Organocatalyzed Phospha-Michael Addition: A Highly Efficient Synthesis of Customized Bis(acyl)phosphane Oxide Photoinitiators

Addition of the P−H bond in bis(mesitoyl)phosphine, HP(COMes)₂ (BAPH), to a wide variety of activated carbon–carbon double bonds as acceptors was investigated. While this phospha-Michael addition does not proceed in the absence of an additive or catalyst, excellent results were obtained with stoichiometric basic potassium or caesium salts. Simple amine bases can be employed in catalytic amounts, and tetramethylguanidine (TMG) in particular is an outstanding catalyst that allows the preparation of bis(acyl)phosphines, R−P(COMes)₂, under very mild conditions in excellent yields after only a short time. All phosphines RP(COMes)₂ can subsequently be oxidized to the corresponding bis(acyl)phosphane oxides, RPO(COMes)₂, a substance class belonging to the most potent photoinitiators for radical polymerizations known to date. Thus, a simple and highly atom economic method has been found that allows the preparation of a broad range of photoinitiators adapted to their specific field of application even on a large scale.     

Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation

The rapidly growing interest for new heterogeneous catalytic systems providing high atomic efficiency along with high stability and reactivity triggered an impressive progress in the field of single-atom catalysis. Nevertheless, unravelling the factors governing the interaction strength between the support and the adsorbed metal atoms remains a major challenge. Based on periodic density functional theory (DFT) calculations, this paper provides insight into the adsorption of single late transition metals on a defect-free anatase surface. The obtained adsorption energies fluctuate, with the exception of Pd, between −3.11 and −3.80 eV and are indicative of a strong interaction. Depending on the considered transition metal, we could attribute the strength of this interaction with the support to i) an electron transfer towards anatase (Ru, Rh, Ni), ii) s-d orbital hybridisation effects (Pt), or iii) a synergistic effect between both factors (Fe, Co, Os, Ir). The driving forces behind the adsorption were also found to be strongly related to Klechkowsky's rule for orbital filling. In contrast, the deviating behaviour of Pd is most likely associated with the lower dissociation enthalpy of the Pd−O bond. Additionally, the reactivity of these systems was evaluated using the Fermi weighted density of states approach. The resulting softness values can be clearly related to the electron configuration of the catalytic systems as well as with the net charge on the transition metal. Finally, these indices were used to construct a model that predicts the adsorption strength of CO on these anatase-supported d-metal atoms. The values obtained from this regression model show, within a 95 % probability interval, a correlation of 84 % with the explicitly calculated CO adsorption energies.     

Local and non‐local ductile damage and failure modelling at large deformation with applications to engineering

The numerical analysis of ductile damage and failure in engineering materials is often based on the micromechanical model of Gurson [1]. Numerical studies in the context of the finite‐element method demonstrate that, as with other such types of local damage models, the numerical simulation of the initiation and propagation of damage zones is strongly mesh‐dependent and thus unreliable. The numerical problems concern the global load‐displacement response as well as the onset, size and orientation of damage zones. From a mathematical point of view, this problem is caused by the loss of ellipticity of the set of partial di.erential equations determining the (rate of) deformation field. One possible way to overcome these problems with and shortcomings of the local modelling is the application of so‐called non‐local damage models. In particular, these are based on the introduction of a gradient type evolution equation of the damage variable regarding the spatial distribution of damage. In this work, we investigate the (material) stability behaviour of local Gurson‐based damage modelling and a gradient‐extension of this modelling at large deformation in order to be able to model the width and other physical aspects of the localization of the damage and failure process in metallic materials.     

Slow Inversion of Coordinated Thioether Groups in SNS-Type Ruthenium Pincer Complexes

The thioether-group-containing SNS-type pincer complex [({EtSCH₂CH₂}₂NH)RuCl(H)(PPh₃)] ( 2 ) exists in three different diastereomers ( 2 a – c ). The molecular structures obtained from single crystal X-Ray diffraction studies of all three isomers reveal a difference in the relative orientation of the respective EtS-groups, while other commonly observed diastereomers as the result of cis-/trans- or fac-/mer-isomerism are not observed. Chemical exchange between the three diastereomers 2 a – c was discovered by phase-sensitive ¹H and ³¹P NOESY NMR spectroscopy, and further quantified by line shape analysis of ¹H NMR spectra. The experimentally derived averaged Gibbs energies of activation for the interconversion of the isomers (65–70 kJ/mol) are in good agreement with the results obtained from DFT calculations, which suggest an inversion of the ligating sulfur atoms, although a dissociative pathway for the configurational inversion can be competitive.     

ChemInform Abstract: The Extended Stability Range of Phosphorus Allotropes.

A complete stability range of known and new crystalline allotropes of phosphorus including recently discovered tubular modifications and not‐yet‐known crystal structures of [P₁₂] nanorods, and not‐yet‐isolated [P₁₄] nanorods is given using quantum chemical DFT calculations.