A new synthetic entry to phosphinophosphinidene complexes. Synthesis and structural characterisation of the first side-on bonded and the first terminally bonded phosphinophosphinidene zirconium complexes [μ-(1,2∶2-η-tBu2PP){Zr(Cl)Cp2}2] and [{Zr(PPhMe2)Cp2}(η1-P–PtBu2)]
The reactions of R2P-P(SiMe3)Li (R = (t)3u, Pr-i, (Pr2N)-Pr-i) with [Cp2MCl2] (M = Zr, Hf), [Cp*CpaCl(2)] and [CpZrCl3] yielded polyphosphorus (mainly hexaphosphorus) compounds which can be viewed as intermediates between R2P-P(SiMe3)Li and derivatives of 1,2,3,4-tetraphosphabicyclo[1.1.0] butane. Thus R2P-P(SiMe3)Li can act as a building block for the formation of the P-2 ligand and the R2P-P(P-2) and R2P-P(P-2)P-PR2 moieties. Solid state structures of zirconium(IV) and hafnium(IV) complexes with R2P-P-2(P-2) and R2P-P(P-2)P-PR2 ligands were established by X-ray studies. (C) 2013 Elsevier Ltd. All rights reserved.