"Z-Selective Metathesis, Alkyne Metathesis, and Deactivation in Metathesis"

烯烃复分解为组装碳-碳键提供了非常强大的化学方法，碳-碳键是分子和先进材料的框架。它在2005年获得了诺贝尔奖，部分原因是它具有巨大的潜力，可以减少化学和制药生产中通过经典合成方法产生的废物比例。然而，迄今为止，使该反应能够进行的强催化剂在工业中基本上未被使用。问题在于它们的寿命短，这导致不经济的过程。我们试图了解为什么这些催化剂是脆弱的，以及它们在使用条件下如何分解。这种理解将是设计下一代长寿命催化剂和实现工业化的有力帮助。 我们还努力扩大这些能力。高灵敏度的催化剂已经被开发用于进行复分解，精确控制新的C=C键的几何形状。这种控制在许多增值应用中是非常需要的：例如，昆虫信息素的性质与特定的C=C几何结构相关，并且在从香料到药物的许多其他情况下也是如此。然而，催化剂固有的脆弱性限制了它们对那些专门处理它们的人的使用。其他同样高度敏感的催化剂能够实现炔复分解，这是一种用于组装三键的技术，它可以获得与先进的膜和电子应用相关的新型形状持久和共轭材料。在这两种情况下，我们寻求开发强大的，易于处理的催化剂，这将把这些强大的分子设计工具交到实践化学家手中。

Olefin metathesis offers exceptionally powerful chemical methods for assembling carbon-carbon bonds, the frameworks of both molecules and advanced materials. It was recognized with the Nobel Prize in 2005, in part because of its enormous potential to reduce the proportion of waste generated via classical synthetic methods in chemical and pharmaceutical manufacturing. To date, however, the powerful catalysts that enable this reaction are essentially unused in industry. The problem lies in their short lifetimes, which results in uneconomic processes. We seek to understand why these catalysts are vulnerable, and how they decompose under conditions of use. Such understanding would be a powerful aid to designing next-generation, long-lived catalysts, and enabling industrial uptake. We also seek to expand these capabilities. Highly sensitive catalysts have been developed to carry out metathesis with precise control over the geometry of the new C=C bonds. Such control is highly desirable in many value-added applications: the properties of insect pheromones, for example, are associated with a specific C=C geometry, and the same is true in many other contexts, ranging from perfumery to pharmaceuticals. However, the inherent fragility of the catalysts has limited their use to those specialized in handling them. Other, likewise highly sensitive catalysts enable alkyne metathesis, a technology for assembling triple bonds, which gives access to novel shape-persistent and conjugated materials relevant to advanced membrane and electronics applications. In both contexts, we seek to develop robust, readily-handled catalysts, which would put these powerful tools for molecular design into the hands of the practicing chemist.