Synthesis of Gold(I)−Trifluoromethyl Complexes and their Role in Generating Spectroscopic Evidence for a Gold(I)−Difluorocarbene Species

Readily prepared and bench-stable [Au(CF₃)(NHC)] compounds were synthesized by using new methods, starting from [Au(OH)(NHC)], [Au(Cl)(NHC)] or [Au(L)(NHC)]HF₂ precursors (NHC=N-heterocyclic carbene). The mechanism of formation of these species was investigated. Consequently, a new and straightforward strategy for the mild and selective cleavage of a single carbon/fluorine bond from [Au(CF₃)(NHC)] complexes was attempted and found to be reversible in the presence of an additional nucleophilic fluoride source. This straightforward technique has led to the unprecedented spectroscopic observation of a gold(I)−NHC difluorocarbene species.     

Gold–Acetonyl Complexes: From Side‐Products to Valuable Synthons

A new synthetic strategy was devised leading to the formation of complexes, such as [Au(IPr)(CH₂COCH₃)]. The approach capitalizes on the formation of a decomposition product observed in the course of the synthesis of [Au(IPr)(Cl)]. A library of gold acetonyl complexes containing the most common N‐heterocyclic carbene (NHC) ligands has been synthesized. These acetonyl complexes are good synthons for the preparation of numerous organogold complexes. Moreover, they have proven to be precatalysts in common gold(I)‐catalyzed reactions.     

Electromagnetic scattering by a homogeneous chiral obstacle in a chiral environment

Time-harmonic electromagnetic waves are scattered by a homogeneouschiral obstacle embedded in a chiral environment. The correspondingtransmission problem is reduced, via Bohren's decomposition,to an integral equation over the interface between the obstacleand the surrounding medium. This integral equation is shownto be uniquely solvable except for a discrete set of electromagneticparameters of the obstacle.     

Ruthenium-catalyzed (2 + 2) intramolecular cycloaddition of allenenes

We report a ruthenium-catalyzed (2 + 2) intramolecular cycloaddition of allenes and alkenes. We have found that the use of the ruthenium complex RuH(2)Cl(2)(P(i)Pr(3))(2), which has previously gone unnoticed in catalytic applications, is crucial for the observed reactivity. The reaction proceeds under mild conditions and is fully diastereoselective, providing a practical entry to a variety of bicyclo[3.2.0]heptane skeletons featuring cyclobutane rings.     

Scenario decomposition of risk-averse multistage stochastic programming problems

For a risk-averse multistage stochastic optimization problem with a finite scenario tree, we introduce a new scenario decomposition method and we prove its convergence. The main idea of the method is to construct a family of risk-neutral approximations of the problem. The method is applied to a risk-averse inventory and assembly problem. In addition, we develop a partially regularized bundle method for nonsmooth optimization.     

Effect of cation site-disorder on the structure and magneto-transport properties of Ln5/8M3/8MnO3 manganites

Five members of Ln_5/8M_3/8MnO₃ series with A-cation size variance (σ²) ranging between 3×10⁻⁴ and 71×10⁻⁴ Å², and the same A-cation size , have been synthesized by the ceramic method. The five manganites are single phase and they crystallize in the Pnma perovskite superstructure. The five compositions display ferromagnetic-paramagnetic transitions at temperatures ranging between 130 and 270 K, for the highest and lowest variance sample, respectively. The samples with smaller variances show sharp magnetization transitions and the samples with the larger variances display broad transitions. These transitions have also been studied by differential scanning calorimetry, DSC, and some enthalpy changes are reported. The resistivity study indicates that all samples display the expected metal-to-insulator transitions at temperatures ranging between 140 and 270 K. The samples have been analysed at room temperature by ultra-high-resolution synchrotron powder diffraction and the structural and microstructural features are reported. Furthermore, Nd_5/8Sr_0.255Ca_0.12MnO₃ () and Sm_0.225Nd_0.4Sr_0.308Ca_0.067MnO₃ () samples have also been studied by synchrotron powder diffraction at 140 K, below the transition temperatures. Both samples are found to be single phase above and below the transition by ultra-high-resolution synchrotron powder diffraction. The microstructure of the samples has been investigated through Williamson-Hall plots. Sample broadenings are markedly anisotropic and strongly dominated by microstrains with average values of the Δd/d term close to 14×10⁻⁴. A direct correlation is found between the microstrain values and the widths of the magnetization transitions.     

Structural and vibrational study of the tautomerism of histamine free-base in solution

Infrared and Raman spectroscopy in H(2)O and D(2)O and quantum Density Functional calculations were used to determine the structure of histamine free-base in aqueous solution. A quantum mechanical study of the tautomeric equilibrium of histamine free-base in solution was performed at the 6-311G level. Electronic correlation energies were included by using the hybrid functional B3LYP. The solvent was simulated as a continuum characterized by a dielectric constant, and the quantum system (solute) was placed in an ellipsoidal cavity. Solute-solvent electrostatic interaction was calculated by means a multipolar moment expansion introduced in the Hamiltonian. Four relevant histamine conformations were optimized by allowing all the geometrical parameters to vary independently, which involved both the gauche-trans and the N3H-N1H tautomerisms. The calculated free energies predicted N3H-gauche as the most stable one of histamine free-base in solution. The order of stability is here completely altered with respect to previous results in gas phase, which presented the N1H-gauche conformer as the most stable structure. Our results also differ from previous Monte Carlo simulations, which obtained the N3H-trans conformer as the most stable in solution, although in this case, the histamine structures were kept frozen to the gas-phase geometry. Vibrational spectroscopy results support theoretical ones. Quadratic force fields for the four histamine conformers were achieved under the same calculation methodology. Previously, a general assignment of the infrared and Raman spectra of histamine free-base was proposed for solutions in both natural and heavy water. This allowed us to compare the experimental set of both wavenumbers and infrared intensities with the calculated ones. The lowest quadratic mean wavenumber deviation was obtained for the N3H-gauche conformer, in agreement with the free-energy calculations. Calculated infrared intensities were also compared to the experimental intensities, supporting this conformer as the relevant structure of histamine free-base in solution. It was then selected for a complete vibrational dynamics calculation, starting with a low-level scaling procedure to fit the set of calculated wavenumbers to the experimental values. The results were presented in terms of quadratic force constants, potential energy distribution, and normal modes.     

Regioselective hydroxylation of phenols by simultaneous photochemical generation of phenol cation-radical and hydroxyl radical

Substituted phenols having pendant isoquinoline N-oxide were synthesized and their photochemical and luminiscent properties studied. Photolysis in an acid medium was found to yield the related photohydroxylation products, in a regioselective process, in addition to the isoquinoline deoxygenated precursor. Photoinduced electron transfer from the donor phenols to the protonated form of the first excited singlet state (S₁) of the pendant isoquinoline N-oxide acting as acceptor leads to a red-shifted emissive charge transfer (CT) state that is in fact a radical/cation-radical pair. Homolysis of the N-OH bond restores the aromatic isoquinoline nucleus and produces a hydroxyl radical that can couple to the required ring carbon in the phenol cation-radical to give the photohydroxylation products in a regioselective process controlled by the spin density of the phenol cation-radical. These photohydroxylation processes efficiently compete with the reported tendency to deprotonation in phenol cation-radicals. The photohydroxylation process by itself, and its regioselectivity, exclude a proton-coupled electron transfer mechanism or a consecutive electron transfer/deprotonation reaction. By contrast, the phenol cation-radical exists long enough to undergo the hydroxyl radical coupling reaction that leads to the photohydroxylation products.