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.

无机、生物无机和有机金属化学项目的目的是发展以非水溶剂分子为唯一配体的铂和铑等金属的络合离子的化学。预计溶剂分子可以很容易地从金属中移位，从而可以合成从金属氯化物开始无法用通常方法制备的配合物。所合成的新化合物作为有机化合物合成的催化剂或试剂具有潜在的价值。以非水溶剂分子（如乙腈）为配体的配合物将被探索作为合成缺乏配体配合物的起始材料。在西格玛给体溶剂（如乙腈）存在下，卤化物配合物与卤化物提取试剂（如六氟磷酸铊或四苯基硼酸钠）反应，可得到溶剂配合物。这些溶剂配合物与一种不寻常的膦，三（2,4,6-三甲氧基苯基）膦，TMPP的反应将被探索。初步结果表明，由于TMPP配体的空间体积，可以获得只有两个TMPP分子与阳离子结合的同色配合物。这些配位不饱和动力学产物预计会表现出高的反应活性，特别是在金属中心对小底物攻击的敏感性方面。将尝试制备TMPP的低价过渡金属配合物，使这些配合物可用于探测一氧化碳、二氧化碳、二氮和二氢等小分子的结合和潜在活化。