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We analyzed the ligand electronic effect in the reaction between a [LAu(I)H]0/− hydride species and CO2, leading to a coordinated formate [LAu(HCOO)]0/−. We explored 20 different ligands, such as carbenes, phosphines and others, carefully selected to cover a wide range of electron‐donor and ‐acceptor properties. We included in the study the only ligand, an NHC‐coordinated diphosphene, that, thus far,...