Tuning Au → M Interactions: d‑Block Metalloligands Enhance Au-Catalyzed CO2 Hydrosilylation

L2Z-type ligands are powerful platforms for fine-tuning π-acidic AuI catalysis. In this paper, we present a series of [(L2Z)AuICl]n+ and [(L2Z)AuI](n+1)+ complexes in which Mn2+, Fe2+, Co2+, Zn2+, Cu+, Ag+, Cd2+, and Tl+ act as Z-type metalloligands. The resulting Au→M bonds are characterized by single-crystal X-ray diffraction analysis and further studied by computational methods. The catalytic activity of these complexes in Au hydride-mediated CO2 to formate hydrosilylation catalysis was explored in detail, including in situ Raman spectroscopic monitoring. The leverage of the metalloligands to fine-tune our AuI catalyst resulted in a TOF50 of up to 2410 h–1 under mild conditions.