Silver(I) and Copper(I) Complexation with Decachloro-Closo-Decaborate Anion

A series of complexation reactions of silver(I) and copper(I) in the presence of a polyhedral weakly coordinating [B10Cl10](2-) anion has been carried out. The effect of the solvent and the presence of Ph3P on the composition and structure of the reaction product were studied. Eight novel complexes were obtained and characterized by B-11 Nuclear magnetic resonance, Infra-Red, and Raman spectroscopies as well as powder and single-crystal X-ray diffraction techniques. The [B10Cl10](2-) anion demonstrated weaker coordinating ability towards coinage metals than [B10H10](2-) at similar reaction conditions. The [B10Cl10](2-) anion remains unreacted in the copper(I) complexation reaction, while in the absence of competing ligands, we obtained the first complexes containing decachloro-closo-decaborate anion directly coordinated by the metal atom. The bonding between metal atoms and the boron cluster anions was studied using the atomic Hirshfeld surfaces. Besides edge and face coordination of the polyhedral anion, this method allowed us to reveal the Ag-Ag bond in crystal of {Ag-2(DMF)(2)[B10Cl10]}(n), the presence of which was additionally supported by the Raman spectroscopy data.