New High Oxidation State Inorganic Complexes of Later Transition Metals. Reaction Chemistry and Properties

后来过渡金属的新型高氧化态无机配合物。

• 批准号: 8714720
• 负责人: Terrence Collins
• 金额: $ 27万
• 依托单位: Carnegie-Mellon University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1987
• 资助国家: 美国
• 起止时间: 1987-12-01 至 1991-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8714720&HistoricalAwards=false
• 关键词: New; Oxidation; State; Inorganic; Complexes

The focus of this project in the Inorganic, Bioinorganic and Organometallic Chemistry Program is the chemistry of high and unusual oxidation states of transition metals, such as copper(III), cobalt(IV) and cobalt(V). The project is expected to result in the discovery of useful and powerful new oxidizing agents, as well as providing biomimetic models of certain metalloenzymes which have recently been found to contain metals in high oxidation states, such as galactose oxidase, which contains copper(III). Square planar cobalt(III) complexes and their anionic precursors will be studied and employed as precursors to highly oxidized organometallic species. These complexes utilize oxidation-resistant polyanionic chelating (PAC) ligands. Oxygen atom transfers catalyzed by these species will be pursued especially by a search for terminal cobalt(IV)-oxo complexes. The recently discovered copper(III) complexes which oxidize alcohols will be studied as biomimetic models of galactose oxidase and related enzymes and will also be used in a general exploration of the role of copper(III) complexes in oxidation processes. Evidence will be sought for intermediates in the oxidation of phosphine to phosphine oxide by molecular oxygen catalyzed by osmium(VI)/(IV) systems. Ruthenium complexes of PAC ligands will be investigated as possible catalysts for alkene oxidations by molecular oxygen. "Thermodynamic ladders" will be developed to interrelate the formal reduction potentials and isomerization equilibria of diastereomeric complexes of the first thermodynamically stable nonplanar amides, and these amides will be compared to their planar analogues. The electrochemistry in liquid sulfur dioxide of new complexes of the highly protected PAC ligands will be explored in a search for solution stable one-electron oxidants with formal reduction potentials greater than 2.5 V vs. NHE. Attempts will be made also to extend the electrochemical measurements to other solvents offering a wide anodic range.

该项目的重点是无机，生物无机和 有机化学计划是高化学和 过渡金属的不寻常氧化态，如 铜（III）、钴（IV）和钴（V）。该项目预计 从而发现了一种有用的、强有力的新氧化剂， 代理商，以及提供某些仿生模型 最近发现含有金属的金属酶 在高氧化态，如半乳糖氧化酶， 含有铜（III）。 正方形平面钴（III）配合物及其阴离子 前体将被研究和用作前体， 氧化的有机金属物质。这些复合物利用 抗氧化聚阴离子螯合（PAC）配体。氧 由这些物种催化的原子转移将继续进行， 特别是通过寻找末端钴（IV）-氧代配合物。 最近发现的铜（III）络合物， 将醇类作为半乳糖的仿生模型进行研究 氧化酶和相关的酶，也将用于一般的 探索铜（III）络合物在氧化中的作用 流程. 将寻找中间体的证据， 用分子氧将膦氧化成氧化膦 锇（VI）/（IV）体系催化。钌配合物 PAC配体将作为可能的催化剂进行研究， 分子氧氧化烯烃。“热力学阶梯” 将被开发为将正式的减少 非对映异构体的异构化平衡 第一类双稳非平面复合物 酰胺，并且这些酰胺将与它们的平面酰胺进行比较。 类似物新硫代硫酸钠在液体二氧化硫中的电化学 将探索高度保护的PAC配体的络合物 在寻找溶液稳定单电子氧化剂时， 形式还原电位大于2.5 V（相对于NHE）。 还将尝试扩展电化学 测量提供了广泛的阳极范围的其他溶剂。