[en] Insertion of a number of model germylenes (Me₂Ge:, [Me₂N]₂Ge:, Cl₂Ge:, MeN(CH₂CH₂O)₂Ge:, MeN(CH₂CH₂NMe)₂Ge:) into substituted germanes, H–GeR₃ (R = Me, p-Tol, Ph, C₆F₅) and digermanes, R₃Ge–GeR₃ (R = Me, p-Tol, Ph, C₆F₅) to yield molecular oligogermanes was analyzed theoretically using density functional theory. All reactions were found to be thermodynamically favorable, but significant values of activation energy made these interactions less profitable. No interaction was observed in the reactions of (p-F₃CC₆H₄)₃GeH with [(Me₃Si)₂N]₂Ge: and (C₆F₅)₃GeGe(p-Tol)₃ with [MeN(CH₂CH₂O)CH₂CPh₂O]Ge:. These results are important for understanding the main principles of the reactivity of group 14 element derivatives. Graphic abstract:

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