The Chemistry of Novel Highly Oxidized Middle Transition Metal Complexes

该奖项在无机，生物无机和有机化学 计划是由特伦斯J.柯林斯博士在化学 卡内基梅隆大学继续致力于 含过渡金属的配位化合物 氧化态 柯林斯开发了大酰胺配体 其不易于氧化并且可用于 保持Mn、Fe、Co和Ni处于不寻常的高氧化态。 这种类型的另外的化合物的合成将在下文描述。 企图。 根据金属和结构的不同， 相应的化合物，它可以作为甲烷的模型 单加氧酶，作为电催化剂或化学传感器， 催化O原子转移剂，或显示反铁磁性 在低温下耦合。 述化合物将 使用多种技术进行表征，包括电子 顺磁共振和穆斯堡尔谱，和循环 伏安法 研究将集中在四个正方形平面复合物， Mn（V），以及5-和6-坐标系。 某些已知锰和铁的氮化物类似物的合成 化合物将被尝试。 氧原子转移反应 还将研究Fe（IV）、Ni（III）和Co（III）。的 稳定的Fe（IV）-O-Fe（IV）物种的反应化学， 已知会发生三次可逆氧化， 详细探索。详细的磁性研究将在 进行的线性聚合物的反铁磁耦合 S=2 Mn（III）中心，显示出不寻常的铁磁性 低温下的相互作用

This award in the Inorganic, Bioinorganic, and Organometallic program is made to Dr. Terrence J. Collins in the Chemistry Department of Carnegie Mellon University to continue work on coordination complexes containing transition metals in high oxidation states. Collins has developed macroamide ligands which are not susceptible to oxidation and can be used to maintain Mn, Fe, Co, and Ni in unusual high oxidation states. Synthesis of additional compounds of this type will be attempted. Depending on the metal and structure of the respective compound, it may serve as a model for methane monooxygenase, as an electrocatalyst or chemical sensor, a catalytic O-atom transfer agent, or exhibit antiferromagnetic coupling at low temperatures. The compounds will be characterized using a variety of techniques, including electron paramagnetic resonance and Mossbauer spectroscopies, and cyclic voltammetry. The investigation will focus on four square-planar complexes of Mn(V) that are known, as well as 5- and 6-coordinate systems. Synthesis of nitrido analogs of some known manganese and iron compounds will be attempted. Oxygen atom transfer reactions of Fe(IV), Ni(III), and Co(III) will also be investigated. The reaction chemistry of a stable Fe(IV)-O-Fe(IV) species, which is known to undergo three reversible oxidations, will be explored in detail. A detailed magnetic study will be undertaken of a linear polymer of antiferromagnetically coupled S=2 Mn(III) centers that shows unusual ferromagnetic interactions at low temperatures.