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21.
22.
The photochemistry of 13 4,4-diphenylcyclohexenones, substituted at carbon-6, was investigated in solution and in the crystalline state. The stereoselectivity was of particular interest. In the solution photochemistry of C-6 monosubstituted enones in benzene, there was a unique preference for migration of the cis-phenyl group with formation of bicyclo[3.1.0]hexanone photoproducts, with the original 6-substituent having an endo configuration at carbon-3 of the product. In methanol the reaction was diverted to afford 3,4-diphenylcyclohex-2-enes understood as arising from a hydrogen-bonded zwitterionic intermediate. The solid-state photochemistry was also investigated. There was a dramatic absence of the 3,4-diphenylcyclohex-2-ene products in accord with the absence of the hydrogen bonding encountered in methanol. Further, the solid-state reactivity correlated with a vector analysis using X-ray atomic coordinates. This established that the migrating phenyl group required an orientation facing the enone beta-carbon. While the interesting preference for the cis-endo migration was not intuitively predicted, ab initio computations on the alternative phenyl-bridged triplet intermediates did lead to an understanding of the selectivity. 相似文献
23.
Briggs CR Allen MJ O'Hagan D Tozer DJ Slawin AM Goeta AE Howard JA 《Organic & biomolecular chemistry》2004,2(5):732-740
The energies of the gauche and anti conformers of 2-fluoroethylamine, 2-fluoroethanol and their protonated analogues are calculated using density functional theory. Unlike the non protonated systems, the protonated systems show a strong gauche effect where the C-F and the C-(+)NH(3) or C-F and C-(+)OH(2) bonds are gauche rather than anti to each other. Single crystal X-ray diffraction studies of 2-fluoroethylammonium compounds identify the same conformational preference. 相似文献
24.
Akutsu H Akutsu-Sato A Turner SS Le Pevelen D Day P Laukhin V Klehe AK Singleton J Tocher DA Probert MR Howard JA 《Journal of the American Chemical Society》2002,124(42):12430-12431
Normal state conductivity and superconductivity together with bulk magnetic susceptibility and magnetization measurements have been measured for two molecular charge-transfer salts: beta' '-(ET)4[(H3O)Ga(C2O4)3]G (ET = bis(ethylenedithio)tetrathiafulvalene, G = pyridine for compound I and nitrobenzene for compound II). With the exception of the included guest molecules (G) the crystal structures are almost identical. Both show minima in their electrical transport at 130 K for I and at 160 K for II, but at lower temperatures their behaviors differ markedly. The resistance of I reaches a maximum at 50 K with a further small peak at 2 K and possible superconductivity only below 2 K, whereas that of II increases continuously down to 7.5 K, where an abrupt transition to a superconducting state occurs. 相似文献
25.
S. T. Howard J. P. Huke I. W. Parsons S. J. Till 《International journal of quantum chemistry》1991,39(1):71-91
The usefulness of the MS -Xα method for calculating molecular transition properties is investigated in a study of NO2. Two-dimensional potential surfaces are obtained in C2v symmetry for the X?2A1/Ã2B2 system. Potential curves that approximately follow the asymmetric stretch coordinate are also presented: On investigation, no symmetry-broken solutions were found. At all nuclear geometries investigated, the muffin-tin sphere radii were chosen by an energy-minimization technique. The inclusion of corrections to the muffin-tin form of the Xα total energy is shown to be essential, if the computed surfaces are to be qualitatively correct. The transition dipole moment connecting the two states is evaluated as a function of nuclear coordinates, using the transition-state approximation. Finally, the radiative decay of a single vibronic level in NO2 is modeled and the relevance to experiment is discussed. 相似文献
26.
27.
Inorganic oxide core, polymer shell nanocomposite as a high K gate dielectric for flexible electronics applications 总被引:1,自引:0,他引:1
Maliakal A Katz H Cotts PM Subramoney S Mirau P 《Journal of the American Chemical Society》2005,127(42):14655-14662
Organic/inorganic core shell nanoparticles have been synthesized using high K TiO(2) as the core nanoparticle, and polystyrene as the shell. This material is easy to process and forms transparent continuous thin films, which exhibit a dielectric constant enhancement of over 3 times that of bulk polystyrene. This new dielectric material has been incorporated into capacitors and thin film transistors (TFTs). Mobilities approaching 0.2 cm(2)/V.s have been measured for pentacene TFTs incorporating the new TiO(2) polystyrene nanostructured gate dielectric, indicating good surface properties for pentacene film growth. This novel strategy for generating high K flexible gate dielectrics will be of value in improving organic and flexible electronic device performance. 相似文献
28.
Howard M. Colquhoun 《Transition Metal Chemistry》1981,6(1):57-59
Summary Ligating dinitrogen, in the complexes,trans-M(N2)2(Ph2PCH2CH2PPh2)2 (where M=Mo or W) may be acylated by trifluoroacetic anhydride, to give trifluoroacetyldiazenido complexes in high yield. Unlike corresponding reactions with acyl halides, trifluoroacetylation proceeds under nonradical conditions, and a mechanism analogous to that of protonation is suggested.Dinitrogen-derived ligands may also be acylated by (CF3CO)2O, so that the methyldiazenido ligand is converted into a methyl (trifluoroacetyl) hydrazido (2-) ligand, and the acetyldiazenido ligand undergoes transacylation to give a trifluoroacetyl diazenido derivative.New complexes were characterised by i.r.,19F and1H n.m.r. spectra, and by elemental analysis.Part 1 is ref. 10 相似文献
29.
Martin R. Bryce Peter J. Skabara Adrian J. Moore Andrei S. Batsanov Judith A.K. Howard Vanessa J. Hoy 《Tetrahedron》1997,53(52):1002-17794
Reactions of tetrathiafulvalenyllithium (TTF-Li) with a range of aldehydes and ketones have been explored for the first time, to provide an efficient route to mono-functionalised TTF derivatives of general formulae TTF-CH(OH)R (R = alkyl, phenyl, tetrathiafulvalenyl and ferrocenyl) and TTF-CR(OH)R′ (R = alkyl, phenyl, R′ = alkyl, phenyl, tetrathiafulvalenyl, ferrocenyl, and R-R′ = fluorenyl). Subsequent transformations involving the reactive alcohol group of some of these compounds are reported. The structures of the three title compounds have been established by single-crystal X-ray analysis. 相似文献
30.
Howard C. Clark Anil B. Goel Chun S. Wong 《Journal of organometallic chemistry》1980,190(4):C101-C104
Simple synthetic routes to the mixed ligand complexes PtLL'X2 and PtLL'XY (L' = PEt3; L = phosphine, arsine, etc.; X = Cl and Y = Cl, H or Me) are described; unexpectedly, these display an extensive chemistry without disproportionation, although in some cases ligand scrambling does occur. 相似文献