Synthesis and reactions of alkoxyzirconium(IV) O,O-alkylen dithiophosphates

Abstract

Reactions of Zr(OPr<em>ⁱ</em>)₄·Pr<em>ⁱ</em>OH with O,O-alkylene dithiophosphoric acids in equimolar ratio yield trisopropoxyzirconium alkylene dithiophosphates, (Pr<em>ⁱ</em>O)₃ ZrS(S)<img src='http://www.niscair.res.in/jinfo/equation3.gif' border=0> (G = - C(Me)₂C(Me)₂-, -CH(Me) CH(Me)-, -CH₂C(Me)₂CH₂- and -CH₂C(Et)₂C₂-) as hydrolysable, white microcrystalline solids, sol ble in common organic solvents and dimeric in nature. Further replacement of isopropoxy group by dithiophosphato moieties is extremely slow but can be carried out up to the formation of (Pr<em>ⁱ</em>O)₂Zr[S(S)<img src='http://www.niscair.res.in/jinfo/equation171.gif' border=0>]₂ which is monomeric in benzene. The IR and NMR (¹H, ¹³C, ³¹P) data of all the compounds are consistent with the presence of chelating dithiophosphate groups and octahedral structures, the dimerisation in the triisopropoxy derivatives occurring through isopropoxy ridges. Alcoholysis reactions of isopropoxy derivatives with butanol have also been studied.