Beryllium gets going, finally. Recent highlights in the organometallic chemistry of ]beryllium

Abstract

Beryllium, despite belonging to the s-block of the periodic table, has long remained a chemical enigma. Its notorious toxicity, stringent handling requirements, and limited availability have collectively stunted the pace of exploratory research compared to its heavier congeners. Yet, in the last decade, pioneering efforts by many research groups have challenged this narrative by uncovering a surprising spectrum of unusual and unprecedented molecular architectures of beryllium compounds. Recent advances have demonstrated that beryllium can engage in bonding and reactivity patterns previously considered inaccessible to s-block elements. These include the realization of multiple-bond character, the stabilization of low-coordinate and open-shell species, and the isolation of compounds featuring unusual electronic structures. Notable achievements encompass the synthesis of beryllium complexes supported by strong donor ligands such as CAACs, the isolation of diberyllocene featuring a Be–Be bond and the first structurally isolated beryllium radical cations and tricoordinate radical species. In parallel, the emergence of heterobimetallic systems featuring polarized Be–M interactions across the s-, p-, and d-blocks has underscored the ability of beryllium to engage in cooperative bonding and reactivity with diverse metal partners. This review aims to comprehensively document the recent breakthroughs in molecular organometallic chemistry of beryllium in the last decade, emphasizing the unusual bonding paradigms and reactivity that redefine the long-standing perception of s-block inertness.