Titanium imido complexes as precursors to titanium nitride

Abstract

Treatment of TiCl 4 with 2-4 fold excess of Bu t N(H)SiMe 3 in CH 2 Cl 2 resulted in the formation of orange crystals of [TiCl 2 (NBu t )(NH 2 Bu t )] 4 , the X-ray crystal structure of which has been determined. In the presence of excess pyridine, the reaction of TiCl 4 with 1 equivalent of Bu t N(H)SiMe 3 resulted in the isolation of the monomeric complex [TiCl 2 (NBu t )(py) 3 ]. Low pressure chemical vapour deposition of [TiCl 2 (NBu t )(py) 3 ] forms thin films of titanium nitride (a = 4.23(1) Å, XPS TiN 0.75 ) at 600 ЊC.

Atmospheric Pressure Chemical Vapour Deposition of TiCl4 and tBuAsH2 to Form Titanium Arsenide Thin Films

“…TiCl 4 /NH 3 ) and singlesource precursors, such as amido and imido titanium(IV) compounds. [4][5][6][7] Additionally, we have used silylamines and azides as precursors, which resulted in high quality TiN films, [8][9][10] and this methodology can be extended to other transition metal nitrides. [11] As the understanding of the roles of the precursor have developed, more user-friendly (i.e.…”

Novel ion pairs obtained from the reaction of titanium(IV) halides with simple arsane ligands

“…The deposition of transition metal pnictide thin films is a growing area of research, owing mainly to the useful properties of these films, examples being TiN (Carmalt et al, 2002;Newport et al, 2002), ZrN (Potts et al, 2009), TiP (Blackman et al, 2004), TiAs (Thomas, Blackman et al, 2010), CoAs (Senzaki & Gladfelter, 1994;Klingan et al, 1995) and MnAs (Lane et al, 1994). Such films are often grown by chemical vapour deposition (CVD).…”

The Progression of Synthetic Strategies to Assemble Titanium Complexes Bearing the Terminal Imide Group

“…For example, secondary amines of the type HNtBu-A C H T U N G T R E N N U N G (SiMe 3 ) react readily with TiCl 4 in CH 2 Cl 2 or THF to generate oligomers with a terminal imide group. [87] However, if a donor such as pyridine is used in the reaction, the monomer [Cl 2 (py) 2 Ti=NtBu] can be obtained. [87] .…”

“…[87] However, if a donor such as pyridine is used in the reaction, the monomer [Cl 2 (py) 2 Ti=NtBu] can be obtained. [87] . [88] Rupture of the N À Si bond in silazanes concurrent with Ti=N bond formation can also be accomplished with strained systems [89,90] and with the aid of nucleophiles.…”

“…Silyl elimination reactions can also lead to terminal titanium imides with both aliphatic and aromatic groups on nitrogen. For example, secondary amines of the type HN t Bu(SiMe 3 ) react readily with TiCl 4 in CH 2 Cl 2 or THF to generate oligomers with a terminal imide group 87. However, if a donor such as pyridine is used in the reaction, the monomer [Cl 2 (py) 2 TiN t Bu] can be obtained 87.…”