Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

The push-out region of an immersed manifold

We consider immersions: and construct a subspace of which corresponds to a set of embedded manifolds which are either parallel to f, tubes around f or, in general, partial tubes around f. This space is invariant under the action of the normal holonomy group, We investigate the case where is non-trivial and obtain some results on the number of connected components of . Received 24 March 2000.     

Covariant Newtonian and relativistic dynamics of (magneto)-elastic solid model for neutron star crust

This work develops the dynamics of a perfectly elastic solid model for application to the outer crust of a magnetised neutron star. Particular attention is given to the Noether identities responsible for energy-momentum conservation, using a formulation that is fully covariant, not only (as is usual) in a fully relativistic treatment but also (sacrificing accuracy and elegance for economy of degrees of gravitational freedom) in the technically more complicated case of the Newtonian limit. The results are used to obtain explicit (relativistic and Newtonian) formulae for the propagation speeds of generalised (Alfven type) magneto-elastic perturbation modes.     

Catalytic air oxidation of ambient temperature hydrocarbons

Catalytic air oxidation of the aliphatic hydrocarbons n-decane, hexanes, gasoline and diesel fuel was conducted at ambient temperature with novel iron catalysts. The concentration of n-decane in water was reduced from 1.42 g in 100 ml to 0.07 g in 100 ml in 5 h at room temperature forming carbon monoxide and water by means of intermediate aldehydes. Results of FT–IR and GC–MS analyses demonstrated formation of aldehydes and unsaturated alcohols. Carbon monoxide was detected on catalyst residues and in the vapor phase. The indicated catalytic reaction mechanisms are discussed.     

Castelnuovo-Mumford regularity by approximation

The Castelnuovo-Mumford regularity of a module gives a rough measure of its complexity. We bound the regularity of a module given a system of approximating modules whose regularities are known. Such approximations can arise naturally for modules constructed by inductive combinatorial means. We apply these methods to bound the regularity of ideals constructed as combinations of linear ideals and the module of derivations of a hyperplane arrangement as well as to give degree bounds for invariants of finite groups.     

Quasioptical Approach for Meniscus Lens Corrected Horn: Application to Cassegrain Systems

The Beam Mode Expansion (BME) approach for corrugated conical feed horn plus meniscus lens is presented. This approach is useful for providing the radiation pattern as it propagates through an optical system. A developed theoretical model has been verified measuring near and far field of a built horn and lens. These results have been used for designing the optical system of a Cassegrain antenna at 100GHz using the fundamental Gaussian beam mode (GBM) of the new approach. Multimode analysis has been performed with the pre-designed system in order to test the fundamental GBM results.     

An anisotropic fibre-network model for mechano-sorptive creep in paper

In this paper a simplified network model for mechano-sorptive creep is presented, which is a further development of an earlier paper [Strömbro, J., Gudmundson, P., 2008. Mechano-sorptive creep under compressive loading – a micromechanical model. International Journal of Solids and Structures 45 (9), 2420–2450.]. It is assumed that the anisotropic hygroexpansion of the fibres leads to large stresses at the fibre bonds when the moisture content changes. The resulting stress state will accelerate creep if the fibre material obeys a constitutive law that is non-linear. Fibre kinks are included in order to capture experimental observations of larger mechano-sorptive effects in compression than in tension. Moisture dependent material parameters and anisotropy in the fibre distribution have been introduced. Theoretical predictions based on the model are compared to experimental results for an anisotropic paper both under tensile and compressive loading at varying moisture content and it is found that the important features in the experiments are captured by the model. Different kinds of drying conditions have also been examined.     

On-line nuclear orientation study of184Au

The¹⁸⁴Au→¹⁸⁴Pt decay, studied on-line with the UNISOR facility at HHIRF, is discussed. Gamma-ray and conversion-electron spectroscopy of¹⁸⁴Pt as well as on-line nuclear orientation measurements of¹⁸⁴Au were done. A new low-lying level scheme of¹⁸⁴Pt is proposed. Two coexisting bands with different deformations and their respective γ-vibrational bands are established. Internal conversion coefficients for interband transitions between states with the same spin are extracted from the spectroscopy measurements. The relative E0 contents of the transitions are determined by combining internal conversion coefficients with E2/M1 mixing ratios deduced from gamma-ray anisotropies measured from oriented nuclei.