184 research outputs found
The role of substituents in retro Diels-Alder extrusion of CO2 from 2(H)-pyrone cycloadducts
YesAn experimental and computational investigation is conducted into the role of substituents in retro Diels-Alder extrusion of CO2 from 2-oxa-bicyclo[2.2.2]oct-5-en-3-ones. We provide the first experimental evidence that loss of CO2 from the cycloadducts significantly depends on the nature and position of the substituents. For example, we show that whilst 5-carboethoxy-2-pyrone undergoes a more facile cycloaddition that 3-carboethoxy-2-pyrone, the cycloadduct from the latter pyrone undergoes a more facile loss of CO2 than the cycloadduct from the former pyrone.EPSRC, Yorkshire Cancer Research, Yorkshire Enterprise Fellowship
Research Data Management 'Green Shoots' Pilot Programme, Final Reports
This document contains the final reports of six Research Data Management Green Shoots projects run at Imperial College in 2014
Special electronic structures and quantum conduction of B/P co-doping carbon nanotubes under electric field using the first principle
Boron (B)/phosphorus (P) doped single wall carbon nanotubes (B-PSWNTs) are
studied by using the First- Principle method based on density function theory
(DFT). Mayer bond order, band structure, electrons density and density of
states are calculated. It concludes that the B-PSWNTs have special band
structure which is quite different from BN nanotubes, and that metallic carbon
nanotubes will be converted to semiconductor due to boron/phosphorus co-doping
which breaks the symmetrical structure. The bonding forms in B-PSWNTs are
investigated in detail. Besides, Mulliken charge population and the quantum
conductance are also calculated to study the quantum transport characteristics
of B-PSWNT hetero-junction. It is found that the position of p-n junction in
this hetero-junction will be changed as the applied electric field increase and
it performs the characteristics of diode.Comment: 11 pages, 6 fiugres, 2 table
Predictions of total and total reaction cross sections for nucleon-nucleus scattering up to 300 MeV
Total reaction cross sections are predicted for nucleons scattering from various nuclei. Projectile energies to 300 MeV are considered. So also are mass variations of those cross sections at selected energies. All predictions have been obtained from coordinate space optical potentials formed by full folding effective two-nucleon (NN) interactions with one body density matrix elements (OBDME) of the nuclear ground states. Good comparisons with data result when effective NN interactions defined by medium modification of free NN t matrices are used. Coupled with analyses of differential cross sections, these results are sensitive to details of the model ground states used to describe nuclei
Nature of the bonding in metal-silane σ-complexes
The nature of metal silane σ-bond interaction has been investigated in several key systems by a range of experimental and computational techniques. The structure of [Cp′Mn(CO)2(η2-HSiHPh2)] 1 has been determined by single crystal neutron diffraction, and the geometry at the Si atom is shown to approximate a trigonal bipyramid; salient bond distances and angles are Mn−H(1) 1.575(14), Si−H(1) 1.806(14), Si−H(2) 1.501(13) Å, and H(1)−Si−H(2) 148.5(8)°. This complex is similar to [Cp′Mn(CO)2(η2-HSiFPh2)] 2, whose structure and bonding characteristics have recently been determined by charge density studies based on high-resolution X-ray and neutron diffraction data. The geometry at the Si atom in these σ-bond complexes is compared with that in other systems containing hypercoordinate silicon. The Mn−H distances for 1 and 2 in solution have been estimated using NMR T1 relaxation measurements, giving a value of 1.56(3) Å in each case, in excellent agreement with the distances deduced from neutron diffraction. Density functional theory calculations have been employed to explore the bonding in the Mn−H−Si unit in 1 and 2 and in the related system [Cp′Mn(CO)2(η2-HSiCl3)] 3. These studies support the idea that the oxidative addition of a silane ligand to a transition metal center may be described as an asymmetric process in which the Mn−H bond is formed at an early stage, while both the establishment of the Mn−Si bond and also the activation of the η2-coordinated Si−H moiety are controlled by the extent of Mn → σ*(X−Si−H) back-donation, which increases with increasing electron-withdrawing character of the X substituent trans to the metal-coordinated Si−H bond. This delocalized molecular orbital (MO) approach is complemented and supported by combined experimental and theoretical charge density studies: the source function S(r,Ω), which provides a measure of the relative importance of each atom’s contribution to the density at a specific reference point r, clearly shows that all three atoms of the Mn(η2-SiH) moiety contribute to a very similar extent to the density at the Mn−Si bond critical point, in pleasing agreement with the MO model. Hence, we advance a consistent and unifying concept which accounts for the degree of Si−H activation in these silane σ-bond complexes
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