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，生物有机和有机金属化学计划中的目的是开发诸如铂和恒白和若i位的复杂离子的化学因素，并以非水溶剂分子为唯一的配体。可以预期，溶剂分子可以轻松从金属中移动，从而可以从金属氯化物开始以通常的方式制备复合物。将合成的新化合物将具有作为催化剂的潜在值，也将作为合成有机化合物的试剂。 具有非水溶剂分子（例如乙腈）的复合物，将探索配体作为合成配体缺陷型复合物的起始材料。溶剂复合物将通过与甲氟二氟磷酸盐或四苯基硼酸钠的反应从卤化物复合物中获得，而在乙腈等乙酰基溶剂（例如乙腈）的情况下。这些溶剂复合物与不寻常的磷酸，Tris（2,4,6-三甲氧基）磷酸TMPP的反应。 初步结果表明，由于TMPP配体的空间，因此只能获得与阳离子结合的两个TMPP分子的同性素络合物。预计这些协调不饱和的动力学产品将表现出较高的反应性，尤其是在金属中心对小底物攻击的敏感性方面。将尝试制备TMPP的低价值过渡金属配合物，以便这些复合物可用于探测小分子的结合和潜在激活，例如一氧化碳，二氧化碳，二耐二硝基原子和二氢。