The crystal structure of tetraphenylphosphonium tetracyanohydroxooxorhenium(V)

Summary The crystal structure of (PPh₄)₂[ReO(OH)(CN)₄]·5H₂O has been determined from three-dimensional x-ray diffraction data. The light brown crystals are monoclinic, space group P2₁/n, with cell dimensionsa=16.753(2),b=19.928(2),c=15.338(2) Å and =101,894(1)°,z=4, D_m=1.45(1) g cm^–3. The anisotropic refinement of the 6088 observed reflections converged to R=0.077.The [ReO(OH)(CN)₄]^2– ion has a distorted octahedral geometry. Bond distances: Re =1.70(1), Re–OH=1.90(1) and ReC_av=2.12(2) Å. The Re atom is displaced by 0.08 Å out of the plane formed by the four carbon atoms towards the terminal oxo ligand.     

121Sb-Mössbauer-Spektren von Antimon(V)-Verbindungen. II

¹²¹Sb Mössbauer Spectra of Antimony (V) Compounds. II The Mössbauer resonance effect of ¹²¹Sb has been studied at 4.2 K in a series of 11 antimony(V) compounds which are in most cases bridged. Isomer shift and quadrupole splitting variations are considered in the light of results of X-ray and vibrational spectroscopy. Preparation and the vibrational spectra of [NMe₄][SbCl₄(n₃)₂] are described. Within the limitations of available structural data related tin compounds are compared with those of corresponding ¹¹⁹Sn Mössbauer spectra.     

Laser-Rf double-resonance studies of the hyperfine structure of metastable atomic states of55Mn

The hyperfine structure (hfs) of the metastable atomic states 3d⁶4s⁶ D _{1/2, 3/2, 5/2, 7/2, 9/2} of⁵⁵Mn was measured using theABMR- LIRF method (atomicbeammagneticresonance, detected bylaserinducedresonancefluorescence). The hfs constantsA andB, corrected for second order hfs perturbations, could be derived from these measurements. The theoretical interpretation of these correctedA- andB-factors was performed in the intermediate coupling scheme taking into account the configurations 3d ⁵4s ², 3d ⁶4s and 3d ⁷. Examining the influence of the composition of the eigenvectors on the hfs parameters \(\left\langle {r^{ - 3} } \right\rangle ^{k_s k_l } \) it was found, that for the configuration 3d ⁶4s the two-body magnetic interaction should be considered in the calculation of the eigenvectors. Investigating second order electrostatic configuration interactions and relativistic effects and using calculated relativistic correction factors we obtained for the nuclear quadrupole moment of the nucleus⁵⁵Mn a value ofQ=0.33(1) barn, which is not perturbed by a shielding or antishielding Sternheimer factor. The following hfs constants have been obtained: $$\begin{gathered} A\left( {{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-\nulldelimiterspace} 2}} \right) = 882.056\left( {12} \right)MHz \hfill \\ A\left( {{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} \right) = 469.391\left( 7 \right)MHzB\left( {{3 \mathord{\left/ {\vphantom {3 2}} \right. \kern-\nulldelimiterspace} 2}} \right) = - 65.091\left( {50} \right)MHz \hfill \\ A\left( {{5 \mathord{\left/ {\vphantom {5 2}} \right. \kern-\nulldelimiterspace} 2}} \right) = 436.715\left( 3 \right)MHzB\left( {{5 \mathord{\left/ {\vphantom {5 2}} \right. \kern-\nulldelimiterspace} 2}} \right) = - 46.769\left( {30} \right)MHz \hfill \\ A\left( {{7 \mathord{\left/ {\vphantom {7 2}} \right. \kern-\nulldelimiterspace} 2}} \right) = 458.930\left( 3 \right)MHzB\left( {{7 \mathord{\left/ {\vphantom {7 2}} \right. \kern-\nulldelimiterspace} 2}} \right) = 21.701\left( {40} \right)MHz \hfill \\ A\left( {{9 \mathord{\left/ {\vphantom {9 2}} \right. \kern-\nulldelimiterspace} 2}} \right) = 510.308\left( 8 \right)MHzB\left( {{9 \mathord{\left/ {\vphantom {9 2}} \right. \kern-\nulldelimiterspace} 2}} \right) = 132.200\left( {120} \right)MHz \hfill \\ \end{gathered} $$      

What’s New with the Neutron and Proton

The existence and importance of the proton radius puzzle, observed via a Lamb shift measurement in muonic atoms, is discussed. Possible resolutions of the puzzle are discussed. Then the broader question of the meaning of the proton radius is addressed and examples of correctly defined charge densities are presented.     

Simulations of full multivariate Tweedie with flexible dependence structure

We employ a variables-in-common method for constructing multivariate Tweedie distributions, based on linear combinations of independent univariate Tweedie variables. The method lies on the convolution and scaling properties of the Tweedie laws, using the cumulant generating function for characterization of the distributions and correlation structure. The routine allows the equivalence between independence and zero correlation and gives a parametrization through given values of the mean vector and dispersion matrix, similarly to the Gaussian vector. Our approach leads to a matrix representation of multivariate Tweedie models, which permits the simulations of many known distributions, including Gaussian, Poisson, non-central gamma, gamma, and inverse Gaussian, both positively or negatively correlated.     

Drying of guaco leaves: experimental and modeling kinetic,equilibrium isotherms and heat of desorption

Journal of Thermal Analysis and Calorimetry - Due to the huge variety of therapeutic properties found in plant leaves, many of these are widely used in traditional medicine. Among these plants,...     

Batch tautomer generation with MolTPC

Besides all their conformational degrees of freedom, drug‐like molecules and natural products often also undergo tautomeric interconversions. Compared to the huge efforts made in experimental investigation of tautomerism, open and free algorithmic solutions for prototropic tautomer generation are surprisingly rare. The few freely available software packages limit their output to a subset of the possible configurational space by sometimes unwanted prior assumptions and complete neglection of ring‐chain tautomerism. Here, we describe an adjustable fully automatic tautomer enumeration approach, which is freely available and also incorporates the detection of ring‐chain variants. The algorithm is implemented in the MolTPC framework and accessible on SourceForge. © 2013 Wiley Periodicals, Inc.     

Mechanistic Insights into the Rhenium‐Catalyzed Alcohol‐To‐Olefin Dehydration Reaction

Rhenium‐based complexes are powerful catalysts for the dehydration of various alcohols to the corresponding olefins. Here, we report on both experimental and theoretical (DFT) studies into the mechanism of the rhenium‐catalyzed dehydration of alcohols to olefins in general, and the methyltrioxorhenium‐catalyzed dehydration of 1‐phenylethanol to styrene in particular. The experimental and theoretical studies are in good agreement, both showing the involvement of several proton transfers, and of a carbenium ion intermediate in the catalytic cycle.