A Cavity-Shaped Gold(I) Fragment Enables CO(2) Insertion into Au–OH and Au–NH Bonds

[Image: see text] A cavity-shaped linear gold(I) hydroxide complex acts as a platform to access unusual gold monomeric species. Notably, this sterically crowded gold fragment enables the trapping of CO(2) via insertion into Au–OH and Au–NH bonds to form unprecedented monomeric gold(I) carbonate and carbamate complexes. In addition, we succeeded in the identification of the first gold(I) terminal hydride bearing a phosphine ligand. The basic nature of the Au(I)-hydroxide moiety is also explored through the reactivity toward other molecules containing acidic protons such as trifluoromethanesulfonic acid and terminal alkynes.