The road travelled : after main‐group elements as transition metals

Weetman, Catherine and Inoue, Shigeyoshi (2018) The road travelled : after main‐group elements as transition metals. ChemCatChem, 10 (19). pp. 4213-4228. ISSN 1867-3880 (

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Since the latter quarter of the twentieth century, main group chemistry has undergone significant advances. Power's timely review in 2010 highlighted the inherent differences between the lighter and heavier main group elements, and that the heavier analogues resemble transition metals as shown by their reactivity towards small molecules. In this concept article, we present an overview of the last 10 years since Power's seminal review, and the progress made for catalytic application. This examines the use of low oxidation state and/or low coordinate group 13 and 14 complexes towards small molecule activation (oxidative addition step in a redox based cycle) and how ligand design plays a crucial role in influencing subsequent reactivity. The challenge in these redox based catalytic cycles still centres on the main group complexes’ ability to undergo reductive elimination, however considerable progress in this field has been reported via reversible oxidative addition reactions. Within the last 5 years the first examples of well‐defined low valent main group catalysts have begun to emerge, representing a bright future ahead for main group chemistry.