Sequential Bi-C bond activation reactions of BiEt3via insertion reactions of RE {R = HC[C(Me)N(2,6-i-Pr2C6H3)]2; E = Al, Ga, In}Dedicated to Prof. M. Jansen on the occasion of his 70th birthday.Electronic supplementary information (ESI) available: Experimental procedure and characterization of 1-5 including crystallographic data for 1-3 and 5. CCDC 1011108 (1), 1011107 (2), 1011105 (3), and 1011106 (5). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4cc0502

Two of the Bi-C bonds of BiEt 3 are sequentially activated by mono-valent RM {R = HC[C(Me)N(2,6-i-Pr 2 C 6 H 3 )] 2 ; M = Al, Ga, In}. The first Bi-C bond activation leads to the formation of insertion complexes, [RMEt(BiEt 2 )] (M = Al 1 ; Ga 2 ; In 3 ), whereas the consecutive second activation proceeds through a reductive elimination of RMEt 2 (M = Al 4 , Ga 5 ), elemental Bi and BiEt 3 . Reactions of RM {R = HC[C(Me)N(2,6-i-Pr 2 C 6 H 3 )] 2 ; M = Al, Ga, In} with BiEt 3 yield the insertion complexes [RMEt(BiEt 2 )] (M = Al 1 ; Ga 2 ; In 3 ), which subsequently react to RMEt 2 , Bi and BiEt 3 at high temperature.