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

Academic Article


  • 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[,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 for the conversion of 3a into 3b was determined to be 3.33 × 10-5 min-1, with an activation energy Ea of 16.4 ± 0.7 kcal mol-1.
  • Authors

  • Wang, Shuai
  • McCrea-Hendrick, Madison L
  • Weinstein, Cory M
  • Caputo, Christine
  • Hoppe, Elke
  • Fettinger, James C
  • Olmstead, Marilyn M
  • Power, Philip P
  • Status

    Publication Date

  • May 17, 2017
  • Has Subject Area

    Digital Object Identifier (doi)

    Pubmed Id

  • 28399365
  • Start Page

  • 6596
  • End Page

  • 6604
  • Volume

  • 139
  • Issue

  • 19