Just before splitting: A mechanistic model has been proposed for H2 activation by sterically demanding phosphine–borane Lewis pairs. There is theoretical evidence for noncovalent intermolecular association of donor–acceptor molecules to form a flexible but energetically strained complex, which provides preorganized active centers for heterolytic HH bond cleavage (see picture).

A density functional theory study of the atomic structure, formation energy, and vibrational properties of nitrogen-vacancy-oxygen defects in silicon A density functional theory study of CO oxidation on Ru(0001) at low coverage Equilibrium geometries, bond dissociation energies, dipole moments, harmonic vibrational frequencies, and infrared intensities were calculated for a set often neutral nitrogen oxides (NO, NO z , N0 3 , NzO, sym NzO z , asym N Z 0 3 , sym N Z 0 3 , sym N Z 0 4 , asym N Z 0 4 , and NzOs) by applying one local and two gradient-corrected nonlocal functionals in a Gaussian-type-orbital density functional method. Comparison with available experimental data shows that, except for the bond dissociation energies, the local functional gives very accurate molecular properties. Nonlocal functionals considerably improve the bond dissociation energies, but the results still overestimate the experimental values by about 10 kcallmol on average. For the other properties, the results obtained with nonlocal functionals are not necessarily superior to those calculated with the local functional. The properties of two molecules (sym N 2 0 3 and asym N Z 0 4 ) are predicted for the first time and several reassignments are proposed in the vibrational spectra of di-nitrogen oxides.

The reaction mechanism for the transition metal free direct hydrogenation of bulky imines catalyzed by the Lewis acid B(C6F5)3 is investigated in detail by quantum chemical calculations. A recently introduced mechanistic model of heterolytic hydrogen splitting that is based on noncovalent association of bulky Lewis acid-base pairs is shown to account for the reactivity of imine-borane as well as amine-borane systems. Possible catalytic cycles are examined, and the results provide solid support for the imine reduction pathway proposed from experimental observations. In addition, the feasibility of an autocatalytic route initiated by amine-borane hydrogen cleavage is demonstrated. Conceptual issues regarding the notion of frustration are also discussed. The observed reactivity is interpreted in terms of thermally induced frustration, which refers to thermal activation of strained dative adducts of bulky Lewis donor-acceptor pairs to populate their reactive frustrated complex forms.

Two alternative qualitative reactivity models have recently been proposed to interpret the facile heterolytic cleavage of H2 by frustrated Lewis pairs (FLPs). Both models assume that the reaction takes place via reactive intermediates with preorganized acid/base partners; however, they differ in the mode of action of the active centers. In the electron transfer (ET) model, the hydrogen activation is associated with synergistic electron donation processes with the simultaneous involvement of active centers and the bridging hydrogen, showing similarity to transition-metal-based and other H2-activating systems. In contrast, the electric field (EF) model suggests that the heterolytic bond cleavage occurs as a result of polarization by the strong EF present in the cavity of the reactive intermediates. To assess the applicability of the two conceptually different mechanistic views, we examined the structural and electronic rearrangements as well as the EFs along the H2 splitting pathways for a representative set of reactions. The analysis reveals that electron donations developing already in the initial phase are general characteristics of all studied reactions, and the related ET model provides qualitative interpretation for the main features of the reaction pathways. On the other hand, several arguments have emerged that cast doubt on the relevance of EF effects as a conceptual basis in FLP-mediated hydrogen activation.

Car–Parrinello simulations have been performed to study the interaction of water with pyrite (100) surface. The stability and the structural and electronic properties of both the molecular and dissociative adsorptions have been addressed. We found a very strong preference for molecular adsorption on the surface iron sites, in agreement with experiment. The dissociative chemisorption of water is energetically disfavored and is even locally unstable; the dissociated fragments transform back to the stable molecular form in a short molecular dynamics run. The calculations revealed that hydrogen bonding plays an important role in the stabilization of the adsorbed water for both the molecular and the dissociative states. We have shown that water forms a coordinative covalent bond with the surface iron atoms by donating electron to the empty iron dz2 orbitals which are the lowest empty states on the clean surface. At full coverage, the sulfur 3p states thus become the lowest available empty states and therefore the subject of possible electron-transfer reactions.

Using a first-principles approach, we characterize dangling bond defects at Si-SiO2 interfaces by calculating hyperfine parameters for several relaxed structures. Interface models, in which defect Si atoms remain close to crystalline sites of the substrate upon relaxation, successfully describe P(b) and P(b0) defects at (111) and (100) interfaces, respectively. On the basis of calculated hyperfine parameters, we discard models of the P(b1) defect containing a first neighbor shell with an O atom or a strained bond. A novel model consisting of an asymmetrically oxidized dimer yields hyperfine parameters in excellent agreement with experiment and is proposed as the structure of the P(b1) center.

ABSTRACT:A detailed molecular orbital treatment of the heterolytic hydrogen splitting by bulky Lewis acid-base pairs is presented. The frontier molecular orbitals of the proposed reactive intermediate are shown to be preorganized but otherwise practically identical to those of the free acid and base molecules. The concerted interaction of the Lewis centers with hydrogen leading to the polarization and, ultimately, to the cleavage of the HOH bond is examined, and the bridge role of hydrogen molecule in the electron transfer is pointed out. The formation of the new covalent bonds is monitored by bond order and natural localized molecular orbital calculations, and found to be synchronous. The stability of the product is interpreted on the basis of favorable orbital interactions. A comparison of various hydrogen activation mechanisms emphasizes the common donation/back-donation motifs and the different ways of making them feasible.

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