Catalysts for Diyne Metathesis

二炔复分解催化剂

• 批准号: 245590931
• 负责人: Professor Dr. Matthias Tamm
• 金额: --
• 依托单位: Institut für Anorganische und Analytische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2023-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/245590931?language=en
• 关键词: Catalysts; Diyne; Metathesis

Alkyne metathesis, i.e. the reversible cleavage and formation of carbon-carbon triple bonds, has gained increasing importance in recent years through the development of efficient catalysts in organic synthesis, supramolecular chemistry, and materials science. For the related metathesis of conjugated diynes, however, only a few catalysts exist so far. Building on the results of the previous proposal, new diyne metathesis catalysts will be developed and used in transformations such as diyne cross-metathesis, ring-closing diyne metathesis, and diyne depolymerization- macrocyclization. Structure-activity relationships are to be developed by variation of the ligand sphere and determined by theoretical methods, e.g. hybrid QM/MM approaches. To develop and support the mechanistic understanding of catalytic diyne metathesis and competing diyne disproportionation, central intermediates such as propargylidyne complexes and alkynyl-substituted metallacyclobutadienes are to be isolated and structurally characterized.

炔复合反应，即碳碳三键的可逆裂解和形成，近年来随着高效催化剂的发展，在有机合成、超分子化学和材料科学中越来越重要。然而，对于共轭双炔的相关复合反应，目前存在的催化剂很少。在上述研究成果的基础上，将开发新的二炔复分解催化剂，并将其应用于二炔交叉复分解、合环二炔复分解和二炔解聚-大环化等转化。结构-活性关系将通过配体球体的变化来发展，并通过理论方法确定，例如混合QM/MM方法。为了发展和支持对催化二炔复分解和竞争二炔歧化机理的理解，中心中间体如丙炔配合物和炔基取代金属环丁二烯将被分离和结构表征。