Exploring the reactivity of homoleptic organozincs towards SO: synthesis and structure of a homologous series of organozinc sulfinates.

Studies on the reactivity of zinc alkyl compounds towards SO are relatively less explored than either oxygenation or hydrolysis reactions. We report on the environmentally friendly and efficient syntheses of a homologous series of [(RSO)ZnR] complexes from reactions involving homoleptic RZn (R = Me, Bu, Ph) compounds and SO. Diffusion ordered spectroscopy experiments indicate that the resulting compounds predominately occur as solvated dimers, [(RSO)ZnR(THF)], in THF solution irrespective of the character of the group bonded to the zinc centres. In turn, these organozinc sulfinates exhibit structurally diversified molecular and supramolecular arrangements in the solid state, as evidenced by single-crystal X-ray diffraction studies. The methyl compound crystallises as a one-dimensional polymer, [(MeSO)ZnMe], and the use of BuZn and PhZn leads to molecular aggregates, a tetramer [(BuSO)ZnBu], and a solvated [(PhSO)ZnPh]·2THF dimer, respectively. In addition, new theoretical insights have been gained by modelling the direct trapping of homoleptic organozinc compounds with SO using DFT calculations.