Abstract
The autoionization reaction of neutral bis(imino)pyridine and SnX2 led to three compounds [{ArN=CPh}(2)(NC5H3)]SnX+SnX3- (Ar = 2,6-(2,5-(Bu2C6H3)-Bu-t), X = Cl, Br; Ar = 2,6-(2,6-Me2C6H3), X = Cl) which display, within the same species, cations and anions possessing Sn(II) centers. Computational analysis compared the ligated Sn(II) cations with bis(imino) pyridine In(I) complexes that showed unprecedented weak metal-ligand covalent interactions, consistent with the In(I) 5s(2) electrons remaining as an inert nonbonding pair. Analysis of the metal-ligand bonding indicates that the chloride ligand of the Sn(II) complex induces promotion of the metal 5s2 electron pair to a stereochemically active hybridized orbital, which, in turn, allows strong coordination of the bis(imino)pyridine to Sn.