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

摘要

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 ZrCl_4 with LH_2 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(_2PPNtBu}{K·(eta~6-C_7H_8_)}·0.5C_7H_8] (2). The molecular structures of 1 and 2 have been determined by X-ray diffraction. In the crystalline state of 2 and eta~1-L ligand, an imido moiety (NtBu) and two amido nitrogen atoms [eta~2-(NtBu)_2PPNtBu] bnd to the zirconium center, and the coordination sphere of K is occupied by three amido nitrogen atoms [eta~3-(NtBu)_2PPNtBu], and eta~6-C_7H_8 molecule and two Me groups.