Synthesis,Structures, and Properties of Branched Oligogermanes

Abstract

We have employed the hydrogermolysis reaction for the preparation of rare branched oligogermanes, and have obtained for the first time the X-ray crystal structures of several branched tetragermanes, including (Ph₃Ge)₃GePh, (Ph₃Ge)₃GeH, and (Ph₃Ge)₃GeX (X = Cl or Br). We also have at our disposal branched tetragermanes having the formula (EtOCH₂CH₂Bu ⁿ ₂Ge)₃GePh, where the ethoxyethyl substituent serves as a protecting group for a germanium–hydride active site. These reagents have been employed for the stepwise synthesis of higher branched systems having up to 13 bonded germanium atoms in the oligomer backbone. The synthesis, structures, and physical characteristics of these systems are described.

GRAPHICAL ABSTRACT     

Re-examination of the photochemical reaction of octaisopropylcyclotetragermane

The photochemistry of octaisopropylcyclotetragermane was studied by laser flash photolysis and trapping experiments. Upon irradiation of the cyclotetragermane, the main reaction was a ring opening to form octaisopropyltetragermane-1,4-diyl biradical (λ_max = 310 and 550 nm), but generations of diisopropylgermylene and tetraisopropyldigermene are negligible.