Journal article
Synthesis, structure and reactivity of mononuclear paramagnetic complexes of zirconium and hafnium
Polyhedron, Vol.15(4), pp.689-703
1996
DOI: 10.1016/0277-5387(95)00287-3
Abstract
The reduction of the zirconium(IV) precursor Zr(
η
5-C
5H
5)Cl
2[N(SiMe
2 CH
2PPr
2
i)
2] with sodium-amalgam under argon or vacuum generates the mononuclear Zr
III complex Zr(
η
5-C
5H
5)Cl[N(SiMe
2CH
2PPr
2
i)
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(
η
5-C
5H
5)R[N(SiMe
2CH
2PPr
2
i)
2] (RPh, Me, Et, CH
2Ph and CH
2SiMe
3) were prepared as well as the heteroatom derivatives Zr(
η
5-C
5H
5)X[N(SiMe
2CH
2PPr
2
i)
2)
2] (X OPh, NPh
2 and PPh
2); all of the hydrocarbyl and heteroatom substituted Zr
III derivatives are mononuclear and were characterized by ESR spectroscopy. In addition, the hafnium(III) complex Hf(
η
5-C
5H
5)Cl[N(SiMe
2CH
2PPr
2
i)
2] could be isolated via the same procedure but in this case, one could observe the analogous Zr
III complex as an impurity Oxidation of the Zr
III and Hf
III complexes could be effected by the addition of TiCl
3, PbCl
2 or PhSSPh. Two crystal structures are also included: Zr(
η
5-C
5H
5)Ph[N(SiMe
2CH
2PPr
2
i
2] and Zr(
η
5-C
5H
5)CH
2SiMe
3[N(SiMe
2CH
2PPr
2
i)
2].
Details
- Title: Subtitle
- Synthesis, structure and reactivity of mononuclear paramagnetic complexes of zirconium and hafnium
- Creators
- Michael D FryzukMurugesapillai MylvaganamMichael J ZawarotkoLeonard R MacGillivray
- Resource Type
- Journal article
- Publication Details
- Polyhedron, Vol.15(4), pp.689-703
- Publisher
- Elsevier Ltd
- DOI
- 10.1016/0277-5387(95)00287-3
- ISSN
- 0277-5387
- Language
- English
- Date published
- 1996
- Academic Unit
- Pharmaceutical Sciences and Experimental Therapeutics; Chemistry
- Record Identifier
- 9984216583702771
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