The hitherto elusive monobridged Ge(μ-H)GeH (X1 A') molecule was prepared in the gas phase by bimolecular reaction of atomic germanium with germane (GeH4 ). Electronic structure calculations revealed that this reaction commenced on the triplet surface with the formation of a van der Waals complex, followed by insertion of germanium into a germanium-hydrogen bond over a submerged barrier to form the triplet digermanylidene intermediate (HGeGeH3 ); the latter underwent intersystem crossing from the triplet to the singlet surface. On the singlet surface, HGeGeH3 predominantly isomerized through two successive hydrogen shifts prior to unimolecular decomposition to Ge(μ-H)GeH isomer, which is in equilibrium with the vinylidene-type (H2 GeGe) and dibridged (Ge(μ-H2 )Ge) isomers. This reaction leads to the formation of cyclic dinuclear germanium molecules, which do not exist on the isovalent C2 H2 surface, thus deepening our understanding of the role of nonadiabatic reaction dynamics in preparing nonclassical, hydrogen-bridged isomers carrying main group XIV elements.
Keywords: gas-phase reactions; germane; germanium; group 14 elements; reaction dynamics.
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