Alkylzinc diorganophosphates: synthesis, structural diversity and unique ability to incorporate zincoxane units

Equimolar reactions between ZntBu2 and diphenyl phosphate (dpphe-H) or dimethyl phosphate (dmphe-H) result in the formation of [tBuZn(O2P(OR')2)]-type compounds which crystallize as tetranuclear aggregates, [tBuZn(dpphe)]4 (14) or [tBuZn(dmphe)]4 (24), with the phosphate ligands spanning 4-coordinate Zn centers. The utility of ZnMe2 instead of ZntBu2 dramatically changes the reaction outcome and leads to [MeZn(O2P(OR')2)]-type moieties incorporating zincoxane units, i.e., pentanuclear [{MeZn(dpphe)}3(Me2Zn2O)(THF)2] (3) and nonanuclear [{MeZn(dmphe)}6(Me2Zn3O2)] (4) aggregates. The resulting compounds were characterized by 1H and 31P NMR spectroscopy and single-crystal X-ray diffraction analysis.