Reactivity of NHI-Stabilized Heavier Tetrylenes towards CO and N O.

A heteroleptic amino(imino)stannylene (TMS N)(I BuN)Sn: (TMS=trimethylsilyl, I Bu=C[(N- Bu)CH] ) as well as two homoleptic NHI-stabilized tetrylenes, (I BuN) E: (NHI=N-heterocyclic imine, E=Ge, Sn) are presented. VT-NMR investigations of (I BuN) Sn: (2) reveal an equilibrium between the monomeric stannylene at room temperature and the dimeric form at -80 °C as well as in the solid state. Upon reaction of the homoleptic tetrylenes with CO , both compounds insert two equivalents of CO , however differing bonding modes can be observed. (I BuN) Sn: (2) inserts one equivalent of CO into each Sn-N bond, giving carbamato groups coordinated κ O,O' to the metal center. With (I BuN) Ge: (3), the Ge-N bonds stay intact upon activation, being bridged by one molecule of CO respectively, forming 4-membered rings. Furthermore, the reactivity of 2 towards N O was investigated, resulting in partial oxidation to form stannylene dimer [((I BuN) SnO)(I BuN)Sn:] (6).