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.

该项目的目的是在无机，生物无机和 有机化学计划是发展化学的 铂、铑等金属的络离子与 非水溶剂分子作为唯一的配体。是 预期溶剂分子可以容易地被置换 从金属中，允许合成复合物， 不能以通常的方式从金属开始制备 氯化物。将要合成的新化合物将 具有作为催化剂或作为试剂的潜在价值， 有机化合物的合成 与非水溶剂分子的络合物，例如 乙腈作为配体将被探索作为起始材料 用于合成配体缺陷复合物。溶剂 络合物将通过反应从卤化物络合物获得 用卤化物提取试剂，如六氟铊， 磷酸盐或四苯硼钠，在一种 σ-供体溶剂，例如乙腈。这些反应 溶剂络合物与一种不寻常的膦， 三（2，4，6-三甲氧基苯基）膦，TMPP将被探索。 初步结果表明，均配络合物与 只能得到两个与阳离子结合的TMPP分子， 由于TMPP配体的空间体积。这些协调 不饱和动力学产物预期表现出高的 反应性，特别是关于敏感性的 金属中心受到小衬底的攻击。尝试将 制备低价过渡金属络合物， TMPP，因此这些复合物可用于探测结合 和小分子如碳的潜在活化 一氧化碳、二氧化碳、二氮和二氢。