The Chemistry of Novel Highly Oxidized Middle Transition Metal Complexes

卡内基梅隆大学化学系的Terrence J. Collins博士获得了无机、生物无机和有机金属项目的奖项，以表彰他在含高氧化态过渡金属的配位配合物方面的持续研究。Collins开发了一种不易氧化的大酰胺配体，可用于维持Mn， Fe， Co和Ni处于不寻常的高氧化状态。将尝试合成这种类型的其他化合物。根据各自化合物的金属和结构，它可以作为甲烷单加氧酶的模型，作为电催化剂或化学传感器，催化o原子转移剂，或在低温下表现出反铁磁偶联。这些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光谱，以及循环伏安法。该研究将集中于已知的四种方形平面Mn(V)配合物，以及5和6坐标系。将尝试合成一些已知的锰和铁化合物的硝基类似物。Fe(IV), Ni（III）和Co（III）的氧原子转移反应也将被研究。一个稳定的Fe(IV)-O-Fe（IV）的化学反应，这是已知的三个可逆氧化，将被详细探讨。将对一种具有反铁磁耦合S=2 Mn（III）中心的线性聚合物进行详细的磁性研究，该聚合物在低温下表现出不寻常的铁磁相互作用。

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.