Making and Breaking Si–Si Bonds under Mechanochemical Conditions

Abstract

Mechanochemistry offers a sustainable alternative to solution-based synthesis, yet its potential in main-group chemistry remains largely untapped. Here we demonstrate that both the formation and cleavage of Si–Si bonds can be efficiently achieved under mechanochemical conditions. Solvent-free Wurtz-type couplings enable rapid access to disilanes, higher silanes, and cyclic silicon frameworks, while controlled ball-milling with alkali metal bases allows the quantitative generation of silanide and disilanide species. These reactive intermediates undergo clean and selective derivatization with a range of electrophiles, frequently affording higher yields than reported solution-phase protocols. The methodology is operationally simple, scalable, and enables multistep transformations without intermediate workup. This work establishes mechanochemistry as a powerful platform for silicon–silicon bond manipulation and highlights its potential for advancing sustainable main-group synthesis