Insights into the Composition and Structural Chemistry of Gallium(I) Triflate
Josef T. Boronski, Matthew P. Stevens, Bono van IJzendoorn, Adrian C. Whitwood, John M. Slattery
Abstract
Abstract “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− .