Abstract
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 11B 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 {Ag2(DMF)2[B10Cl10]}n, the presence of which was additionally supported by the Raman spectroscopy data.
Highlights
Boron cluster anions and their analogs, carboranes and metallocarboranes [1,2,3,4], are fascinating objects in modern inorganic and organoboron chemistry because of their geometric and electronic structures and promising properties
Boron clusters and their derivatives are considered as soft Lewis bases because of their large size and relatively low charge; quite logically, they form a great variety of inner-sphere complexes with metals that are soft Lewis acids, such as silver(I), copper(I), lead(II), etc
Different positions of metal atoms around a bulky boron cage results in the preparation of positional isomers of mononuclear and binuclear copper(I) and silver(I) complexes, which are discussed in detail in references [16,17,18]
Summary
Boron cluster anions and their analogs, carboranes and metallocarboranes [1,2,3,4], are fascinating objects in modern inorganic and organoboron chemistry because of their geometric and electronic structures and promising properties. Boron cluster anions form complexes and salts with different composition and structure [8,9,10]. [11,12,13,14,15] Boron clusters and their derivatives are considered as soft Lewis bases because of their large size and relatively low charge; quite logically, they form a great variety of inner-sphere complexes with metals that are soft Lewis acids, such as silver(I), copper(I), lead(II), etc. Different positions of metal atoms around a bulky boron cage results in the preparation of positional isomers of mononuclear and binuclear copper(I) and silver(I) complexes, which are discussed in detail in references [16,17,18]
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