Novel heterometallic complexes for C-F and C-H bond activation

Abstract

The interest in bimetallic systems stems from the principle that ‘two metals are better than one’. In other words, cooperation between two metals can enable in some cases modes of reactivity that are inaccessible for the individual monometallic species. Furthermore, the presence of two (or more) metals in close proximity gives rise to unusual coordination modes and bonding configurations. In this thesis, new transition metal – main group heterometallic systems have been prepared. Highly unusual structural motifs have been identified and studied carefully. For instance, the reaction coordinate for the addition of Mg–H and Zn–H bonds to Pd and Pt has been analysed, by generating structural snapshots along the reaction coordinates and computationally interrogating their bonding. One of the first simple, molecular transition metal complexes possessing a hexagonal planar geometry around the metal has been disclosed. The reactivity of these novel complexes has also been explored, with a focus on the activation and functionalisation of C–F and C–H bonds. Detailed mechanistic studies have revealed the intimate role of heterometallic intermediates in the processes of bond breaking and bond formation. This allowed for the development of novel approaches to bond functionalisation, such as Pd catalysed C–H bond magnesiation or zincation reactions.