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

L₂Z-type ligands are powerful platforms for fine-tuning π-acidic Au^I catalysis. In this paper, we present a series of [(L₂Z)Au^ICl]ⁿ⁺ and [(L₂Z)Au^I]⁽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 Au^I catalyst resulted in a TOF₅₀ of up to 2410 h^-1 under mild conditions.