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An NHC‐coordinated diphosphene is employed as ligand for the synthesis of a hydrocarbon‐soluble monomeric AuI hydride, which readily adds CO2 at room temperature yielding the corresponding AuI formate. The reversible reaction can be expedited by the addition of NHC, which induces β‐hydride shift and the removal of CO2 from equilibrium through the formation of an NHC‐CO2 adduct. The AuI formate is...
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