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 effect of construction material, contents and room geometry on the sound field in dwellings at low frequencies

An experimentally validated finite element method is used to model the sound level in rooms at low frequencies. It is demonstrated that the dimensions of rectangular rooms strongly influence the sound pressure level difference. Additional factors were investigated which are not normally considered in the frequency range where diffuse sound field conditions can be assumed. Three effects were investigated: room damping due to wall vibrations, furniture, the effect of small deviations from simple rectangular shapes. It is confirmed by field measurements that the vibrations of masonry walls and floors introduce less damping than surfaces of lightweight construction. Assigning to the FE model a damping equivalent to a surface absorption of 0.02 reproduces the effect of walls of heavyweight construction. Damping equivalent to a surface absorption of 0.15 reproduces the effects of plastered timber-frame walls, floors and ceilings. The work was briefly extended to a room pair built with heavyweight and lightweight material of construction. The modification of the shape of the room frequency response highlights well the effect of material of construction. In-situ and laboratory measurements show that furniture has little effect on steady-state room response below 100 Hz. Modelling a wall recess smaller than 0.5 m improved the agreement between prediction and measurements but the assumption of a simple rectangular room remains appropriate.     

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.     

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.     

Magnetisation reversal in media with perpendicular anisotropy

In this paper, we discuss two key aspects of magnetisation reversal in magnetic thin films with perpendicular anisotropy. Firstly, a study has been made of the additional field required to erase data written perpendicular to a thin film recording disk as the linear data density is increased. It has been found that an increase in data density from 40 to 360 kfci results in an increase of 1.25 kOe in the field required to erase the data. Secondly, the effect of varying the level of exchange coupling by co-sputtering CoCrPt samples with SiO₂ has been studied using a characterisation technique that is independent of the self-demagnetising field. It has been found that the samples are fully exchange de-coupled when the film contains >9.8% SiO₂ and the activation volume of reversal remains constant for higher levels of SiO₂.