Cationic molybdenum oxo alkylidenes stabilized by N-heterocyclic carbenes: from molecular systems to efficient supported metathesis catalysts

Cationic d⁰ group 6 olefin metathesis catalysts have been recently shown to display in most instances superior activity in comparison to their neutral congeners. Furthermore, their catalytic performance is greatly improved upon immobilization on silica. In this context, we have developed the new family of molecular cationic molybdenum oxo alkylidene complexes stabilized by N-heterocyclic carbenes of the general formula [Mo(O)(CHCMe₃)(IMes)(OR)[X⁻]] (IMes = 1,3-dimesitylimidazol-2-ylidene; R = 1,3-dimesityl-C₆H₃, C₆F₅; X⁻ = B(3,5-(CF₃)₂C₆H₃)₄⁻, B(Ar^F)₄, tetrakis(perfluoro-t-butoxy)aluminate (PFTA)). Immobilization of [Mo(O)(CHCMe₃)(IMes)(O-1,3-dimesityl-C₆H₃)⁺B(Ar^F)₄⁻] on silica via surface organometallic chemistry yields an active alkene metathesis catalyst that shows the highest productivity towards terminal olefins amongst all existing molybdenum oxo alkylidene catalysts.

The first cationic molybdenum oxo complexes were synthesized and immobilized on partially dehydroxylated silica. Vastly enhanced catalytic activity for terminal olefins was found compared to their neutral congeners.     

De Novo Designed α-Helical Coiled-Coil Peptides as Scaffolds for Chemical Reactions

Coiled coils (CCs) are well-understood protein-folding motifs. They appear in a variety of oligomer states and as homo- and heteromeric assemblies. This versatility and the general accessibility by de novo design makes them ideal building blocks for synthetic biology. This Minireview highlights the efforts being made in designing small peptide catalysts or reaction templates based on the CC scaffold. The first reports described autocatalysis or mediation of peptide ligation based on CC recognition. Over the years, the designs became more advanced, catalyzing ester hydrolysis, acyl transfer and redox reactions with partial enzyme-like reactivity. Due to the ability to control CC assembly, and, in heterodimeric systems, the association and dissociation, the CC motif has become a common peptide tag in chemical biology.     

Three-stage melting of an annelide-type copper complex. A new type of organized phase: Tegma crystals

The solid—solid phase transition of an annlide type copper complex are described. As the temperature is raised, three different constituents of the complex successively melt. In the temperature range 77–95°C, the polyethylene oxide chains and the paraffinic tail are both in a very mobile state while the copper complex sub-units still form a two-dimensional crystalline array.     

Anionic polymerization with alkaline earth counterion. III. Aging of oligo- and polystyryl-barium and -strontium in THF

The self-deactivation of polystyryl-barium and polystyryl-strontium in tetrahydrofuran (THF) results essentially from protonation by the solvent. The deactivation constant k_d of this reaction is independent of carbanion concentration, length, and functionality of chains. Relations of k_d with temperature are: polystyryl-barium: k_d = 6.25 × 10⁷ exp(-18,900/RT) sec^?1; polystyryl-strontium: k_d = 4.1 × 10⁶ exp(?16,000/RT) sec^?1. The self-deactivation of α,ω-dicarbanionic oligostyryl-barium is a nonrandomlike reaction. Residual living oligomers are left dicarbanionic even if an important deactivation occurs.     

Study of complexes between lysozyme and sodium alkyl sulfates in the solid state

Complexes between lysozyme and sodium alkyl sulfates (decyl, dodecyl, tetradecyl and hexadecyl) in the solid state were prepared by mixing aqueous solutions of lysozyme and of the surfactant, separating the precipitated complex and purifying it. The stoichiometry of the complexes was investigated by elemental analysis and was found to correspond to about 8ǃ alkyl sulfate ions per lysozyme. Low- and wide-angle X-ray scattering were used to investigate the structure of the complexes. The scattering curves showed one fairly large scattering maximum, revealing a low state of organization of the complexes. The characteristic length characterizing the complexes was calculated from the value of the wave vector corresponding to the maximum of the scattered intensity. This length increased by about 0.233 nm per additional methylene group in the surfactant alkyl chain. A model where spherical aggregates of alkyl sulfate ions are arranged in a disordered simple cubic structure, dispersed in a matrix of lysozyme, provides a possible explanation of the results.