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

Małgorzata Wolska-Pietkiewicz,^a* Adam Świerkosz,^a* Iwona Justyniak,^b Agnieszka Grala,^b Kamil Sokołowski,^b Janusz Lewiński,^ab

^a Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
^b Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

DOI: 10.1039/c6dt03324e
First published online 24 Aug 2016.
Cover of Chem. Commun.
Paper on the publisher's website.

Equimolar reactions between ZntBu₂ and diphenyl phosphate (dpphe-H) or dimethyl phosphate (dmphe-H) result in the formation of [tBuZn(O₂P(OR’)₂)]-type compoundswhich 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 ZnMe₂instead 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.