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.     

Enzyme-Catalyzed Synthesis of O-Glycopeptide Building Blocks

Abstract

In 1988, MOSBACH et aL¹ reported the synthesis of a-D-mannopyranosy1-L-serine and Q -D-N-acetylgalactosamino-L-serine by reversing the hydrolytic activity of a -mannosidase from jack beans and a -N-acetylgalactosaminidase from beef liver, respectively. The yields in these equilibrium-controlled syntheses² using high concentrations of monosaccharide and serine were highly dependent on the enzyme concentration and ranged from 5 to 10 percent in both cases.     

Eigenvalues of a statistical mechanics matrix

We consider the problem of finding the spectrum of an n × n matrix which arises in the study of a certain model of long-range interactions in a one-dimensional statistical mechanics system. Our analysis exhibits a curious resemblance of the suitably normalized distribution of eigenvalues to the Marčenko–Pastur law in the limit n → ∞.     

Time-resolved vibrational spectroscopy

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Time-resolved vibrational spectroscopy     

On the theory of collective motion in nuclei. III. From Hamiltonian dynamics to vortex-free fluidity

It is assumed that the Hamiltonian for collective motion in nuclei is invariant under the orthogonal group O(n, $\text{R}$). For degenerate orbits in phase space it is shown that the classical Hamiltonian equations reduce to the equations of a vortex-free fluid with a velocity field determined by independent equations of motion.     

Control of continuous sedimentation of ideal suspensions as an initial and boundary value problem

We present the control of continuous sedimentation in an ideal thickener as an initial and boundary value problem and construct the entropy solution.     

Induced product representations of extended Cuntz algebras

Let _H be the extended Cuntz algebra over the Hilbert space H. Since its zero grade part _H⁰ is the C^*-inductive limit of B(H^r), we look for some family of representations on an inductive limit of H^r as r. When such construction is shaped according to the structure of _H⁰, von Neumanns notion of a reference sequence of unit vectors for Hilbert infinite tensor products emerges; after a further Rieffel induction step, a class IPR[H] of representations of _H arises. For any two such representations, we describe explicitly their associated intertwiners. Any two representations in IPR[H] are either disjoint or unitarily equivalent. Actions of the group by translation on sequences of unit vectors are involved, as well as the ideals of .