Germane vs. digermane formationDedicated to Prof. H. J. Frohn on the occasion of his 70th birthday.Electronic supplementary information (ESI) available: Experimental details, NMR spectra of 2-8; bond lengths and angles of 1-6. CCDC 1009920 (1lt), 1009921 (1ht), 1009925 (2), 1009924 (3), 1009923 (4), 1009922 (5), 1019789 (6) and 1010028 (8). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4cc07921c

Oxidative addition reactions of dialkylchalcogenanes R 2 E 2 and [Me 2 Si(N t -Bu) 2 ]Ge 1 yielded bis(alkylchalcogeno)germanes Me 2 Si(N t -Bu) 2 Ge(ER) 2 (R = Et, E = S 2 , Se 3 ; R = Me, E = Se 4 ) and digermanes [Me 2 Si(N t -Bu) 2 Ge(EEt)] 2 (E = S 5 , Se 6 ). The reaction of 1 with Et 2 Te 2 proceeds with formation of Me 2 Si(N t -Bu) 2 Ge(TeEt) 2 7 , which slowly converts into the Te-bridged complex [Me 2 Si(N t -Bu) 2 GeTe] 2 8 . 1-6 and 8 were characterized by single crystal X-ray diffraction. Oxidative addition reactions of dialkylchalcogenanes R 2 E 2 and [Me 2 Si(N t -Bu) 2 ]Ge yielded germanes Me 2 Si(N t -Bu) 2 Ge(ER) 2 and digermanes [Me 2 Si(N t -Bu) 2 Ge(ER)] 2 , while the reaction with Et 2 Te 2 gave Me 2 Si(N t -Bu) 2 Ge(TeEt) 2 , which converts to the Te-bridged complex [Me 2 Si(N t -Bu) 2 GeTe] 2 .