Gas Phase Formation of Methylgermylene (HGeCH3)

Chemphyschem. 2020 Sep 2;21(17):1898-1904. doi: 10.1002/cphc.202000392. Epub 2020 Aug 11.

Abstract

The methylgermylene species (HGeCH3 ; X1 A') has been synthesized via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with germane (GeH4 ) under single collision conditions in crossed molecular beams experiments. Augmented by electronic structure calculations, this elementary reaction was found to proceed through barrierless insertion of the methylidyne radical in one of the four germanium-hydrogen bonds on the doublet potential energy surface yielding the germylmethyl (CH2 GeH3 ; X2 A') collision complex. This insertion is followed by a hydrogen shift from germanium to carbon and unimolecular decomposition of the methylgermyl (GeH2 CH3 ; X2 A') intermediate by atomic hydrogen elimination leading to singlet methylgermylene (HGeCH3 ; X1 A'). Our investigation provides a glimpse at the largely unknown reaction dynamics and isomerization processes of the carbon-germanium system, which are quite distinct from those of the isovalent carbon system thus providing insights into the intriguing chemical bonding of organo germanium species on the most fundamental, microscopic level.

Keywords: carbon-germanium bond; gas-phase reactions; germanium; methylgermylene; reaction dynamics.