1. Insights into the Composition and Structural Chemistry of Gallium(I) Triflate
- Author
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Josef T. Boronski, Matthew P. Stevens, Bono IJzendoorn, Adrian C. Whitwood, and John M. Slattery
- Subjects
Main‐Group Chemistry ,Chemistry(all) ,chemistry.chemical_element ,low-valent gallium ,Catalysis ,Coordination complex ,Reactivity (chemistry) ,Gallium ,Bimetallic strip ,X-ray crystallography ,chemistry.chemical_classification ,Communication ,General Medicine ,General Chemistry ,Nuclear magnetic resonance spectroscopy ,Communications ,main-group chemistry ,Crystallography ,chemistry ,density functional calculations ,coordination chemistry ,Trifluoromethanesulfonate - 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, 71Ga 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 GaI 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 [Ag4{Ga(OTf)3}4(μ‐Ga)6(OTf)4]2−., Gallium(I) triflate is a promising new source of low‐valent gallium for synthesis and catalysis. However, little is known about its composition and structural chemistry. Here it is demonstrated that speciation is quite complex in this system, with compounds containing Ga in multiple oxidation states being isolated from arene solutions. more...
- Published
- 2020
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