86013-27-6Relevant articles and documents
Transition Metal-Phosphide Chemistry: Synthesis of (M(η-C5H5)2(PR2)2) (M=Zr, R=Ph; M=Hf, R=Ph or cyclo-C6H11) and ((M(η-C5H5)2(PR2))2) (M=Ti, R=Ph or Me; M=Zr or Hf, R=Me), and their Reactions with Protic and Halogen-containing Species
Wade, Steven R.,Wallbridge, Malcolm G. H.,Willey, Gerald R.
, p. 2555 - 2560 (2007/10/02)
Reactions of the metallocene dichlorides (M(cp)2Cl2) (M=Ti, Zr, or Hf; cp=η-C5H5) with stoicheiometric amounts of LiPR2 (R= Me, Ph, or cyclo-C6H11) yield either the direct exchange products (M(IV)(cp)2(PR2)2) (M=Zr, R=Ph; M=Hf, R=Ph or C6H11) or the reduced species ((M(III)(cp)2 (PR2))2) M=Ti, R=Me or Ph; M=Zr or Hf, R=Me).Spectral (i.r. and (1)H n.m.r.) characterisation of these compounds is presented and discussed with suggestions of possible structures.Treatment of (Zr(cp)2(PPh2)2) with PPh3Cl affords the 'mixed' chloro-phosphido-compound (Zr(cp)2Cl(PPh2)).Reactions of both the M(IV) and M(III) species with halogen-containing and protic reagents have been investigated.Each series reacts with smooth cleavage of the M-P bond(s), but whereas the compounds (M(cp)2(PR2)2) (M=Ti, Zr, or Hf) show simple metathetical exchange, ((M(cp)2(PR))2)usually (and in the case of M=Zr or Hf exclusively) also incorporate metal oxidation M(III) M(IV) into their reactions.
