Insights into the Composition and Structural Chemistry of Gallium(I) Triflate

“GaOTf” is a simple, convenient source of low‐valent gallium for synthetic chemistry and catalysis. However, little is currently known about its composition or reactivity. In this work, (71)Ga NMR spectroscopy shows the presence of [Ga(arene)(n)](+) salts on oxidation of Ga metal with AgOTf in arene solvents. However, a more complex picture of speciation is uncovered by X‐ray diffraction studies. In all cases, mixed‐valence compounds containing Ga‐arene and Ga‐OTf coordination motifs, in addition to an unusual “naked” [Ga](+) ion, are found. Addition of 18‐crown‐6 allows for the isolation of a discrete Ga(I) crown complex. Evidence of a potential intermediate in the formation of “GaOTf” has been isolated in the form of the bimetallic silver(I)/gallium(I) cluster anion [Ag(4){Ga(OTf)(3)}(4)(μ‐Ga)(6)(OTf)(4)](2−).