The Reaction and Materials Chemistry of [Sn6 (O)4 (OSiMe3 )4 ]: Chemical Vapour Deposition of Tin Oxide.

[Sn6 (O)4 (OSiMe3 )4 ] and [{Sn(OSiMe3 )2 }2 ] have been used to deposit SnO thin films by chemical vapour deposition. Films derived from [Sn6 (O)4 (OSiMe3 )4 ] comprise uniform cubes and are highly oriented, whereas those deposited from [{Sn(OSiMe3 )2 }2 ] are made up of a continuous non-oriented layer with oriented cubes on the surface. The structure of a co-crystal, 2 Sn6 (O)4 (OSiMe3 )4 ⋅[Sn(OSiMe3 )2 ]2 ⋅4 THF, shows that [{Sn(OSiMe3 )2 }2 ], a liquid at room temperature, adopts a μ-OSiMe3 -bridged dimeric structure. [Sn6 (O)4 (OSiMe3 )4 ] reacts with O2 in a controlled manner to afford the novel oxo-cluster [Sn4( O)(OSiMe3 )8 ], the structure of which is reported. In addition, a crystal of {[Sn4 (O)(OSiMe3 )5 ]+ 2 [Sn(O)(OSiMe3 )4 Cl]+ 2 }[Cl]- 4 has been fortuitously isolated from the presence of SnCl2 in the starting material for the preparation of [Sn6 (O)4 (OSiMe3 )4 ], and has been shown to incorporate two novel cationic oxo-tin clusters.