Oxidation-Reduction Mechanisms

氧化还原机制

• 批准号: 9120158
• 负责人: Henry Taube
• 金额: $ 42万
• 依托单位: Stanford University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-02-01 至 1995-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9120158&HistoricalAwards=false
• 关键词: Oxidation; Reduction; Mechanisms

Dr. Henry Taube, Chemistry Department, Stanford University, supported by an award from the Inorganic, Bioinorganic, and Organometallic Program, will conduct research in three areas. First, he will study vanadium complexes in non-aqueous solvents. The effects of back-bonding on the chemistry of V(II) will be explored using acetonitrile as a solvent, but some effort will also be devoted to characterizing the higher oxidation states of vanadium and generating higher oxidation state species by aerobic oxidation. The second area is the study of mixed valence molecules. Here work on molecular hysteresis will continue. In specific systems in which electron transfer is accompanied by structural change, light of energy corresponding to that of the mixed valence band will be used to convert one isomeric form to the other and determine the efficiency of the conversion. Also, molecules based on aromatic poly-ring systems with osmiumammines bound in the eta-2, -4 or -6 modes will be investigated. Linkage isomerism in mixed valence molecules based on simple derivatives of benzene will be studied. In the third area, the mechanism of activation for substitution on a ligand by a co-ligand which is an oxidizing agent will be explored. The particular system will involve cyclopentadienone bound to Ru(II), the effect of which on the rate of substitution of co-ligand cyclopentadienide has been measured. %%% These fundamental studies involve electron transfer and substitution reactions of transition metal complexes of vanadium, ruthenium and osmium. The results of these studies are relevant to the mechanism of action of catalysts for organic reactions and to conversion of solar to electrical energy.

斯坦福大学化学系亨利陶贝博士， 由无机，生物无机和 组织者计划，将在三个领域进行研究。 首先，他将在非水溶液中研究钒络合物， 溶剂. 背面键合对化学性质的影响 V（II）将使用乙腈作为溶剂进行探索，但 一些努力也将致力于表征更高的 钒的氧化态和产生更高的氧化 状态物种通过有氧氧化。 第二个领域是 混合价态分子的研究。 这里的工作分子 滞后将继续。 在特定的系统中， 电子转移伴随着结构的变化， 对应于混合价带的能量将是 用于将一种异构形式转化为另一种异构形式， 转换的效率。 此外，分子基于 芳香族多环系统与锇胺结合在 将研究eta-2、eta-4或eta-6模式。 连锁异构 在混合价态分子中， 将研究苯。 在第三个领域， 通过共配体活化配体上的取代，所述共配体 将探索氧化剂。 特定系统 将涉及与Ru（II）结合的环己烯酮， 其取决于共配体的取代速率 已经测量了环己内酯。 %%% 这些基础研究涉及电子转移和 过渡金属配合物的取代反应 钒、钌和锇。 这些研究的结果 与催化剂的作用机制有关， 有机反应和太阳能转化为电能 能源