Bromide alkoxides of zirconium

The reaction of zirconium isopropoxide and acetyl bromide has been studied and the compounds ZrBr(OPri)3 · PriOH, ZrBr2(OPri) 2 · PriOH and ZrBr4 · 2PriOAc have been isolated. The first two are stable to heat, but the third decomposes on heating even under reduced pressure giving lower bromides. It has been shown for comparison that zirconium tetrachloride reacts with butyl acetate in a similar manner. ZrBr4 · 2PriOAc has been isolated by carrying out the reaction between Zr(OPri)4 and AcBr under milder conditions and was found to react with isopropanolto give an equimolecularmixture of ZrBr2(OPri) 2 and ZrBr3(OPri). The great ease with which these compounds exchange their radicals has been demonstrated by the reaction between dibromide and tetraisopropoxide when the monobromide compound crystallises out in quantitative yield. The mono and dibromide isopropoxide derivatives react with butanols or butyl acetates to give products in which the isopropoxy groups have been replaced. A number of new normal and secondary butoxide derivatives have been isolated, but side reactions occur in the case of tertiary butoxides