Synthesis and characterization of tin containing polyhedral oligometallasilsesquioxanes (POMSS)

Abstract

Tin silicate species have shown good catalytic activity in various oxidation reactions. In an attempt to mimic surface tin species, several tin containing silsesquioxanes have been synthesized. Incompletely condensed silsesquioxanes ( c-C ₅H ₉) ₇Si ₇O ₉(OH) ₃ and ( c-C ₅H ₉) ₇Si ₇O ₉(OSiMe ₃)(OH) ₂ were reacted with common tin-precursors, which afforded several silsesquioxane ligated tin compounds. Divalent stannasilsesquioxanes form dimers of the type [( c-C ₅H ₉) ₇Si ₇O ₁₁(OX)Sn] ₂ (X = H, SiMe ₃) with three-coordinated tin centers. The three-coordinated tin( II) are hydrolytically unstable whereas the octahedrally surrounded tetravalent stannasilsesquioxanes [( c-C ₅H ₉) ₇Si ₇O ₁₁(OX)]Sn(acac) ₂ (X = H, OSiMe ₃) are hydrolytically robust. An unprecedented anionic trimeric cluster, {[( c-C ₅H ₉) ₇Si ₇O ₁₂Sn] ₃(μ ₂-OH) ₃(μ ₃-OH)} ⁻{HNEt ₃} ⁺, stabilized by bridging hydroxyl groups was formed when the product formed upon reacting ( c-C ₅H ₉) ₇Si ₇O ₉(OH) ₃ with SnCl ₄ was slowly hydrolyzed. The stannasilsesquioxanes showed no catalytic activity in oxidation reactions.