Thermal Decomposition of Methyl Titanium Chlorides

McCowan, James D.; Hanlan, J. F.

doi:10.1139/v72-114

Cited by 17 publications

(3 citation statements)

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“…24 h. As is evident from Figures 1 and 2, Me 2 TiCl 2 decomposes in all phases with the production of methane and a brown, involatile solid of indeterminate composition. 32 The present study yielded no IR spectrum in which bands arising from methane were absent. Inspection of Figures 1 and 2 and of Tables 8-11 reveals two features of note.…”

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confidence: 53%

“…The decomposition of Me 2 TiCl 2 in solution has previously been examined by McCowan et al ., who concluded that the reaction pathway was complex but that in dilute halocarbon solution the compound has a half-life of ca. 24 h. As is evident from Figures and , Me 2 TiCl 2 decomposes in all phases with the production of methane and a brown, involatile solid of indeterminate composition . The present study yielded no IR spectrum in which bands arising from methane were absent.…”

Section: Methodsmentioning

confidence: 99%

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Infrared Spectrum and Structure of Me₂TiCl₂ and Quantum Mechanical Calculations of Geometries and Force Fields for MeTiCl₃ and Me₂TiCl₂

McGrady¹,

Downs²,

Bednall³

et al. 1997

J. Phys. Chem. A

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Infrared spectra have been studied over the range 4000-200 cm -1 for (CH 3 ) 2 TiCl 2 , (CD 3 ) 2 TiCl 2 , (CH 2 D) 2 -TiCl 2 , and (CHD 2 ) 2 TiCl 2 in the gas and matrix phases. Some new spectral observations are also reported for CH 3 TiCl 3 and CD 3 TiCl 3 . Equilibrium geometries and force fields are calculated for both Me 2 TiCl 2 and MeTiCl using both ab initio (MP2) and DFT approaches. Scale factors for the force fields were first determined in MeTiCl 3 and then transferred to Me 2 TiCl 2 so as to provide accurate estimates and facilitate the assignment of the spectra of Me 2 TiCl 2 . Quantum mechanical (QM) calculations of infrared intensity proved to be vital in this process. A number of Fermi resonances involving skeletal bending modes below 200 cm -1 are postulated. Combination and overtone evidence for these modes suggests that they occur close to their predicted positions in all cases except one. The infrared evidence from the C-H and C-D stretching regions indicates that the C-H bonds in each methyl group in Me 2 TiCl 2 are equivalent and slightly weaker than those in MeTiCl 3 . The H-C-H angle in Me 2 TiCl 2 is found to be 109 ( 1°, about 1°less than in MeTiCl 3 . These results are largely reproduced by the DFT calculations, whereas the ab initio values indicate little difference between the two compounds. The skeletal interbond angles in Me 2 TiCl 2 are particularly sensitive to the type of QM calculation, but all calculations agree on a reduced C-Ti-C and an enlarged Cl-Ti-Cl angle, compared with the tetrahedral value. Problems arising in customary scaling procedures are addressed. The mode of thermal decomposition of the molecule is discussed.

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confidence: 53%

Section: Methodsmentioning

confidence: 99%

Infrared Spectrum and Structure of Me₂TiCl₂ and Quantum Mechanical Calculations of Geometries and Force Fields for MeTiCl₃ and Me₂TiCl₂

McGrady¹,

Downs²,

Bednall³

et al. 1997

J. Phys. Chem. A

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“…was found to be the technique of choice to study formation and decomposition of methyl titanium trichloride and dimethyl titanium dichloride (12) since the starting material and decomposition products all display well resolved, single line resonances. Nuclear magnetic resonance data on the related species reported herein were obtained to assist us in our assignment and to provide additional 'Present address: N.C.R.L., The National Gallery of Canada, Ottawa, Canada.…”

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confidence: 99%

Infrared and Nuclear Magnetic Resonance Spectra of Methyl Titanium Halides

Hanlan¹,

McCowan²

1972

Can. J. Chem.

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Nuclear magnetic resonance and infrared spectra have been obtained for CH,TiCI,, (CH,),TiCI,, and some related materials. The rather unusual n.m.r. data for these compounds and for C2H5TiC1, are compared with the results for related species involving Group IVA elements and the variations are discussed in terms of n.m.r. and bonding parameters. Exchange of methyl groups between CH,TiCl, and (CH,),TiCI, and between each of these compounds and (CH,),Zn has been studied by this means. Infrared data remain difficult to interpret, and unambiguous assignment of bands has not been achieved.Les spectres r.m.n. et infrarouges de CH,TiCI,, (CH3),TiC1, et de quelques substances apparentees, ont bte obtenues. Les donnCes r.m.n. inhabituelles obtenues pour ces composks et pour C,H5TiCI, sont compartes avec les rbsultats obtenus pour des espkces apparentbes impliquant les elements du groupe IVa; les variations observees sont discutkes en termes de paramttres de liaison et r.m.n. L'bchange des groupes mCthyles entre CH,TiCI, et (CH,),TiCI, et entre chacun de ces composks et (CH,),Zn, a btb btudii. par ces moyens. Les donntes infrarouges demeurent difficiles a interpreter et une attribution dbfinitive des bandes n'a pas kt15 effectuee.

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ChemInform Abstract: NMR‐ UND MASSENSPEKTROSKOPISCHE UNTERSUCHUNG DER THERMISCHEN ZERS. VON METHYLTITANTRICHLORID UND DIMETHYLTITANDICHLORID IN TETRACHLORAETHYLEN UND BENZOL

McCowan¹,

Hanlan²

1972

Chemischer Informationsdienst

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Thermal Decomposition of Methyl Titanium Chlorides

Cited by 17 publications

References 5 publications

Infrared Spectrum and Structure of Me₂TiCl₂ and Quantum Mechanical Calculations of Geometries and Force Fields for MeTiCl₃ and Me₂TiCl₂

Infrared Spectrum and Structure of Me₂TiCl₂ and Quantum Mechanical Calculations of Geometries and Force Fields for MeTiCl₃ and Me₂TiCl₂

Infrared and Nuclear Magnetic Resonance Spectra of Methyl Titanium Halides

ChemInform Abstract: NMR‐ UND MASSENSPEKTROSKOPISCHE UNTERSUCHUNG DER THERMISCHEN ZERS. VON METHYLTITANTRICHLORID UND DIMETHYLTITANDICHLORID IN TETRACHLORAETHYLEN UND BENZOL

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Thermal Decomposition of Methyl Titanium Chlorides

Cited by 17 publications

References 5 publications

Infrared Spectrum and Structure of Me2TiCl2 and Quantum Mechanical Calculations of Geometries and Force Fields for MeTiCl3 and Me2TiCl2

Infrared Spectrum and Structure of Me2TiCl2 and Quantum Mechanical Calculations of Geometries and Force Fields for MeTiCl3 and Me2TiCl2

Infrared and Nuclear Magnetic Resonance Spectra of Methyl Titanium Halides

ChemInform Abstract: NMR‐ UND MASSENSPEKTROSKOPISCHE UNTERSUCHUNG DER THERMISCHEN ZERS. VON METHYLTITANTRICHLORID UND DIMETHYLTITANDICHLORID IN TETRACHLORAETHYLEN UND BENZOL

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Infrared Spectrum and Structure of Me₂TiCl₂ and Quantum Mechanical Calculations of Geometries and Force Fields for MeTiCl₃ and Me₂TiCl₂

Infrared Spectrum and Structure of Me₂TiCl₂ and Quantum Mechanical Calculations of Geometries and Force Fields for MeTiCl₃ and Me₂TiCl₂