Catalysts for Diyne Metathesis

近年来，随着高效催化剂在有机合成、超分子化学和材料科学中的发展，炔烃歧化反应，即碳-碳三键的可逆裂解和形成，得到了越来越多的重视。然而，对于共轭二炔类化合物的相关歧化反应，到目前为止只有几种催化剂存在。在前述研究成果的基础上，将开发新的联炔歧化催化剂，并将其用于联炔交叉复分解、开环联炔复分解、联炔解聚-大环化等转化反应。结构-活性关系是通过改变配位体的球体来建立的，并通过理论方法来确定，例如QM/MM混合方法。为了发展和支持对催化二炔歧化和竞争二炔歧化反应机理的理解，需要分离和表征中心中间体，如炔丙基配合物和炔基取代的金属环丁二烯。

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.