The gas phase oxidation of HCOOH by Cl and NH2 radicals. Proton coupled electron transfer versus hydrogen atom transfer*

ABSTRACT

The reaction of formic acid (HCOOH) with chlorine atom and amidogen radical (NH₂) have been investigated using high level theoretical methods such BH&HLYP, MP2, QCISD, and CCSD(T) with the 6–311?+?G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and extrapolation to CBS basis sets. The abstraction of the acidic and formyl hydrogen atoms of the acid by the two radicals has been considered, and the different reactions proceed either by a proton coupled electron transfer (pcet) and hydrogen atom transfer (hat) mechanisms. Our calculated rate constant at 298?K for the reaction with Cl is 1.14?×?10^?13?cm³?molecule^?1?s^?1 in good agreement with the experimental value 1.8?±?0.12/2.0?×?10^?13?cm³?molecule^?1?s^?1 and the reaction proceeds exclusively by abstraction of the formyl hydrogen atom, via hat mechanism, producing HOCO+ClH. The calculated rate constant, at 298?K, for the reaction with NH₂ is 1.71?×?10^?15?cm³?molecule^?1?s^?1, and the reaction goes through the abstraction of the acidic hydrogen atom, via a pcet mechanism, leading to the formation of HCOO+NH₃.     

Performance of density functional theory in computing nonresonant vibrational (hyper)polarizabilities

A set of exchange‐correlation functionals, including BLYP, PBE0, B3LYP, BHandHLYP, CAM‐B3LYP, LC‐BLYP, and HSE, has been used to determine static and dynamic nonresonant (nuclear relaxation) vibrational (hyper)polarizabilities for a series of all‐trans polymethineimine (PMI) oligomers containing up to eight monomer units. These functionals are assessed against reference values obtained using the Møller–Plesset second‐order perturbation theory (MP2) and CCSD methods. For the smallest oligomer, CCSD(T) calculations confirm the choice of MP2 and CCSD as appropriate for assessing the density functionals. By and large, CAM‐B3LYP is the most successful, because it is best for the nuclear relaxation contribution to the static linear polarizability, intensity‐dependent refractive index second hyperpolarizability, static second hyperpolarizability, and is close to the best for the electro‐optical Pockels effect first hyperpolarizability. However, none of the functionals perform satisfactorily for all the vibrational (hyper)polarizabilities studied. In fact, in the case of electric field‐induced second harmonic generation all of them, as well as the Hartree–Fock approximation, yield the wrong sign. We have also found that the Pople 6–31+G(d) basis set is unreliable for computing nuclear relaxation (hyper)polarizabilities of PMI oligomers due to the spurious prediction of a nonplanar equilibrium geometry. © 2013 Wiley Periodicals, Inc.     

Self‐Assembled Tetragonal Prismatic Molecular Cage Highly Selective for Anionic π Guests

The metal‐directed supramolecular synthetic approach has paved the way for the development of functional nanosized molecules. In this work, we report the preparation of the new nanocapsule 3? (CF₃SO₃)₈ with a A₄B₂ tetragonal prismatic geometry, where A corresponds to the dipalladium hexaazamacrocyclic complex Pd‐1 , and B corresponds to the tetraanionic form of palladium 5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin ( 2 ). The large void space of the inner cavity and the supramolecular affinity for guest molecules towards porphyrin‐based hosts converts this nanoscale molecular 3D structure into a good candidate for host–guest chemistry. The interaction between this nanocage and different guest molecules has been studied by means of NMR, UV/Vis, ESI‐MS, and DOSY experiments, from which highly selective molecular recognition has been found for anionic, planar‐shaped π guests with association constants (K_a) higher than 10⁹ M ^?1, in front of non‐interacting aromatic neutral or cationic substrates. DFT theoretical calculations provided insights to further understand this strong interaction. Nanocage 3? (CF₃SO₃)₈ can not only strongly host one single molecule of M(dithiolene)₂ complexes (M=Au, Pt, Pd, and Ni), but also can finely tune their optical and redox properties. The very simple synthesis of both the supramolecular cage and the building blocks represents a step forward for the development of polyfunctional supramolecular nanovessels, which offer multiple applications as sensors or nanoreactors.     

Diels–Alder and Retro‐Diels–Alder Cycloadditions of (1,2,3,4,5‐Pentamethyl)cyclopentadiene to La@C2v‐C82: Regioselectivity and Product Stability

One of the most important reactions in fullerene chemistry is the Diels–Alder (DA) reaction. In two previous experimental studies, the DA cycloaddition reactions of cyclopentadiene (Cp) and 1,2,3,4,5‐pentamethylcyclopentadiene (Cp*) with La@C_2v‐C₈₂ were investigated. The attack of Cp was proposed to occur on bond 19 , whereas that of Cp* was confirmed by X‐ray analysis to be over bond o . Moreover, the stabilities of the Cp and Cp* adducts were found to be significantly different, that is, the decomposition of La@C_2v‐C₈₂Cp was one order of magnitude faster than that of La@C_2v‐C₈₂Cp*. Herein, we computationally analyze these DA cycloadditions with two main goals: First, to compute the thermodynamics and kinetics of the cycloadditions of Cp and Cp* to different bonds of La@C_2v‐C₈₂ to assess and compare the regioselectivity of these two reactions. Second, to understand the origin of the different thermal stabilities of the La@C₈₂Cp and La@C₈₂Cp* adducts. Our results show that the regioselectivity of the two DA cycloadditions is the same, with preferred attack on bond o . This result corrects the previous assumption of the regioselectivity of the Cp attack that was made based only on the shape of the La@C₈₂ singly occupied molecular orbital. In addition, we show that the higher stability of the La@C₈₂Cp* adduct is not due to the electronic effects of the methyl groups on the Cp ring, as previously suggested, but to higher long‐range dispersion interactions in the Cp* case, which enhance the stabilization of the reactant complex, transition state, and products with respect to the separated reactants. This stabilization for the La@C₈₂Cp* case decreases the Gibbs reaction energy, thus allowing competition between the direct and retro reactions and making dissociation more difficult.     

Penultimate Approximations in Statistics of Extremes and Reliability of Large Coherent Systems

In reliability theory any coherent system can be represented as either a series-parallel or a parallel-series system. Its lifetime can thus be written as the minimum of maxima or the maximum of minima. For large-scale coherent systems it is sensible to assume that the number of system components goes to infinity. Then, the possible non-degenerate extreme value laws either for maxima or for minima are eligible candidates for the system reliability or at least for the finding of adequate lower and upper bounds for the reliability. The identification of the possible limit laws for the system reliability of homogeneous series-parallel (or parallel-series) systems has already been done under different frameworks. However, it is well-known that in most situations such non-degenerate limit laws are better approximated by an adequate penultimate distribution. Dealing with regular and homogeneous parallel-series systems, we assess both theoretically and through Monte-Carlo simulations the gain in accuracy when a penultimate approximation is used instead of the ultimate one.     

Catalytic Reduction of Oximes to Hydroxylamines: Current Methods,Challenges and Opportunities

Catalytic reduction of oximes represents a direct efficient approach to synthesize valuable hydroxylamine derivatives. However this transformation presents significant challenges: oximes are hard to reduce and, if reactive, reductive cleavage of the weak N−O bond often leads to primary amine side products. The first suitable systems involved the use of platinum-based heterogeneous catalysts with hydrogen as reductant and stoichiometric amounts of a strong Brønsted acid. More recently metal-free and transition-metal-based homogeneous catalysts have been developed, which display the highest turnovers (up to 4000). In the asymmetric variants, the E/Z-geometry of the oxime double bond affects significantly the stereoselectivity, sometimes requiring extra synthetic efforts in substrate preparation. This minireview provides an overview of the advances and limitations in catalytic oxime to hydroxylamine reduction. Emphasis is put on highlighting and comparing the practical aspects of the existing methods, such as their reaction conditions and substrate scope. Additionally, future directions for improving this young research area are suggested.     

Imaging the Magnetic Reversal of Isolated and Organized Molecular‐Based Nanoparticles using Magnetic Force Microscopy

In the race towards miniaturization in nanoelectronics, magnetic nanoparticles (MNPs) have emerged as potential candidates for their integration in ultrahigh‐density recording media. Molecular‐based materials open the possibility to design new tailor‐made MNPs with variable composition and sizes, which benefit from the intrinsic properties of these materials. Before their implementation in real devices is reached, a precise organization on surfaces and a reliable characterization and manipulation of their individual magnetic behavior are required. In this paper, it is demonstrated how molecular‐based MNPs are accurately organized on surfaces and how the magnetic properties of the individual MNPs are detected and tuned by means of low‐temperature magnetic force microscopy (LT‐MFM) with variable magnetic field. The magnetization reversal on isolated and organized MNPs is investigated; in addition, the temperature dependence of their magnetic response is evaluated.