174135-70-7Relevant academic research and scientific papers
Synthesis, structure and reactivity of mononuclear paramagnetic complexes of zirconium and hafnium
Fryzuk, Michael D.,Mylvaganam, Murugesapillai,Zaworotko, Michael J.,MacGillivray, Leonard R.
, p. 689 - 703 (1996)
The reduction of the zirconium(IV) precursor Zr(n5-C5H5)Cl2[N(SiMe2 CH2PPr12)2] with sodium-amalgam under argon or vacuum generates the mononuclear ZrIII complex Zr(n5-C5H5)Cl[N(SiMe2CH 2PPr12)2] as a thermally stable, crystalline material. Further functionalization of the remaining chloride is possible by the addition of a variety of organometallic reagents, as well as heteroatom nucleophiles. Thus, the hydrocarbyl complexes Zr(n5-C5H5)R[N(SiMe2CH 2PPr12)2] (R = Ph, Me, Et, CH2Ph and CH2SiMe3) were prepared as well as the heteroatom derivatives Zr(n5-C5H5)X[N(SiMe2CH 2PPr12)2] (X = OPh, NPh2 and PPh2); all of the hydrocarbyl and heteroatom substituted ZrIII derivatives are mononuclear and were characterized by ESR spectroscopy. In addition, the hafnium(III) complex Hf(n5-C5H5)Cl[N(SiMe2CH 2PPr12)2] could be isolated via the same procedure but in this case, one could observe the analogous ZrIII complex as an impurity. Oxidation of the ZrIII and HfIII complexes could be effected by the addition of TiCl3, PbCl2 or PhSSPh. Two crystal structures are also included : Zr(n5-C5H5)Ph[N(SiMe2CH 2PPr12)2] and Zr(n5-C5H5)CH2SiMe 2[N(SiMe2CH2PPr12) 2].
