Synthesis of new iron–NHC complexes as catalysts for hydrosilylation reactions

A series of new piano‐stool iron(II) complexes comprising N‐heterocyclic carbene ligands [Fe(Cp)(CO)₂(NHC)]I (NHC = 1,3‐disubstituted imidazolidin‐2‐ylidene) have been synthesized and analyzed by ¹H NMR, ¹³C NMR, IR, elemental analysis and mass spectrometric techniques. These compounds were easily prepared from the reaction of disubstituted imidazolidin‐2‐ylidene with [FeI(Cp)(CO)₂] in toluene at room temperature. These complexes were tested in the catalytic hydrosilylation reaction of aldehydes and ketones with phenylsilane in solvent‐free conditions. After a basic hydrolysis step, the corresponding alcohols were obtained in good yields. Copyright © 2013 John Wiley & Sons, Ltd.     

Electronic Structure and Magnetic Anisotropy of an Unsaturated Cyclopentadienyl Iron(I) Complex with 15 Valence Electrons

The 15 valence-electron iron(I) complex [Cp^ArFe(IiPr₂Me₂)] ( 1 , Cp^Ar=C₅(C₆H₄-4-Et)₅; IiPr₂Me₂=1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene) was synthesized in high yield from the Fe^II precursor [Cp^ArFe(μ-Br)]₂. ⁵⁷Fe Mössbauer and EPR spectroscopic data, magnetic measurements, and ab initio ligand-field calculations indicate an S= 3/2 ground state with a large negative zero-field splitting. As a consequence, 1 features magnetic anisotropy with an effective spin-reversal barrier of U_eff=64 cm⁻¹. Moreover, 1 catalyzes the dehydrogenation of N,N-dimethylamine–borane, affording tetramethyl-1,3-diaza-2,4-diboretane under mild conditions.     

Combination of nitroxide‐mediated polymerization and SET‐LRP for the synthesis of high molar mass branched and star‐branched poly(n‐butyl acrylate) characterized by size exclusion chromatography and rheology

Branched and star‐branched polymers were successfully synthesized by the combination of two successive controlled radical polymerization methods. A series of linear and star poly(n‐butyl acrylate)‐co‐poly(2‐(2‐bromoisobutyryloxy) ethyl acrylate) statistical copolymers, P(nBA‐co‐BIEA)_x, were first synthesized by nitroxide‐mediated polymerization (NMP at T > 100 °C). The subsequent polymerization of n‐butyl acrylate by single electron transfer‐living radical polymerization (SET‐LRP at T = 25 °C), initiated from the brominated sites of the P(nBA‐co‐BIEA)_x copolymer, produced branched or star‐branched poly(n‐butyl acrylate) (PnBA). Both types of polymerizations (NMP and SET‐LRP) exhibited features of a controlled polymerization with linear evolutions of logarithmic conversion versus time and number‐average molar masses versus conversion for final M_n superior to 80,000 g mol^?1. The branched and star‐branched architectures with high molar mass and low number of branches were fully characterized by size exclusion chromatography. The Mark–Houwink Sakurada relationship and the analysis of the contraction factor (g′ = ([η]_branched/[η]_linear)_M) confirmed the elaboration of complex PnBA. The zero‐shear viscosities of the linear, star‐shaped, branched, and star‐branched polymers were compared. The modeling of the rheological properties confirmed the synthesis of the branched architectures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Origin of the Enantioselectivity in Organocatalytic Michael Additions of β‐Ketoamides to α,β‐Unsaturated Carbonyls: A Combined Experimental,Spectroscopic and Theoretical Study

The organocatalytic enantioselective conjugate addition of secondary β‐ketoamides to α,β‐unsaturated carbonyl compounds is reported. Use of bifunctional Takemoto’s thiourea catalyst allows enantiocontrol of the reaction leading either to simple Michael adducts or spirocyclic aminals in up to 99 % ee. The origin of the enantioselectivity has been rationalised based on combined DFT calculations and kinetic analysis. This study provides a deeper understanding of the reaction mechanism, which involves a predominant role of the secondary amide proton, and clarifies the complex interactions occurring between substrates and the catalyst.     

Unsteady rheometry: can we characterize weak gels with a controlled stress rheometer?

This paper is concerned with the influence of apparatus inertia effects in controlled stress rheometry. As evidenced on creep experiments, the coexistence of apparatus inertia and viscoelasticity leads to a coupling frequency. For weak gels, this coupling frequency is typically between 1 and 100 Hz. Therefore, frequency sweeps around and above this coupling frequency also corresponds to an effective shear stress sweep evolution due to a non-trivial resonant effect. In other words, frequency sweep experiments are not made at constant shear stress. The detailed modelling and analysis of this inertia effect on a typical weak gel shows a clear and fundamental limitation for its characterization using a controlled stress rheometer. Also, alternative approaches to standard rheometer software analysis are proposed to take this coupling effect into account. This paper was presented at the 3rd Annual Rheology Conference, AERC 2006, April 27-29, 2006, Crete, Greece.     

Two-dimensional motion of a set of particles in a free surface flow with image processing

A method to analyze bed load with image processing was developed. The motion of coarse spherical particles on a mobile bed entrained by a shallow turbulent flow down a steep channel was filmed with a high-speed camera. The water free surface and the particle positions were detected combining classical image processing algorithms. We developed a particle-tracking algorithm to calculate all particle trajectories and motion regimes, rolling or saltation. At constant slope, the contribution of the rolling particles to the solid discharge only slightly differed when the particle supply was increased. At a slope of 10%, it represented about 40%. In contrast, rolling became the major regime when the slope increased, at a slope of 15% it represented up to 80% of the total solid discharge.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Mortar physical properties evolution in extrusion flow

Extrusion is not a common way to form firm cement-based material. Due to material frictional behaviour, drainage phenomenon appears and leads to process blockage. The properties of the extrusion multiphase flow of such specific materials have to be highlighted to understand the properties of the process flow. An extrudible mortar is formulated according to extrusion criteria provided by literature tests developed to describe the evolution of the paste undergoing extrusion. To study the relationship between flow properties, extrusion force and material consolidation, a technique based on the measurement of paste hardness in the billet zone is developed. Measurements of the local paste density and flow visualisation are also performed. Results show that in the range of used ram velocities, filtration occurs between fluid and solid phases. This creates zones of preferential flow and of non-flowing consolidated material. Paper presented at the 3rd Annual European Rheology Conference held on April 27–29, 2006, Crete, Greece.