Quantum mechanical modeling for the GeX₂/GeHX + GeH₄ reactions (X = H, F, Cl, and Br)

A systematic theoretical investigation was carried out to study the reactions of various germylenes with germane. Molecular structures of the reactants (GeX₂ and GeHX, where X = H, F, Cl and Br) plus GeH ₄, transition states, and products have been optimized to understand the effects of halo-substituted germylenes. The basis set used is of double-ζ plus polarization quality with additional s- and p-type diffuse functions. Consistent with experiment, the theoretical gas-phase reaction GeH₂ + GeH₄ → Ge₂H₆ possesses a negative activation energy. The predicted activation energies reveal interesting trends for both mono- and di- halo-substituted germylenes, - 1.5 [GeH₂], + 20.5 [GeHF], +59.9 [GeF₂], +18.0 [GeHCl], +46.8 [GeCl₂], +17.3 [GeHBr], and +42.9 kcal mol^-1 [GeBr ₂]. There is a noteworthy relationship between the activation energies and the singlet-triplet splittings of the divalent germylenes. We report for the first time rate constants for the transfer of hydrogen, evaluated using standard transition-state theory with tunneling corrections. These results are analyzed and compared to the available experimental and previous theoretical findings for the gas-phase reactions involving germylene derivatives and germanium analogues.