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

Alkyltin trihydride [(Me 3 Si) 2 CHSnH 3 ] 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 Sn 4 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 Sn 9 ‐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 MesSnH 3 . 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 [Trip 6 Sn 6 ] are reported.