Studies on the reaction of zinc alkyls with O2 are reported which demonstrate that the selective oxygenation of organozinc compound is viable. The reaction of [EtZn(azol)]n (azol = deprotonated 1-aziridineethanol) with an excess of dry O2 in toluene affords the zinc ethylperoxide [EtOOZn(azol)]2[EtZn(azol)]2, while the analogous reaction between Me2Zn and O2 results in the isolation of the Me6Zn7(OMe)8 cluster in high yield.

We demonstrate a mechanochemical strategy that allowed the first successful mechanosynthesis of IRMOFs based on an oxo-centred secondary building unit (SBU). The presented study indicates that controlling the acid-base relationship between reagents is key to mechanochemical synthesis of IRMOFs, revealing a pre-assembled oxo-zinc amidate cluster as an efficient precursor for IRMOF mechanosynthesis.