The formation of an imidozirconium compound by migration of the imido group from phosphorus to zirconium

Abstract

The eta(3)/eta(1)-bis(tert-butylamido)cyclodiphosph(III)azane zirconium chloride (eta(3)-L)(eta(1)-LH) ZrCl [1; L = (PNtBu)(2)(-)(NtBu)(2)] has been synthesized from the reaction of ZrCl4 with LH2 and nBuLi in toluene. Further reaction of 1 with K-Na alloy in toluene leads to the cleavage of two P-N bonds of the eta(3)-L ligand and the migration of the NtBu group from P to Zr, with the formation of the amidoimidozirconium potassium complex [(eta(1)-LH) Zr=NtBu{(NtBu)(2)PPNtBu}{K.(eta(6)-C7H8)}.0.5C(7)H(8)] (2). The molecular structures of 1 and 2 have been determined by X-ray diffraction. In the crystalline state of 2 an eta(1)-L ligand, an imido moiety (NtBu) and two amido nitrogen atoms [eta(2)-(NtBu)(2)PPNtBu] bind to the zirconium center, and the coordination sphere of K is occupied by three amido nitrogen atoms [eta(3)-(NtBu)(2)PPNtBu], an eta(6)-C7H8 molecule and two Me groups.