Synthesis, Structure, and Reactivities of Doubly Bonded Compounds Between Heavier 14 Group Elements and Oxygen

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With the intention of synthesizing the title compounds, we took advantage of a bulky bowl-type substituent, 4-t-butyl-2,6-bis[(2,2",6,6"-tetramethyl-m-terpheny1-2'-yl)methyl]phenyl(Bmt). BmtBr was converted into Bmt(R)GeH_2[R=t-Bu or Tip(2,4,6-triisopropylphenyl)], which were then allowed to react with sulfur to afford Bmt(R)GeS_4(1a : R=t-Bu, 1b:R=Tip).The desulfurization of la in the presence of 2,3-dimethyl-1,3-butadiene gave a [4+2] adduct of germanethione Bmt(R)Ge=S (2a) with the diene, while the dimer of 2a was obtained in the absence of the diene. By contrast, in the absence of the diene, 1b gave 2b, which is expected to be a good precursor of Bmt(Tip)Ge=O. Similarly, reductive dechlorination of Bmt(Tip)SiCl_2, followed by reaction with sulfur, gave Bmt(Tip)SiS_4 which is expected to be a precursor of Bmt(Tip)Si=S.