Tin—Tin π Bonding as a Conduit for Alkali‐Metal Reduction
Abstract
Abstract Reactions of the doubly reduced distannynes, [Ar′SnSnAr′M 2 ], (Ar′ = C 6 H 3 ‐2,6‐Dipp; M = Li, Na, K), with the successively heavier group 1 elements (M′) result in reduction of M and the isolation of [Ar′SnSnAr′M′ 2 ]. Although the viability of these observations, along with the reversible formation of [Ar′SnSnAr′K 2 ] by treatment of [Ar′SnSnAr′Rb 2 ] with potassium, is successfully predicted by a combined theoretical and thermochemical analysis, assessment of the bonding within [Ar′SnSnAr′M 2 ] suggests that any M + n s valence orbital contribution should be too high in energy to effect M + reduction. Based on a consideration of the Sn─Sn π bonding and theoretical assessment of the resultant frontier orbitals, however, we suggest that the electron transfer necessary for M + reduction, occurs intramolecularly and via a suitably disposed π* SOMO of the putative radical anions, [Ar′SnSnAr′M 2 ] •− .
Article Details
Authors (6)
Agustín Morales
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Kyle G. Pearce
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Louis J. Morris
Department of Chemistry University of Bath Claverton Down Bath BA2 7AY UK
Michael S. Hill
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Claire L. McMullin
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Emma Richards
Cardiff Catalysis Institute School of Chemistry Cardiff University Maindy Road Cardiff CF24 4HQ UK