Silicon and Germanium Chalcogenides with Nor- and Bisnor-adamantane Structures

Abstract

A series of chalcogen cage compounds are derived from removal of chalcogen of adamantane (II a)and double-decker(IIb) sesquichalcogenide. These chalcogenide are termed nor-adamantane (VIIIa), bisnor-adamantane (VIIb), nor-doubledecker (VIIIb)a nd bisnor-doubledecker (IXb ), respectively. After trichloromonogermane ([1a] and [1b]), trichloromonosilane ([8a] and [8b]), trichloromonostannane ([10a]and[10b]) were subjected to sulfation reaction using H₂S/pyridine, Li₂S, Na₂S, (NH₄)₂S₅, and (Me₃Si)₂S, only trichloromonogermane ([la] and [1b]) produced tetrakis(t-butylgermane)pentasulfide as minor products, which has Ge-Ge bonds. As major products, adamantane sesquisulfides ([9a], [9b], [lla], and [11b]) were formed from trichloromonosilane, trichloromonostannan e as well as trichloromonogermane. On the contrary, the sulfation and selenation of tetrachlorodisilane [12] and tetrachlorodigermane [15] disclosed with efficient formation of tetrakis[t-butylsilane (germane) ]pentasulfide and pentaselenide ([13a], [13b], and [5a]). The X-ray analysis of [13a], and [13b] established nor-adamantane structures, which are formed from Si-Si bonds cleavage. Interestingly, tetrachlorodigermane also produced tetrakis(t-butylgermane)tetrasulfide (DC), which is derived without Ge-Ge bond cleavage. X-ray analysis confirmed bisnor-adamantane structure for [16].