Oxygenation of RZn(N,O)-type complexes as an efficient route to zinc alkoxides not accessible via the classical alcoholysis pathElectronic supplementary information (ESI) available: All experimental details and characterization data. CCDC 1555507-1555509. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7cc05818g

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. The oxygenation of alkylzincs incorporating 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 or a heterocubane [(L)Zn(μ 3 -OEt)] 4 .