The reaction of titanium(IV) halides with some aliphatic amines

Cowdell, Richard; Fowles, G. W. A.; Walton, Richard A.

doi:10.1016/0022-5088(63)90052-3

Cited by 14 publications

(3 citation statements)

References 9 publications

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“…The crystallite size was determined to be as small as 8.23 nm for TiN synthesized at 4001C but obviously increased with heat-treatment temperature because of the expected grain growth. N-H 2 rocking 683 26,27 Ti-Cl stretching 447 erates of nano-sized spherical crystallites with diameter approximately % 10 nm, which is in close agreement with the calculated value using XRD peak broadening. Figure 5 shows the histogram depicting the crystallite size distribution calculated for a total of 60 crystallite (Gaussian function) of TiN synthesized at 5001C.…”

Section: August 2005supporting

confidence: 85%

“…The as‐prepared powder shows mainly ammonium chloride bands with additional bands at 1599, 1254, 828, 683, and 447 cm −1 . The bands at 1599 and 683 cm −1 are the NH bending and NH 2 rocking bands from the amide groups bonded to titanium, respectively, 26,27 whereas the broad band around 3300–3000 cm −1 is the NH stretching mode, 26,27 the additional bands at 1254 and 828 cm −1 are likely to be related to NH 2 wagging and twisting bands 28,29 . The band at 447 cm −1 is the Ti–Cl stretching band indicating the presence of chlorine with amides 30 .…”

Section: Resultsmentioning

confidence: 99%

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Synthesis of Nanostructured TiN Using a Two‐Step Transition Metal Halide Approach

Choi

Kumta

2005

Journal of the American Ceramic Society

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A two‐step transition metal halide approach has been developed for synthesizing uniform ultra‐fine titanium nitride (TiN) nano‐crystallites (<10 nm) at relatively low temperatures of 400°C. The nano‐sized TiN crystallites were obtained by reacting liquid titanium tetrachloride dissolved in anhydrous chloroform with anhydrous NH3 gas at room temperature followed by heat treatment under ultra‐high‐purity Ar, N2, and anhydrous NH3 atmosphere. The synthesized TiN nano‐crystallites were characterized by X‐ray diffraction, Brunauer–Emmett–Teller, pycnometer, differential thermal analysis/thermo‐gravimetric analysis, and high‐resolution transmission electron microscopy. The effect of the heat treatment temperature and atmosphere (Ar, N2, and NH3) on the specific surface area, density, crystal structure, and composition is discussed.

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Section: August 2005supporting

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Synthesis of Nanostructured TiN Using a Two‐Step Transition Metal Halide Approach

Choi

Kumta

2005

Journal of the American Ceramic Society

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“…T h e extent of solvolysis could not be determined since it was not possible t o separate the amine hydrochloride from the titanium complex. Attempts t o wash out the amine hydrochloride with either the parent amine or a solution of the amine in benzene (16) were not successful, and in general there was further reaction between amine and the titanium complex. However, complete solvolysis of the titanium-halogen bond did not occur, a t least in the chlorides, as an absorption band in the region 360-390 cm-I could be assigned t o the Ti-Cl stretching mode (5).…”

Section: Results a N D Discussionmentioning

confidence: 99%

The Infrared Spectra of Some Titanium (Iv) Complexes With Primary Diamines

Horley¹,

Torrible²

1965

Can. J. Chem.

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A series of titanium(1V) halide -diamine complexes have been prepared and their infrared spectra measured in the solid state between 4 000 and 300 cnl-'. The configuration of the ligand and extent of aminolysis of the titanium-halide bond are discussed in relation to the spectra. Some assignments are proposed in the 600-300 cm-I region for the ethylenediamine complexes. INTRODUCTION An extensive study of the reaction between titaniuin(1V) halides and primary monoamines has shown that the primary arnines solvolyze the metal-halogen bond (1). By comparison, little is known of the reaction with primary diamines. Fowles and i\'IcGregor (2) reported an ethylenediainine (en) complex, TiCl2[HN(CH2)2NHz]z(en)z, and suggested that the ligands were chelated t o the metal. More recently Sumarokova and Sakenova (3, 4) claimed no aminolysis of the Ti-Cl bond occurred in the complexes TiC14.2en, TiC14. 3en, and TiC14.4en. However, there was evidence for aminolysis in the reaction with hexamethylenediarnine (HMD), and the compounds TiCl3[HN(CH2)6NH?1 .nHI\IID, where n = 1, 2, and 3, were reported (4). No spectroscopic examination of these compounds has been offered t o date. I n this paper we describe the preparation of a number of titanium(1V) halide -diarnine complexes including a series of 1 : 1 adducts. T h e infrared data for these compounds in the range 4 000 t o 300 cm-I is given in Table I. E X P E R I M E N T A L Materials and Manipz~lationSpecial precautions were taken to exclude water from the apparatus and chemicals, and all reactions were conducted in an atmosphere of dry nitrogen. The amines and solvents were dried by refluxing over sodium and then fractionally distilled. The titanium halides were distilled or sublimed into the reaction vessels immediately before use.The complexes were all prepared by the same general method. Solutions of the reactants in benzene were mixed in known molar ratios. Reaction was generally immediate and heat was evolved. The resulting mixture was stirred and occasionally heated for a period of time. The products, which were all insoluble, were filtered, washed with hot benzene, and dried in vacuo. All the products reacted vigorously with water and were hydrolyzed rapidly in air. The complexes were nonvolatile and insoluble in any solvent with which they did not react.The infrared spectra were all determined as mulls in Nujol and l~exachlorobutadiene-1,3 between NaCl or KRS-5 plates on a Beckman I.R. 10 grating instrument.Analyses were obtained as previously described ( 5 ) and the data is presented in Table 11. RESULTS A N D DISCUSSIONA number of questions remain to be answered with regard to the titaniurn(1V) halidediamine complexes so far reported in the literature: (a) the extent t o which arninolysis of the Ti-X bond (X = C1, Br, or I) occurs; (b) whether the diamine is acting as a chelate or as a trans bridging unit between two different metal atoms thus forming polymeric chains; and (c) a t what value of n in the chain HzN(CH2),NH2 would there be a possible change f...

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