Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

On the spectral norm of algebraic numbers

In this paper we continue to study the spectral norms and their completions ([4]) in the case of the algebraic closure $ \overline {\mathbb Q} $ of ? in ?. Let $ \widetilde{\overline{\mathbb{Q}}} $ be the completion of $ \overline {\mathbb Q} $ relative to the spectral norm. We prove that $ \widetilde{\overline{\mathbb{Q}}} $ can be identified with the R‐subalgebra of all symmetric functions of C(G), where C(G) denotes the ?‐Banach algebra of all continuous functions defined on the absolute Galois group G = Gal$ {\overline {\mathbb Q}} / {\mathbb Q} $. We prove that any compact, closed to conjugation subset of ? is the pseudo‐orbit of a suitable element of $ \widetilde{\overline{\mathbb{Q}}} $. We also prove that the topological closure of any algebraic number field in $ \widetilde{\overline{\mathbb{Q}}} $ is of the form $\widetilde{\mathbb{Q}[x]}$ with x in $ \widetilde{\overline{\mathbb{Q}}} $.     

Variations of constants and red-shift in 6D cosmology

On the basis of the general class of solutions of 6D vacuum Einstein equations and using well-known results of the 6D geometric model of electroweak and gravitational interactions, the variations of fundamental physical constants and their influence on the observed red-shift of galaxies are investigated. By considering the interpretation of extra components of the 6D metric as reproducing the properties of matter in the 4D curved space-time, the effective quantities of matter are obtained. In particular, the states of dust and radiation are shown. The corresponding 5D models were also investigated.     

Extreme behavior of bivariate elliptical distributions

This paper exploits a stochastic representation of bivariate elliptical distributions in order to obtain asymptotic results which are determined by the tail behavior of the generator. Under certain specified assumptions, we present the limiting distribution of componentwise maxima, the limiting upper copula, and a bivariate version of the classical peaks over threshold result.     

New vertex invariants and topological indices of chemical graphs based on information on distances

By applying information theory to the set of topological distances from one vertex to all other graph vertices, one obtains four new types of vertex invariants (u _i,v _i,x _i,Y _i) which are real numbers (as opposed to integers). They may be combined in many ways to afford new topological indices. One such type leads to indicesU, V, X andY which show no degeneracy for alkanes with up to 15 vertices.     

Hardy type inequalities with exponential weights for a class of convolution operators

In this paper we consider operators of the form H=λ(-i∇), with λ analytic in a strip and with some specific growth conditions at infinity, and prove Hardy type estimates in L ²(ℝ ⁿ ) with exponential weights. In fact we extend our previous results [19] from bounded analytic functions on a strip to analytic functions with polynomial growth in that strip.     

A result on sets,with applications to vector optimization

In this paper there is stated a result on sets in ordered linear spaces which can be used to show that some properties of the sets are inherited by their convex hulls under suitable conditions. As applications one gives a characterization of weakly efficient points and a duality result for nonconvex vector optimization problems.