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The controlled oxygenation of alkylzinc complexes supported by a 2-ester substituted pyrrolate ligand (L) leads to zinc alkoxides with an uncommon structural motif in the solid state: a trimer [(L)Zn(μ-O t Bu)] 3 with the central [Zn 3 (μ-OR) 3 ] ring and a tetramer [(L)Zn(μ 3 -OEt)] 4 with a heterocubane-type structure. Strikingly, these seemingly simple zinc alkoxides are not accessible via the classical alcoholysis route.

Oxygenation of RZn(N,O)-type complexes as an efficient route to zinc alkoxides not accessible via the classical alcoholysis path