Reactions of In-Zn bonds with organic azides: products that result from hetero- and homo-bimetallic behaviour.

The indyl anion, K[In(NON)] (NON = [O(SiMeNDipp)], Dipp = 2,6-iPrCH) reacts with group 12 compounds M(BDI)Cl (M = Zn, Cd; BDI = [HC{C(Me)NR}], R = 2,4,6-MeCH (Mes), Dipp) to afford the heterobimetallic compounds (NON)In-M(BDI) that contain the first In-Zn and In-Cd bonds. The reactivity of the In-Zn bonds towards organic azides, R'N (R' = Mes, Dipp, Ph) was investigated. (NON)In-Zn(BDI) reduces MesNvia an isolable triazenide intermediate to generate the bridging imido compound, (NON)In-(μ-NMes)-Zn(BDI). Similar reactivity is noted from early-late heterobimetallic complexes. Under the same conditions, PhN reacts to afford a product that contains a bridging tetraazenide ligand, which is formed from the formal (2 + 3)-cycloaddition of second azide to an indium-imido bond. However, increasing the bulk of the BDI-ligand in (NON)In-Zn(BDI) leads to reductive coupling of PhN to give the hexazene complex. This mode of reactivity is reminiscent of the reductive behaviour of homobimetallic compounds.