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DOI: 10.1039/A705246D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 553-558

Titanium(IV)azido and imido complexes as potential precursors to titanium nitride

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Claire J. Carmalt, Sandra R. Whaley, Pindy S. Lall, Alan H. Cowley, Richard A. Jones, Brian G. McBurnett and John G. Ekerdt

Abstract

Synthetic and structural studies have been performed for two imido complexes of titanium(IV). The reaction between [{Ti(NBut)Cl2(NH2But)2}3] and 6 equivalents of Me3SiN3 at room temperature in the presence of pyridine resulted in the substitution of only one chloride per titanium atom and formation of the dimeric complex [{Ti(NBut)Cl(N3)(py)2}2] (py = pyridine). An alternative approach to such complexes, which involved the reaction between [Ti(NMe2)2(N3)2(py)2] and 1 equivalent of CyNH2 at room temperature, resulted in the dimeric bis(azide) complex [{Ti(NCy)(N3)2(py)2}2] (Cy = cyclohexyl). The two new complexes have been characterised by X-ray crystallography; the solid state of each comprises dimeric units in which the two titanium atoms are bridged by a pair of azide ligands. A gas-phase pyrolysis study has been conducted on [Ti(NMe2)2(N3)2(py)2] and preliminary CVD experiments on the two new complexes revealed that they are not effective titanium nitride precursors.

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