Compounds with Low-Valent p-Block Elements for Small Molecule Activation and Catalysis

Abstract The past decade has witnessed staggering progress in the chemistry of compounds with low‐valent main‐group elements. Although these discoveries are mostly fundamental by nature, these compounds show promising reactivity towards small molecule activation. The reactivity of these compounds stems from the modest HOMO–LUMO energy gap; a characteristic known for the transition metals. The journey began in 2005 with the facile activation of dihydrogen by an alkyne analog of germanium [ArGe≡GeAr; Ar=2,6‐Trip 2 ‐C 6 H 3 (Trip=2,4,6‐ i Pr 3 ‐C 6 H 2 )]. Subsequently, tremendous progress has been achieved in understanding and elucidating the potential of these compounds to activate small molecules as well as to use them in a variety of stoichiometric and catalytic transformations. In this review, we focus on developments in the activation of H 2 , NH 3 , CO, and CO 2 by compounds with multiply bound or open shell main‐group elements. Emphasis will be given to their catalytic activity.