Tin(II) Hydrides as Intermediates in Rearrangements of Tin(II) Alkyl Derivatives

Reactions of the Sn(II) hydrides [ArSn(μ-H)]2 (1) (Ar = AriPr4 (1a), AriPr6 (1b); AriP4 = C6H3-2,6-(C6H3-2,6-iPr2)2, AriPr6 = C6H3-2,6-(C6H2-2,4,6-iPr3)2) with norbornene (NB) or norbornadiene (NBD) readily generate the bicyclic alkyl-/alkenyl-substituted stannylenes, ArSn(norbornyl) (2a or 2b) and ArSn(norbornenyl) (3a or 3b), respectively. Heating a toluene solution of 3a or 3b at reflux afforded the rearranged species ArSn(3-tricyclo[2.2.1.02,6]heptane) (4a or 4b), in which the norbornenyl ligand is transformed into a nortricyclyl group. 1H NMR studies of the reactions of 4a or 4b with tert-butylethylene indicated the existence of an apparently unique reversible β-hydride elimination from the bicyclic substituted aryl/alkyl stannylenes 2a or 2b and 3a or 3b. Mechanistic studies indicated that the transformation of 3a or 3b into 4a or 4b occurs via a β-hydride elimination of 1a or 1b to regenerate NBD. Kinetic studies showed that the conversion of 3a or 3b to 4a or 4b is first order. The rate constant k...