Aza-substitution,benzo-annulation effects and catalytic activity of <Emphasis Type="Italic">β</Emphasis>-octaphenyl-substituted tetrapyrrolic macroheterocyclic cobalt complexes. I. heterogeneous catalysis

The influence of the size of conjugated π-system on catalytic activity of cobalt complex with β-octaphenylporphyrin and its tetraaza-, tetrabenzo and tetrabenzotetraaza derivatives was studied in present work. It is found that catalytic activity for oxidation of sulfur-containing compounds increases under extension of conjugated macrocycle system according to the following series CoP < CoBP ≤ CoPz < CoPPz ? CoPc.     

Oxidation of bridging groups by carboxylate coordinated ligands in palladium clusters

Thermolysis of tetranuclear palladium clusters Pd₄(-Q)₄ Pd₄(-Q)₄(-O₂CR)₄ (Q=CPh₂ or CO;R=Me, CMe₃, Ph, CH₂Cl or CF₃) has been found to involve innersphere oxidation of carbene or carbonyl ligands during which an oxygen atom transfer occurs from the carboxylate group to the carbene or carbonyl ligand. The thermolysis of the carbonyl clusters gives rise to the products of CO₂ insertion into the C–H bond of benzene or toluene used as solvents forming benzoic acid from benzene and a mixture of phenylacetic and toluic acids from toluene. The reaction of [Pd(OAc)₂(PPh₃)]₂ with HCO₂H includes the transfer of an O atom from formate ligand to the P atom and cleavage of the P-Ph bond accompanied by transfer of the Ph group from PPh₃ ligand to the palladium atom. The structure of the complex formed, [Pd(-O₂PPh₂)(C₆H₅)(PPh₃)]₂, has been resolved by X-ray analysis.     

Modeling of Solute-Solvent Interactions Using an External Electric Field—From Tautomeric Equilibrium in Nonpolar Solvents to the Dissociation of Alkali Metal Halides

An implicit account of the solvent effect can be carried out using traditional static quantum chemistry calculations by applying an external electric field to the studied molecular system. This approach allows one to distinguish between the effects of the macroscopic reaction field of the solvent and specific solute–solvent interactions. In this study, we report on the dependence of the simulation results on the use of the polarizable continuum approximation and on the importance of the solvent effect in nonpolar solvents. The latter was demonstrated using experimental data on tautomeric equilibria between the pyridone and hydroxypyridine forms of 2,6-di-tert-butyl-4-hydroxy-pyridine in cyclohexane and chloroform.     

1,3,5-Triaza-7-Phosphaadamantane (PTA) as a 31P NMR Probe for Organometallic Transition Metal Complexes in Solution

Due to the rigid structure of 1,3,5-triaza-7-phosphaadamantane (PTA), its ³¹P chemical shift solely depends on non-covalent interactions in which the molecule is involved. The maximum range of change caused by the most common of these, hydrogen bonding, is only 6 ppm, because the active site is one of the PTA nitrogen atoms. In contrast, when the PTA phosphorus atom is coordinated to a metal, the range of change exceeds 100 ppm. This feature can be used to support or reject specific structural models of organometallic transition metal complexes in solution by comparing the experimental and Density Functional Theory (DFT) calculated values of this ³¹P chemical shift. This approach has been tested on a variety of the metals of groups 8–12 and molecular structures. General recommendations for appropriate basis sets are reported.     

Monitoring and Statistical Analysis of Formation of Organochlorine and Organobromine Compounds in Drinking Water of Different Water Intakes

The main drawback of drinking water chlorination involves the formation of quite hazardous disinfection by-products (DBPs), represented mainly by halogenated species. Based on the authors’ monitoring data since 2002, the prevalence of chlorine over bromine in the composition of volatile DBPs was shown for the drinking water in Ufa (Russia). However, the situation was completely reversed in the case of semi-volatile DBPs. The principal goal of the present study involved rationalization of the results of the long-term monitoring. Gas chromatography–mass spectrometry (GC-MS) was used for the qualitative and quantitative analysis of volatile DBPs. Identification of semi-volatile compounds was carried out with GC-MS, while gas chromatography with an atomic emission detector (GC-AED) was used for their quantification. A significant contribution of oxygen to the composition of semi-volatile compounds proves the decisive role of the dissolved organic matter oxidative destructive processes. Statistical analysis revealed notable linear correlations for trihalomethane and haloacetic acid formation vs. chlorine dose. On the contrary, halogenated semi-volatile products do not demonstrate any correlations with the water quality parameters or chlorine dose. Principal component analysis (PCA) placed them into separate groups. The results allow for proposing that formation of the organohalogenated species involved the fast penetration of bromine into the humic matter molecules and, further, their oxidative destruction by active chlorine.     

Are there reliable DFT approaches for 13C NMR chemical shift predictions of fullerene C60 derivatives?

The relationships between experimental and theoretical ¹³C NMR chemical shifts of a pristine fullerene C₆₀, monoadducts from [2 + n] cycloaddition (n = 1–3), and one [2 + 1] bis‐adduct are systematically analyzed for the first time by using diverse quantum‐chemical levels of theory. These levels involved B3LYP, B3PW91, B97‐2, mPW1PW91, PBE1PBE, and X3LYP hybrid functionals combined with 3‐21G, 6‐31G, 6‐31G(d), 6‐31G(d,p), 6‐31G(d,2p), LanL2DZ, and SDDAll basis sets. X3LYP/6‐31G approach is determined to have the lowest deviations from the ¹³C NMR experimental data compared to the other methods for all the fullerene compounds (mean absolute error value is 0.856 ppm and root mean squared error value is 1.197 ppm). The highest deviations are characteristic for α (sp² C2/C5/C8/C10) and β (sp² C6/C7/C11/C12) carbon atoms relative to a functionalization site and for those (sp³ C1/C9) directly attached with a side fragment in the [2 + n] monoadducts (n = 1–3). A probable reason of such deviation is that the approaches do not take into account a contribution of paramagnetic ring currents to ¹³C NMR chemical shifts. The results will be useful in design of novel fullerene derivatives and in performing unambiguous ¹³C NMR chemical shift assignments with modern quantum chemistry calculations.     

Subset currents on free groups

We introduce and study the space ${{\mathcal{S}{\rm Curr} (F_N)}}$ of subset currents on the free group F _N , and, more generally, on a word-hyperbolic group. A subset current on F _N is a positive F _N -invariant locally finite Borel measure on the space ${{\mathfrak{C}_N}}$ of all closed subsets of ?F _N consisting of at least two points. The well-studied space Curr(F _N ) of geodesics currents–positive F _N -invariant locally finite Borel measures defined on pairs of different boundary points–is contained in the space of subset currents as a closed ${{\mathbb{R}}}$ -linear Out(F _N )-invariant subspace. Much of the theory of Curr(F _N ) naturally extends to the ${{\mathcal{S}\;{\rm Curr} (F_N)}}$ context, but new dynamical, geometric and algebraic features also arise there. While geodesic currents generalize conjugacy classes of nontrivial group elements, a subset current is a measure-theoretic generalization of the conjugacy class of a nontrivial finitely generated subgroup in F _N . If a free basis A is fixed in F _N , subset currents may be viewed as F _N -invariant measures on a “branching” analog of the geodesic flow space for F _N , whose elements are infinite subtrees (rather than just geodesic lines) of the Cayley graph of F _N with respect to A. Similarly to the case of geodesics currents, there is a continuous Out(F _N )-invariant “co-volume form” between the Outer space cv _N and the space ${{\mathcal{S}\;{\rm Curr} (F_N)}}$ of subset currents. Given a tree ${{T \in {\rm cv}_N}}$ and the “counting current” ${{\eta_H \in \mathcal{S}\;{\rm Curr} (F_N)}}$ corresponding to a finitely generated nontrivial subgroup H ≤  F _N , the value ${{\langle T, \eta_H \rangle}}$ of this intersection form turns out to be equal to the co-volume of H, that is the volume of the metric graph T _H /H, where ${{T_H \subseteq T}}$ is the unique minimal H-invariant subtree of T. However, unlike in the case of geodesic currents, the co-volume form ${{{\rm cv}_N \times \mathcal{S}\;{\rm Curr}(F_N)\; \to [0,\infty)}}$ does not extend to a continuous map ${{\overline{{\rm cv}}_N \times \mathcal{S}\; {\rm Curr} (F_N) \to [0,\infty)}}$ .     

On Numerical Ranges of Rank-Two Operators

Possible shapes of numerical ranges of rank-two operators are studied. In particular it is proved that for 4-by-4 unitarily irreducible matrices with an eigenvalue of geometric multiplicity two, the numerical ranges have at most one flat portion on the boundary and there are no multiply generated round boundary points.     

Tensor Rank: Matching Polynomials and Schur Rings

We study the polynomial equations vanishing on tensors of a given rank. By means of polarization we reduce them to elements  $A$ of the group algebra ${\mathbb {Q}}[S_n\times S_n]$ and describe explicit linear equations on the coefficients of  $A$ to vanish on tensors of a given rank. Further, we reduce the study to the Schur ring over the group $S_n\times S_n$ that arises from the diagonal conjugacy action of  $S_n$ . More closely, we consider elements of ${\mathbb {Q}}[S_n\times S_n]$ vanishing on tensors of rank $n-1$ and describe them in terms of triples of Young diagrams, their irreducible characters, and nonvanishing of their Kronecker coefficients. Also, we construct a family of elements in ${\mathbb {Q}}[S_n\times S_n]$ vanishing on tensors of rank $n-1$ and illustrate our approach by a sharp lower bound on the border rank of an explicitly produced tensor. Finally, we apply this construction to prove a lower bound $5n^2/4$ on the border rank of the matrix multiplication tensor (being, of course, weaker than the best known one $(2-\epsilon )\cdot n^2$ , due to Landsberg, Ottaviani).     

On stability of minimizers in convex programming

In this paper, we establish conditions ensuring Hölder and Lipschitz continuity of minimizers in convex programming. Lipschitz continuity is proved by establishing and applying a generalized version of the implicit function theorem.