Cooperative reactivity between transition metals and ligands, or between two metals, has created significant opportunities for the development of new transformations that would be difficult to carry out with a single metal. Here we explore cooperativity between transition metals and divalent heavier group 14 elements (tetrylenes), a less-explored facet of the field of cooperativity. Tetrylenes combine their strong σ-donor properties with an empty p-orbital that can accept electron density. This ambiphilicity has allowed them to form metal tetrylene and metallotetrylene complexes that place a reactive site adjacent to the metal. We have selected examples to demonstrate what has been achieved so far regarding cooperative reactivity, as this already spans metal-, tetrylene- or multi-site-centred bond cleavage, cycloaddition, migration, metathesis, and insertion. We also highlight some challenges that need to be overcome for this cooperativity to make it to catalysis.
Keywords: Cooperative effects; Group 14 elements; Main group elements; Multi-site activation; Tetrylenes.
© 2021 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.