Synthetic Coordination Chemistry

合成配位化学

• 批准号: 8917666
• 负责人: Christopher Reed
• 金额: $ 22.75万
• 依托单位: University of Southern California
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1989
• 资助国家: 美国
• 起止时间: 1989-12-15 至 1992-11-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8917666&HistoricalAwards=false
• 关键词: Synthetic; Coordination; Chemistry

This project in the Inorganic, Bioinorganic and Organometallic Chemistry Program deals with the synthesis and exploitation of weakly coordinating anions. These are negatively charged ions which are designed to have little tendency to form bonds either to metal atoms or to positively charged ions in general. The need for new anions which approach the ideal of a non-coordinating anion is general throughout chemistry, and wide application in synthetic chemistry and in mechanistic studies is envisioned. The main focus of the project will be the pseudo-icosahedral carborane anion B11CH12- and its derivatives, which will be investigated as counterions for reactive cations. Substitution at both the C-H and B-H bonds will be used to increase the size of the anion, lower its nucleophilicity, and lower its tendency towards oxidation. The new weakly-coordinating anions are expected to enable the structural characterization of long sought after ions such as the silicenium ion, the formation of complexes of very weak donors (e.g. xenon, hydrocarbons, fluorocarbons), the improvement of cationic homogeneous catalysts and an expansion of scope and diversity of Lewis acid and electrophile-promoted chemistry.

该项目在无机，生物无机和有机 化学课程涉及合成和开发 弱配位阴离子。这些是带负电荷的离子 它们被设计成几乎没有形成键的倾向， 金属原子或带正电的离子。的 需要新的阴离子，接近理想的 非配位阴离子在整个化学中是普遍的，并且 广泛应用于合成化学和机械化学 研究是预见。 该项目的主要重点将是伪二十面体 碳硼烷阴离子B11 CH 12-及其衍生物， 作为活性阳离子的抗衡离子进行研究。取代 在C-H键和B-H键上的键将用于增加尺寸 降低其亲核性，并降低其倾向 走向氧化。新的弱配位阴离子是 预计将使长期的结构表征 寻求硅离子等离子，形成 非常弱的给体（例如氙，烃， 碳氟化合物），改善阳离子均相 催化剂和刘易斯酸的范围和多样性的扩大 和亲电促进化学。