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

该研究奖属于 NSF 化学部的化学合成 (SYN) 项目，支持 Macalester 学院的 Paul J. Fischer 教授的工作，即合成和探测中性半夹心有机金属配合物的反应性，该配合物的特征是第 VIII 族金属（M = Fe、Ru、Os）上有一个形式 1 电荷，配体主链内的 B 原子上有一个形式 -1 电荷。 相关带正电荷的第 VIII 族络合物是金属催化有机转化的中间体；该项目探讨了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。 这种 M-B 分子内电荷分离所提供的电子稳定程度将通过研究具有未知阳离子类似物的中性配合物的合成来探测。 该项目通过教授学生一系列有机和无机化合物的合成和表征的关键技能，对马卡莱斯特学院化学专业的化学合成专业学生进行培训。 学生将从他们的研究经验中获得实验室技能和作为实验人员的成熟能力，参与研究生水平合成研究项目的各个方面。分子内电荷分离对有机金属络合物反应性的影响为催化剂设计策略提供信息；通过这项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。

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.