Size- and shape-adaptable mixed-alkoxide-aggregates: encapsulation of tetrafluoroborate and butadiynediide

Abstract

Treatment of silyl compounds with excess sodium tert-butoxide results in encapsulation of the released anion. While the BF4− anion just fits in a spherical sodium alkoxide hull, the butadiyenediide dianion pierces its hull resulting in dimerisation.

Scalable Transition-Metal-Free Synthesis of Aryl Amines from Aryl Chlorides through X@RONa-Catalyzed Benzyne Formation

“…A hydride-encapsulated cluster was also evidenced with the aid of crown ether ( [15-c-5-Na][H@ t- BuONa] ; Figure S2). Detailed structure features of these intricate “fluxional” clusters have also been discussed by other scientists before and during our work. − In our cases, they were easily made by heating t -BuONa with chloride sources such as prenyl chloride, chloranil, or even a fine powder of NaCl in nonpolar solvent. The X@RONa clusters seemed to be thermodynamically more favored than other types of sodium alkoxide aggregates. , Spontaneous generation of X@RONa was always observed as long as halide anions were present, suggesting that NaH would behave similarly, although the direct observation of cluster formation cored by solid NaH was prohibitively difficult.…”