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

[Sn-6(O)(4)(OSiMe3)(4)] and [{Sn(OSiMe3)(2)}(2)] have been used to deposit SnO thin films by chemical vapour deposition. Films derived from [Sn-6(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, 2Sn(6)(O)(4)(OSiMe3)(4)[Sn(OSiMe3)(2)](2)4THF, shows that [{Sn(OSiMe3)(2)}(2)], a liquid at room temperature, adopts a -OSiMe3-bridged dimeric structure. [Sn-6(O)(4)(OSiMe3)(4)] reacts with O-2 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 {[Sn-4(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 [Sn-6(O)(4)(OSiMe3)(4)], and has been shown to incorporate two novel cationic oxo-tin clusters.