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(+) ns 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)](•-).