Reactivity consequences of electronic and spin state effects in organometallic chemistry

我提出了一个综合的合成、机械和计算研究，以选择性地探索电子构型和自旋态对有机金属催化基本化学计量反应的影响。金属性质和配体设计的仔细相互作用将允许化合物的合成，其中对配体球体外围的空间和/或电子修饰将调整金属中心的轨道分裂和配对能量，无论是通过感应还是通过调整配位几何，从而选择性地调整化合物的自旋态能量。这将允许在相似的配位环境中合成具有相同金属和氧化态的对或系列化合物，但基态自旋不同，允许系统的机制研究复合物的自旋状态如何单独影响组成有机金属催化循环的反应的热力学和动力学。

I propose an integrated synthetic, mechanistic, and computational study to probe selectively the effects of electronic configuration and spin state on the stoichiometric reactions fundamental to organometallic catalysis. Careful interplay of metal properties and ligand design will allow for the synthesis of compounds wherein steric and/or electronic modification to the periphery of the ligand sphere will adjust the orbital splitting and pairing energies at the metal centre, either inductively or by adjusting the coordination geometry, thereby selectively tuning the spin state energies of the compound. This will allow for the synthesis of pairs or series of compounds with identical metals and oxidation states in similar coordination environments, but differing ground state spin, permitting a systematic mechanistic study of how the spin state of a complex alone affects the thermodynamics and kinetics of the reactions that make up organometallic catalytic cycles.