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Reactivity of [AuF3 (SIMes)]: Pathway to Unprecedented Structural Motifs
Marlon Winter1, Mathias A Ellwanger1,2, Niklas Limberg1
1Fachbereich Biologie, Chemie, Pharmazie, Institut für Chemie und Biochemie - Anorganische Chemie, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany.
Abstract:
We report on a comprehensive reactivity study starting from [AuF3 (SIMes)] to synthesize different motifs of monomeric gold(III) fluorides. A plethora of different ligands has been introduced in a mono-substitution yielding trans-[AuF2 X(SIMes)] including alkynido, cyanido, azido, and a set of perfluoroalkoxido complexes. The latter were better accomplished via use of perfluorinated carbonyl-bearing molecules, which is unprecedented in gold chemistry. In case of the cyanide and azide, triple substitution gave rise to the corresponding [AuX3 (SIMes)] complexes. Comparison of the chemical shift of the carbene carbon atom in the 13 C{1 H} NMR spectrum, the calculated SIMes affinity and the Au-C bond length in the solid state with related literature-known complexes yields a classification of trans-influences for a variety of ligands attached to the gold center. Therein, the mixed fluorido perfluoroalkoxido complexes have a similar SIMes affinity to AuF3 with a very low Gibbs energy of formation when using the perfluoro carbonyl route.
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