Added Complexity!-Mechanistic Aspects of Heterobimetallic Complexes for Application in Homogeneous Catalysis

Inspired by multimetallic assemblies and their role in enzyme catalysis, chemists have developed a plethora of heterobimetallic complexes for application in homogeneous catalysis. Starting with small heterobimetallic complexes with s-donating and p-accepting ligands, such as N-heterocyclic carbene and carbonyl ligands, more and more complex systems have been developed over the past two decades. These systems can show a significant increase in catalytic activity compared with their monometallic counterparts. This increase can be attributed to new reaction pathways enabled by the presence of a second metal center in the active catalyst. This review focuses on mechanistic aspects of heterobimetallic complexes in homogeneous catalysis. Depending on the type of interaction of the second metal with the substrates, heterobimetallic complexes can be subdivided into four classes. Each of these classes is illustrated with multiple examples, showcasing the versatility of both, the types of interactions possible, and the reactions accessible.

Automated summary

Inspired by the role of multimetallic assemblies in enzyme catalysis, a wide range of heterobimetallic complexes have been developed for use in homogeneous catalysis. These complexes, starting from simple ones with s-donating and p-accepting ligands, have evolved into more complex systems over the past two decades. The presence of a second metal center in the active catalyst allows for new reaction pathways and significantly increased catalytic activity. This review focuses on the mechanistic aspects of heterobimetallic complexes in homogeneous catalysis, showcasing their versatility and the different types of interactions and reactions they enable.