Molecular Addition Compounds of Titanium Tetrachloride with Several Ethers<sup>1</sup>

Hamilton, Paul M.; McBeth, R.L.; Bekebrede, William; Sisler, Harry H.

doi:10.1021/ja01108a027

Cited by 47 publications

(19 citation statements)

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“…In the case of the methoxy group (entries 7–10), Hamilton and co-workers demonstrated that TiCl 4 are able to coordinate with several ethers [ 31 ], but it showed a weaker coordination effect in comparison with the hydroxyl one. Hence, the steric hindrance had a considerable effect on the formylated position.…”

Section: Resultsmentioning

confidence: 99%

Formylation of Electron-Rich Aromatic Rings Mediated by Dichloromethyl Methyl Ether and TiCl4: Scope and Limitations

et al. 2015

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Abstract:Here the aromatic formylation mediated by TiCl4 and dichloromethyl methyl ether previously described by our group has been explored for a wide range of aromatic rings, including phenols, methoxy-and methylbenzenes, as an excellent way to produce aromatic aldehydes. Here we determine that the regioselectivity of this process is highly promoted by the coordination between the atoms present in the aromatic moiety and those in the metal core.

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Section: Resultsmentioning

confidence: 99%

Formylation of Electron-Rich Aromatic Rings Mediated by Dichloromethyl Methyl Ether and TiCl4: Scope and Limitations

et al. 2015

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“…From relative permittivity studies, (7,8) it is known that C 5 H 5 N forms intermolecular complexes with CHCl 3 and CHClCCl 2 in the liquid state, and solid-liquid phase equilibrium studies have revealed (5,9) the formation of a 1:2 complex of C 5 H 5 N with CCl 4 , and a 1:1 complex with CHCl 3 . Further, the solid-liquid phase equilibrium studies show that C 6 H 5 OCH 3 forms a 1:1 complex (10)(11)(12) with TiCl 4 , and a 1:1 complex (13) with CCl 4 , and the values of the excess relative permittivities (14) indicate that there exist specific interactions between the components of the systems of C 6 …”

Section: Introductionmentioning

confidence: 99%

Speeds of sound in and isentropic compressibilities of (1,1,2,2,-tetrachloroethane + anisole, 1,4-dioxane, methylethylketone, and pyridine) atT= 303.15 K

Nath

1996

The Journal of Chemical Thermodynamics

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“…The powder shows a ЊC. [31] However, the fact that carbide is still seen in the present approach leads us to believe that stable adducts are combination of ring and spot diffraction patterns ( Figure 7(a)). The ring pattern was indexed to the TiC phase (Figure formed which do not completely decompose.…”

Section: Resultsmentioning

confidence: 99%

Chemically induced reduction: A viable process for synthesizing γ-TiAl based intermetallic matrix composite powders containing nanocrystalline TiC

Kim

Kumta

Chang

2000

Metall Mater Trans B

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A chemically induced reduction process has been developed for synthesizing intermetallic matrix composites (IMCs) consisting of titanium aluminide and titanium carbide. The process involves the reduction of metal chlorides (TiCl 4 and AlCl 3 ) with metallic lithium in polar organic solvents such as acetonitrile (MeCN) and tetrahydrofuran (THF) to form a colloidal precursor. The as-prepared precursors have been either directly heat treated in ultra-high-purity argon (UHP-Ar) or pretreated in hydrogen (H 2 ) followed by further heat treatment in UHP-Ar. The powders have been characterized primarily using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Results of the structural analyses conducted on the heat-treated precursors derived using MeCN as a solvent indicate the formation of either single-phase titanium carbide (TiC) or a composite mixture of ␥-TiAl and nanocrystalline TiC, depending on the heat-treatment conditions. The formation of TiC is related to the strong interaction between TiCl 4 and the polar organic solvents, resulting in the formation of adducts which contain primary Ti-C linkages. Pretreatment of the precursors derived using MeCN as a solvent in H 2 promotes the removal of carbon and results in the formation of the composite mixture of ␥-TiAl and TiC after subsequent Ar treatment at 1200 ЊC. At this stage, washing the pretreated powders in water helps to minimize and even eliminate any impurity phases to a large extent, leaving behind phase-pure composites containing ␥-TiAl and TiC after the final Ar treatment. However, extended pretreatment in H 2 appears to be ineffective toward removal of additional carbon and leads to formation of hydride-phase impurities. On the other hand, the reductive reaction conducted using THF as a solvent results in minimizing the amount of carbon while inducing the formation of ␥-TiAl during direct Ar treatment of the precursors. This is because of the weaker interaction between TiCl 4 and THF. Transmission electron microscopy was used to characterize the size distribution of the constituent phases. The analysis shows that the composite synthesized using these chemical approaches consist of discrete nanocrystalline TiC particles (Ͻ20 nm) that are uniformly distributed intermixed with submicron sized ␥-TiAl (0.1 to 0.2 m). Thus, the new chemical process proposed in this study demonstrates the potential for synthesizing in situ composites containing fine distribution of ␥-TiAl and nanocrystalline TiC. Such composites could potentially exhibit unique mechanical properties and deformation behavior useful for high-temperature structural applications.

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Molecular Addition Compounds of Titanium Tetrachloride with Several Ethers¹

Cited by 47 publications

References 2 publications

Formylation of Electron-Rich Aromatic Rings Mediated by Dichloromethyl Methyl Ether and TiCl4: Scope and Limitations

Formylation of Electron-Rich Aromatic Rings Mediated by Dichloromethyl Methyl Ether and TiCl4: Scope and Limitations

Speeds of sound in and isentropic compressibilities of (1,1,2,2,-tetrachloroethane + anisole, 1,4-dioxane, methylethylketone, and pyridine) atT= 303.15 K

Chemically induced reduction: A viable process for synthesizing γ-TiAl based intermetallic matrix composite powders containing nanocrystalline TiC

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Molecular Addition Compounds of Titanium Tetrachloride with Several Ethers1

Cited by 47 publications

References 2 publications

Formylation of Electron-Rich Aromatic Rings Mediated by Dichloromethyl Methyl Ether and TiCl4: Scope and Limitations

Formylation of Electron-Rich Aromatic Rings Mediated by Dichloromethyl Methyl Ether and TiCl4: Scope and Limitations

Speeds of sound in and isentropic compressibilities of (1,1,2,2,-tetrachloroethane + anisole, 1,4-dioxane, methylethylketone, and pyridine) atT= 303.15 K

Chemically induced reduction: A viable process for synthesizing γ-TiAl based intermetallic matrix composite powders containing nanocrystalline TiC

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Molecular Addition Compounds of Titanium Tetrachloride with Several Ethers¹