Interconversion of derivatives of germane using heavy-metal salts: synthesis of germyl carboxylates

Abstract

Reactions of bromogermane with silver(I) and lead(II) salts have been investigated more fully than hitherto, resulting in the preparation and full characterization of three carboxylato-derivatives of germane, germyl formate, acetate, and trifluoroacetate. The wider scope of conversions using lead rather than the more reactive silver salts are illustrated by facile synthesis of (i) digermyl ether from PbO or Pb[CO₃] and (ii) the silyl formate from bromosilane with Pb[CO₂H]₂. l.r., Raman, mass-spectroscopic, and ¹H n.m.r. data for the compounds are discussed in relation to those for their silyl analogues, for which Raman spectra have also been measured. Protolysis reactions of GeH₃(NCS) are of limited value in the synthesis of germane derivatives but afford GeClH₃, GeH₃(SMe), and [Mn(CO)₅(GeH₃)] from HCl, MeSH, and [Mn(CO)₅H] respectively.