Transition metal complexes with Girard reagent-based ligands

The ligand, salicylaldehyde Girard-T hydrazonium chloride, [H₂SalGT]Cl (1), and two complexes [Cu(HSalGT)X₂]·H₂O (X = Br(2); Cl(3)) were synthesized and their crystal structures were determined by single-crystal X-ray analysis. In the two isostructural complexes, the Cu(II) is located in a square-pyramidal environment, with the chelating ligand and one halogen atom in the basal plane and the second halogen in the apical position. The most apparent structural difference between the 1 and its complexes 2 and 3 is the orientation of the N(CH₃)₃ group: in 1, it is practically coplanar to the rest of the molecule, while in 2 and 3 it is oriented to the side of the axially bonded halogen, which can be explained by the C–H…X intramolecular interactions. The compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and electronic absorption spectra.     

Group additive values for the gas phase standard enthalpy of formation of hydrocarbons and hydrocarbon radicals

A complete and consistent set of 95 Benson group additive values (GAV) for the standard enthalpy of formation of hydrocarbons and hydrocarbon radicals at 298 K and 1 bar is derived from an extensive and accurate database of 233 ab initio standard enthalpies of formation, calculated at the CBS-QB3 level of theory. The accuracy of the database was further improved by adding newly determined bond additive corrections (BAC) to the CBS-QB3 enthalpies. The mean absolute deviation (MAD) for a training set of 51 hydrocarbons is better than 2 kJ mol(-1). GAVs for 16 hydrocarbon groups, i.e., C(C(d))(3)(C), C-(C(d))(4), C-(C(t))(C(d))(C)(2), C-(C(t))(C(d))(2)(C), C-(C(t))(C(d))(3), C-(C(t))(2)(C)(2), C-(C(t))(2)(C(d))(C), C-(C(t))(2)(C(d))(2), C-(C(t))(3)(C), C-(C(t))(3)(C(d)), C-(C(t))(4), C-(C(b))(C(d))(C)(H), C-(C(b))(C(t))(H)(2), C-(C(b))(C(t))(C)(H), C-(C(b))(C(t))(C)(2), C(d)-(C(b))(C(t)), for 25 hydrocarbon radical groups, and several ring strain corrections (RSC) are determined for the first time. The new parameters significantly extend the applicability of Benson's group additivity method. The extensive database allowed an evaluation of previously proposed methods to account for non-next-nearest neighbor interactions (NNI). Here, a novel consistent scheme is proposed to account for NNIs in radicals. In addition, hydrogen bond increments (HBI) are determined for the calculation of radical standard enthalpies of formation. In particular for resonance stabilized radicals, the HBI method provides an improvement over Benson's group additivity method.     

How electrons guard the space: shape optimization with probability distribution criteria

Efficient formulas for computing the probabilities of finding exactly electrons in an arbitrarily chosen volume ³ for Hartree–Fock wavefunctions are presented. These formulas allow the use of shape optimization techniques, such as level set methods, for optimizing with respect to various criteria involving such probabilities. The criterion defined as the difference between the Hartree–Fock and the independent-particle model probabilities of finding electrons in stresses the quantum effects due to the Pauli principle. We have implemented a 2D level set method for optimizing this criterion in order to study spatial separation of electron pairs in linear molecules. The method is described and the illustrative example of the BH molecule is reported.Contribution to the Jacopo Tomasi Honorary Issue     

Direct quantitative determination of surface Brønsted acidity of solids by H/D exchange using D2O

A highly flexible method for direct and quantitative determination of surface Br?nsted acidity of solids in terms of number, type and strength of the acid sites based on quantitative H/D exchange kinetics between the acid solid and gaseous D2O has been developed and applied to materials covering the whole range of acidity.     

The mass spectra of 2- and 4-monohydroxy- and 2, 4-dihydroxy-1, X-naphthyridines

The mass spectra of 2-and 4-monohydroxy-and 2, 4-dihydroxy-1, 5-, -1, 6-, -1, 7-and 1, 8-naphthyridines are reported. Fragmentation mechanisms are proposed and discussed.