Isolation and Molecular Structure of the Organo-persulfuranes [12−S−6(C6)]

Reactions of bis(2,2‘-biphenylylene)sulfuranyl bis(tetrafluoroborate) [(8−S−4(C4)]2+ with organo-lithium reagents (PhLi and MeLi) gave bis(2,2‘-biphenylylene)di-C-substituted persulfuranes as a first persulfurane [12−S−6(C6)] having only carbon ligands. These compounds have been characterized by 1H and 13C NMR and mass spectroscopies. The structure of the dimethyl derivative was determined by X-ray crystallographic analysis, revealing that it has a distorted octahedral geometry with the two methyl ligands cis to each other, and subsequently, it was analyzed by an ab initio calculation.