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Issue 10, 1996
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Homoleptic hydroxylamides of titanium, zirconium and hafnium


The homoleptic N,N-dimethylhydroxylamides of titanium (1), zirconium (2) and hafnium (3), M(ONMe2)4, have been prepared in high yield by the reactions of the corresponding metal tetrakis(dimethylamides) and N,N-dimethylhydroxylamine in diethyl ether. The compounds have been characterised by 1H and 13C NMR and IR spectroscopy as well as by nominal and high-resolution mass spectrometry and elemental analysis. Compounds 1 and 2 are crystalline solids, which dissolve in ethers and hydrocarbons. They can be sublimed at 90 and 100 °C (0.1 mbar) respectively. These volatility data are discussed in comparison to those of the isoelectronic titanium and zirconium tetra(isopropoxides) and Ti(ONEt2)4 and in the context of their molecular complexities and structures. Compounds 1 and 2 are monomeric both in benzene solution and in the solid state, as shown by cryoscopy and single-crystal X-ray diffraction, respectively. The Ti and Zr atoms occupy an eight-co-ordinate environment with the ONMe2 ligands co-ordinated in a bidentate fashion. Crystallographic C2 axes pass through the metal atoms in 1 and 2. The non-equivalent ONMe2 ligands in one molecule have been found to exhibit markedly different geometries, which are discussed in the context of the molecular geometry of free Me2NOH.

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Article type: Paper
DOI: 10.1039/DT9960002089
Citation: J. Chem. Soc., Dalton Trans., 1996,0, 2089-2093

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    Homoleptic hydroxylamides of titanium, zirconium and hafnium

    N. W. Mitzel, S. Parsons, A. J. Blake and D. W. H. Rankin, J. Chem. Soc., Dalton Trans., 1996, 0, 2089
    DOI: 10.1039/DT9960002089

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