Infrared Spectroscopic Study of the Cryogenic Thin Film and Matrix-Isolated Complexes of TiCl4 with NH3 and (CH3)3N

Matrix Isolation Study of the Reaction of TiCl4 with CH3OH: Synthesis and Characterization of Cl3TiOCH3

“…10,11 In a complex, the two subunits are perturbed, yet retain their structural integrity. Multiple reaction products were observed under the different deposition conditions employed in this study.…”

A four coordinate parent imidevia a titanium nitridyl

“…For example, the 15 N NMR spectrum displays a new doublet at 394 ppm ( 1 J NH = 58 Hz) indicative of retention of the NH group. Further analysis of the new product by 1 H NMR shows the 15 N-H resonance also as a doublet at 5.78 ppm ( 1 J HN = 58 Hz). As a result, we propose that deprotonation of the nacnac b-methyl group has occurred.…”

“…Parent imides of titanium, [L n TiQNH], are rare entities which is rather surprising given their presumed involvement in industrially important processes such as the fabrication of thin metal nitride films (via MOCVD methods). 1,2 Likewise, parent imides are intermediates in the Chatt-cycle involved in the generation of NH 3 from N 2 , protons and electrons, 3 hence playing an important role enroute to molecular metal nitrides. To date, the only example of a terminal parent imide of titanium (or a group 4 transition metal) is the complex [(Ph 3 PO) 2 TiQNH(Cl) 2 ] reported by Winter and co-workers.…”

2 Matrix isolation

“…With NH 3 and Me 3 N, 1+1 complexes are formed. 21 For the ammonia complex intense IR spectral features at 440 and 457 cm -1 were assigned to n asym (Ti-Cl) modes (the parent n asym (Ti-Cl) mode of TiCl 4 occurs at 503 cm -1 ), while the NH 3 symmetric deformation mode was seen to shift by some 200 cm -1 from the parent band position. The spectra suggested a trigonal bipyramidal arrangement about the central titanium atom with the NH 3 group in an axial position.…”