reactions.

NSF化学部化学合成（SYN）计划的这项研究奖支持Macalester学院的Paul J. Fischer教授的工作，以合成和探测中性半夹心有机金属络合物的反应性，该络合物的特征是VIII族金属（M = Fe，Ru，Os）上的形式+1电荷和配体骨架内B原子上的形式-1电荷。 相关的带正电荷的VIII族配合物是金属催化的有机转化的中间体;该项目探讨如何通过采用具有内部电荷分离的中性配合物来调节反应性。 将通过研究与未知阳离子类似物的中性配合物的合成来探讨这种M-B分子内电荷分离所提供的电子稳定程度。 该项目通过教授这些学生一系列合成和表征有机和无机化合物的关键技能来培养Macalester College化学专业的化学合成。 学生将从他们的研究经验与实验室技能和成熟的实验人员参与研究生水平的合成研究项目的各个方面。分子内电荷分离对有机金属配合物反应性的影响通知催化剂设计策略;通过本研究合成的配合物将是交叉偶联，原子转移自由基加成和原子转移自由基环化反应的优秀候选者。