A structural and theoretical study of the monolithiation of hydroxylamines

Dibenzylhydroxylamine, (PhCH2)(2)NOH, is readily monolithiated to yield an unsolvated product, 1. In the solid state 1 is hexameric, with a core of two stacked (OLi)(3) rings. The metal centres are further coordinated by virtue of intra-monomer chelation using hydroxylamide N-centres, yielding three-membered NOLi rings. Ab initio M.O. calculations have been used to probe the structural options available for lithium hydroxylamide itself, [H2NOLi](n) (n = 1-4,6,8,9). The calculational findings shed light on why a hexameric structure is found in the experimental system. (C) 1998 Elsevier Science S.A.