Abstract
AbstractIn the last 15 years, methandiide ligands have given access to a new class of carbene complexes with unique electronic properties. The metal–carbon interactions in these complexes cover a range of bonding situations, from highly polar interactions to metal–carbon double bonds. This flexibility has allowed the isolation of complexes with metals covering the whole periodic table, including metals that had long been reluctant to form multiple bonds with carbon atoms. Thus, recent years have seen the revelation of many unusual carbene species with interesting reactivities. In this microreview, we focus on the latest developments in the chemistry of methandiides and their use as ligands in carbene complexes. We give an overview of the geminal dianionic compounds, their properties, and molecular and electronic structures, with special focus on those compounds that are applied in transition metal chemistry. The second part of the article deals with the preparation and electronic structures of methandiide‐derived carbene complexes, and we highlight important examples that display the unique properties and efficiency of the ligands. The last section gives an overview of the reactivity and the non‐innocent behavior of these methandiide ligands.
Published Version
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