title: Tin(II) Hydrides as Intermediates in Rearrangements of Tin(II) Alkyl Derivatives.
abstract: 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 for the conversion of 3a into 3b was determined to be 3.33 × 10-5min-1, with an activation energy Eaof 16.4 ± 0.7 kcal mol-1.
authors.affiliation: Department of Chemistry, University of California, Davis , 1 Shields Avenue, Davis, California 95616, United States.
authors.forename: Shuai
authors.initials: S
authors.lastname: Wang
authors.affiliation: Department of Chemistry, University of California, Davis , 1 Shields Avenue, Davis, California 95616, United States.
authors.forename: Madison L
authors.initials: ML
authors.lastname: McCrea-Hendrick
authors.affiliation: Department of Chemistry, University of California, Davis , 1 Shields Avenue, Davis, California 95616, United States.
authors.forename: Cory M
authors.initials: CM
authors.lastname: Weinstein
authors.affiliation: Department of Chemistry, University of California, Davis , 1 Shields Avenue, Davis, California 95616, United States.
authors.forename: Christine A
authors.initials: CA
authors.lastname: Caputo
authors.affiliation: Department of Chemistry, University of California, Davis , 1 Shields Avenue, Davis, California 95616, United States.
authors.forename: Elke
authors.initials: E
authors.lastname: Hoppe
authors.affiliation: Department of Chemistry, University of California, Davis , 1 Shields Avenue, Davis, California 95616, United States.
authors.forename: James C
authors.initials: JC
authors.lastname: Fettinger
authors.affiliation: Department of Chemistry, University of California, Davis , 1 Shields Avenue, Davis, California 95616, United States.
authors.forename: Marilyn M
authors.initials: MM
authors.lastname: Olmstead
authors.affiliation: Department of Chemistry, University of California, Davis , 1 Shields Avenue, Davis, California 95616, United States.
authors.forename: Philip P
authors.identifier: 0000-0002-6262-3209
authors.initials: PP
authors.lastname: Power