Coordination Chemistry of Reactive Homoleptic Acetonitrile Complexes with an Unusual Bulky Alkoxo-Phosphine Ligand

反应性均配乙腈配合物与异常大的烷氧膦配体的配位化学

• 批准号: 8914915
• 负责人: Kim Dunbar
• 金额: $ 18.64万
• 依托单位: Michigan State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1990
• 资助国家: 美国
• 起止时间: 1990-04-01 至 1993-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8914915&HistoricalAwards=false
• 关键词: Coordination; Chemistry; Reactive; Homoleptic; Acetonitrile

The aim of this project in the Inorganic, Bioinorganic and Organometallic Chemistry program is to develop the chemistry of complex ions of such metals as platinum and rhodium with non-aqueous solvent molecules as the only ligands. It is expected that the solvent molecules be can displaced easily from the metal, allowing the synthesis of complexes which cannot be prepared in the usual way starting with the metal chlorides. The new compounds which will be synthesized will have potential value as catalysts or as reagents for the synthesis of organic compounds. Complexes with non-aqueous solvent molecules, such as acetonitrile, as ligands will be explored as starting materials for the synthesis of ligand-deficient complexes. The solvent complexes will be obtained from halide complexes by reaction with halide abstraction reagents, such as thallium hexafluoro- phosphate or sodium tetraphenylborate, in the presence of a sigma-donor solvent, such as acetonitrile. Reactions of these solvent complexes with an unusual phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, TMPP, will be explored. Preliminary results indicate that homoleptic complexes with only two TMPP molecules bound to the cation can be obtained, due to the steric bulk of the TMPP ligand. These coordinatively unsaturated kinetic products are expected to exhibit high reactivity, especially with regard to susceptibility of the metal center toward attack by small substrates. Attempts will be made to prepare low-valent transition metal complexes of TMPP, so that these complexes may be used to probe the binding and potential activation of small molecules such as carbon monoxide, carbon dioxide, dinitrogen and dihydrogen.

该项目在无机、生物无机和有机金属化学项目中的目的是开发铂和铑等金属的络离子化学，以非水溶剂分子作为唯一的配体。预计溶剂分子可以很容易地从金属上置换出来，从而可以合成不能以金属氯化物开始的常规方法制备的络合物。将合成的新化合物将具有作为有机化合物合成的催化剂或试剂的潜在价值。 将探索以非水溶剂分子（例如乙腈）作为配体的配合物作为合成配体缺陷配合物的起始材料。溶剂络合物将通过与卤化物提取试剂（例如六氟磷酸铊或四苯硼酸钠）在σ供体溶剂（例如乙腈）存在下反应而由卤化物络合物获得。我们将探讨这些溶剂配合物与一种不常见的膦，三(2,4,6-三甲氧基苯基)膦，TMPP 的反应。 初步结果表明，由于 TMPP 配体的空间体积，可以获得仅具有两个与阳离子结合的 TMPP 分子的均配复合物。这些配位不饱和动力学产物预计将表现出高反应性，特别是在金属中心对小基材攻击的敏感性方面。我们将尝试制备TMPP的低价过渡金属配合物，以便这些配合物可用于探测一氧化碳、二氧化碳、氮气和氢气等小分子的结合和潜在活化。