Ligands that include Lewis acid/base functionality have extensive applications in bifunctional catalysis using first row metals. In this work, zinc bis(amido), bis(thiolate) and amido–thiolate SNS complexes were prepared and compared as precatalysts for carbonyl hydroboration using pinacolborane. Mechanistic studies revealed two different ligand-assisted precatalyst activation pathways, both leading to an active and robust zinc alkoxide catalyst. This work furthers our understanding of metal–ligand cooperation in first-row metal catalysis.