Insertion of germylenes into Ge–X bonds giving molecular oligogermanes: theory and practice

Insertion of a number of model germylenes (Me 2 Ge:, [Me 2 N] 2 Ge:, Cl 2 Ge:, MeN(CH 2 CH 2 O) 2 Ge:, MeN(CH 2 CH 2 NMe) 2 Ge:) into substituted germanes, H–Ge R 3 ( R = Me, p -Tol, Ph, C 6 F 5 ) and digermanes, R 3 Ge–Ge R 3 ( R = Me, p -Tol, Ph, C 6 F 5 ) 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 -F 3 CC 6 H 4 ) 3 GeH with [(Me 3 Si) 2 N] 2 Ge: and (C 6 F 5 ) 3 GeGe( p -Tol) 3 with [MeN(CH 2 CH 2 O)CH 2 CPh 2 O]Ge:. These results are important for understanding the main principles of the reactivity of group 14 element derivatives. Graphic abstract