Complexes with carboranyl ligands
The synthesis of salts with the anionic gold (I) complexes [1-(Ph3PAu)-closo-1-CB11H11]−, [1-(Ph3PAu) -closo-1-CB9H9]− and [2-(Ph3PAu)-closo-2-CB9H9]− are the first examples of transition metal complexes of the dianions [closo-1-CB11H11]2−, [closo-1-CB9H9]2− and [closo-2-CB9H9]2− with a two-center two-electron metal Ccluster σ bond. Syntheses for analogue complexes with carba-closo-borate dianions, which also carry functional groups on the boron atoms, are currently being developed. The long-term goal of these studies is to produce coordination polymers and metal macrocycles with linkers that carry anionic boron clusters in the backbone.
Deprotonation of the anions [1-H-closo-1-CB11X11]− (X = H, F, Cl, Br) and reaction with HgCl2 yielded the dianions [Hg (closo-1-CB11X11)2]2− and allowed them to be isolated as Cs+ and [Et4N]+ salts. In contrast to [Hg (closo-1-CB11X11)2]2− (X = H, Cl, Br), a third ligand is coordinated to the Hg atom of [Hg (closo-1-CB11F11)2]2−, which is another example of the unusual properties of highly fluorinated {closo-1-CB11} clusters.
Selected literature: Z. Anorg. Allg. Chem. 2020, 646, 777–783. Chem. Eur. J. 2017, 23, 11684–11693. Eur. J. Inorg. Chem. 2017, 4459-4466. Angew. Chem. Int. Ed. 2016, 55, 10507–10511.; German version: Angew. Chem. 2016, 128, 10663–10667. Organometallics 2012, 31, 1566–1577. Chem. Eur. J. 2009, 15, 9918–9927.
