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

Abstract

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.