The thermal decomposition of dicyclopentadienyldimethyltitanium(IV)

Thermal decomposition of (C₅H₅)₂Ti(CH₃)₂ in alkane or benzene solution yields primarily methane, with only traces of ethane. Methane is produced by hydrogen abstraction from both the cyclopentadienyl rings and from the methyl groups, but never from the alkanes or benzene. A scheme of decomposition is suggested involving two paths, each with a two stage formation of methanes. A very much slower ethane formation competes with the second stage. Strong evidence exists for slow hydrogen exchange between the eyelopentadienyl rings and the methyl groups prior to significant production of ethane. Decomposition in diethyl ether yields methane, much of it arising through hydrogen abstraction from the ether. Decomposition in CCl₄ and C₂Cl₄ yields mainly methane but also some methyl chloride and ethane. Both diethyl ether and C₂Cl₄ almost block methane formation through ring attack.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.     

Performance evaluation of the GastroPlusTM software tool for prediction of the toxicokinetic parameters of chemicals

ABSTRACT

The accurate prediction of toxicokinetic parameters arising from oral, dermal and inhalation routes of chemical exposure is a key element in chemical safety assessments. In this research, the physiologically based pharmacokinetic (PBPK) GastroPlus^TM software was evaluated against a series of chemicals for the prediction of toxicokinetic parameters. Overall, 67% of predicted intrinsic clearance (Clint) values were within 1- to 10-fold of empirical data for 463 compounds, and 87% of the predicted fraction unbounded in plasma (Fup) values were 1- to 3-fold of empirical data for 441 compounds. The r² (coefficient of determination) of predicted C_max (maximum plasma concentration) and AUC (Area Under Curve) values versus the corresponding empirical values from oral, inhalation and dermal exposures ranged from 0.04 to 0.92. Among the three exposures, the highest r² values, ranging from 0.80 to 0.92, were observed for oral exposure predictions, where 88% of the compounds had 1- to 10-fold differences between predicted and empirical values for C_max and AUC. The predicted plasma C_ss (steady-state plasma concentration) values were consistent with those C_ss values calculated by in vitro-to-in vivo extrapolation (IVIVE) approaches using experimental parameters. Based on the evaluation results, GastroPlus? can be used as a QSAR/PBPK tool for toxicokinetic parameter predictions.     

Femtosecond vibrational relaxation of large organic molecules

The intramolecular relaxation time of highly excited states of the vibronic manifold of the first excited singlet state of large organic molecules such as Nile Blue, Rhodamine 640, DODC iodide, Cresyl Violet, and Oxazine 725 in solution is shown to be extremely fast, less than 30 fs. We believe that this is a characteristic time of the relaxation due to anharmonic coupling among the many degrees of freedom of the molecule.     

Azimuthal dependence of impact scattering in electron energy loss spectroscopy

The azimuthal dependence of electron energy loss spectroscopy (EELS) dipole and impact scattering intensity has been measured. Spectra for a saturation coverage of H adsorbed on W(110) exhibit loss peaks due to impact scattering from adsorbate vibrational modes. The intensity of the 160 meV loss peak has been measured as a function of the azimuthal angle between the scattering plane and a mirror plane of the $\text{s}$urface. The angular pattern has strong maxima oriented perpendicular to the <111 > rows of atoms on the surface, and has the C_2v symmetry of the W(110) surface. This azimuthal dependence is strikingly different from the nearly isotropic angular dependence of dipole scattering from Cl adsorbed on W(110). Selection rules for impact scattering account for the general features of the angular pattern based on asymmetric stretch modes associated with bridge site H atoms.We have shown that the azimuthal dependence of the 36 meV Cl/W(110) dipole scattering loss peak is isotropic and that the 160 meV H/W(110) impact scattering loss peak exhibits a striking azimuthal pattern with C_2v symmetry. The symmetry and deep minima suggest that selection rules play a central role in determining the azimuthal pattern. Application of these rules to two orthogonal directions (as in ref. 6) may be misleading, as is clear from Fig. 2, because essential features of the pattern will not be observed. Our analysis of the full pattern has suggested two bridge sites may be occupied at saturation coverage, but has still not resolved certain questions about the H/W(110) system.

1. Impact scattering selection rules for potential adsorbate sites. The listed directions are the intersections of the planes with the (110) surface for the mirror planes and the scattering planes, and the displacement directions for the adsorbate vibrational modes. Modes are assumed to be strictly parallel to the surface. The long bridge site is between two W atoms along the <001 > direction, the short bridge site is between two W atoms along the <$\text{111}\text{-}$ > direction, and the distorted bridge site is displaced from the long bridge site along the <$\text{110}\text{-}$ > direction (ref. 6) The asterisks (*) denote that the scattering amplitude is zero for all directions in the scattering plane, otherwise it is zero only in the specular direction. The <$\text{110}\text{-}$ > mode of the distorted bridge is not covered by the selection rules of ref. 2.

     

20.

Synthesis and properties of a thermally stable methyltitanium(IV) compound: Cyclopentadienylmethyldichlorotitanium(IV)     

Gordon J. Erskine  Graham J.B. Hurst  Erica L. Weinberg  Brian K. Hunter  James D. McCowan 《Journal of organometallic chemistry》1984,267(3):265-269

η⁵C₅H₅Ti(CH₃)Cl₂ and η⁵-C₅H₅Ti(C₂H₅TiCl₂ have been synthesized. The reactivity of the methyl compound is much greater than that of the closely related sandwich compound, (η⁵-C₅H₅)₂Ti(CH₃)Cl, but the thermal stability is comparable.     

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SITE	LONG BRIDGE	SHORT BRIDGE	DISTORTED BRIDGE
MIRROR PLANES	[001], [1$\text{1}\text{-}$0]	NONE	[1$\text{1}\text{-}$0]
2-FOLD ABOUT Z	YES	YES	NO
PARALLEL MODES	[001]	[1$\text{1}\text{-}$0]	[1$\text{1}\text{-}$1]	[$\text{1}\text{-}$12]	[001]	[1$\text{1}\text{-}$0]
DIRECTIONS OF ZERO SCATTERING	[001] * [1$\text{1}\text{-}$0]	[001] * [1$\text{1}\text{-}$0]	[1$\text{1}\text{-}$1] [$\text{1}\text{-}$12]	[1$\text{1}\text{-}$1] [$\text{1}\text{-}$12]	[001] * [1$\text{1}\text{-}$0]	NA

Synthesis and properties of a thermally stable methyltitanium(IV) compound: Cyclopentadienylmethyldichlorotitanium(IV)

η⁵C₅H₅Ti(CH₃)Cl₂ and η⁵-C₅H₅Ti(C₂H₅TiCl₂ have been synthesized. The reactivity of the methyl compound is much greater than that of the closely related sandwich compound, (η⁵-C₅H₅)₂Ti(CH₃)Cl, but the thermal stability is comparable.