En Route to a Molecular Terminal Tin Oxide.

In the pursuit of terminal tin chalcogenides, heteroleptic stannylenes bearing terphenyl- and hexamethyldisilazide ligands were reacted with carbodiimides to yield the respective guanidinato complexes. Further supported by quantum chemical calculations, this revealed that the iso-propyl-substituted derivative provides the maximum steric protection achievable. Oxidation with elemental selenium produced monomeric terminal tin selenides with four-coordinate tin centers. In reactions with N2O as oxygen transfer reagent, silyl migration toward putative terminal tin oxide intermediates gave rise to tin complexes with terminal ─OSiMe3 functionality. To prevent silyl migration, the silyl groups were substituted with cyclohexyl moieties. This analogue exhibited distinctively different reactivities toward selenium and N2O, yielding a 1,2,3,4,5-tetraselenastannolane and chalcogenide-bridged dimeric compounds, respectively.