SILICON AND GERMANIUM CHALCOGENIDES WITH NOR-ADAMANTANE AND BISNOR-ADAMANTANE STRUCTURES

A series of chalcogen cage compounds are derived from removal of chalc ogen of adamantane (II a) and double-decker (IIb) sesquichalcogenide. These chalcogenide are termed nor-adamantane (VIIIa), bisnor-adamantan e (VIIb), nor-doubledecker (VIIIb) and bisnor-doubledecker (IXb), resp ectively. After trichloromonogermane ([1a] and [1b]), trichloromonosil ane ([8a] and [8b]), trichloromonostannane ([10a] and [10b]) were subj ected to sulfation reaction using H2S/pyridine, Li2S, Na2S, (NH4)2S5, and (Me3Si)2S, only trichloromonogermane ([1a] and [1b]) produced tetr akis(t-butylgermane)pentasulfide as minor products, which has Ge-Ge bo nds. As major products, adamantane sesquisulfides ([9a],[9b],[11a], an d [11b]), were formed from trichloromonosilane, trichloromonostannane as well as trichloromonogermane. On the contrary, the sulfation and se lenation of tetrachlorodisilane [12] and tetrachlorodigermane [15] dis closed with efficient formation of tetrakis[t-butylsilane (germane)] p entasulfide and pentaselenide ([13a],[13b], and [5a]). The X-ray analy sis of [13a], and [13b] established nor-adamantane structures, which a re formed from Si-Si bonds cleavage. Interestingly, tetrachlorodigerma ne also produced tetrakis(t-butylgermane)tetrasulfide ([16]), which is derived without Ge-Ge bond cleavage. X-ray analysis confirmed bisnor- adamantane structure for [16].