Reductive Elimination of Hydrogen from Bis(trimethylsilyl)methyltin Trihydride and Mesityltin Trihydride

Abstract

Alkyltin trihydride [(Me₃ Si)₂ CHSnH₃ ] was synthesized and the reductive elimination of hydrogen from this species was investigated. A methyl-substituted N-heterocyclic carbene reacts with the organotrihydride in dependence on stoichiometry and solvent to give a series of products of the reductive elimination and dehydrogenative tin-tin bond formation. Besides characterization of the carbene adduct of the alkyltin(II) hydride, a Sn₄ chain was also isolated, encompassing two stannyl-stannylene sites, which are stabilized each as NHC-adducts. Complete dehydrogenation resulted to give either a carbene-stabilized distannyne or a metalloid Sn₉ -cluster salt. Reductive elimination of hydrogen was also achieved with an excess of diethylmethylamine to give the alkyltin(II) hydride as a Lewis base free tetramer [(RSnH)₄ ]. The method of cluster formation at low temperatures by hydrogen elimination was also transferred to the mesityl-substituted tin trihydride MesSnH₃ . In this case [(MesSn)₁₀ ], showing a [5]prismane structure, was isolated in good yield and characterized. NMR spectroscopic features of the propellane-type cluster [Trip₆ Sn₆ ] are reported.