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 (IIa) and double-decker (Ilb) sesquichalcogenide. These chalcogenide are termed nor-adamantane (VIIa), bisnor-adamantane (VIIb), nor-doubledecker (VIlb) and bisnor-doubledecker (Kb), respectively. After trichloromonogermane ([1a] and [lb]), 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 [lb]) produced tetrakis (t-butylgermane)pen-tasulfide as minor products, which has Ge-Ge bonds. As major products, adamantane sesquisulfides ([9a],[9b],[11a], and [lib]) were formed from trichloromonosilane, trichloromonostannane 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)]pen-tasulfide 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 ([16]), which is derived without Ge-Ge bond cleavage. X-ray analysis confirmed bisnor-adamantane structure for [16]. © 1994, The Chemical Society of Japan. All rights reserved.