The protolytic cleavage of the O-H bond in water and alcohols is a very important reaction, and an important method for producing dihydrogen. Full quantum chemical studies with density functional theory (DFT) reveal that germanium based complexes, such as HC{CMeArB}2GeH (Ar = 2,6-(i)Pr2C6H3), with the assistance of silicon based compounds such as SiF3H, can perform significantly better than the...

An equation relating the strength (bondforming power) of an spd hybrid bond orbital to the angles it makes with other bond orbitals is formulated and applied in the discussion of the structures of transition-metal carbonyls and other substances by the valence-bond method. The rather simple theory gives results that agree well with those obtained by the complicated and laborious calculation of s...

The reaction of Hg(CF3CO2)2 with metalloporphyrins produces mercurated porphyrins regioselectively, the reaction, surprisingly occurring at the most hindered betaB-position; this behavior is in marked contrast to the usual electrophilic substitution reactions of porphyrins, whose reactions produce meso-substituted porphyrins; the obtained mercurated porphyrins are active to transition metal-cat...

A transition metal-free process for the regioselective synthesis of pyrrolo[1,2-a]quinoxalines under mild conditions in one-pot is described. The reaction afforded a variety of products in good to excellent yields. Indolo[1,2-a]quinoxalines were also synthesized from indole-2-carboxamides under the same conditions.

High-resolution photoemission spectra from the 4 f 7/2 levels of Ta~100! have been obtained between 77 K and room temperature. The data show an increase in both the surface and bulk core-level binding energies ~BE’s! as the temperature is raised: between 77 and 293 K the bulk and surface BE’s increase by 3163 and 1362 meV, respectively. A model calculation of the bulk binding-energy increase, w...

In this work, we have described an alternative alkenylation approach to illustrate the metal-like behaviour of iodine in cross-coupling reactions. Alkenylation could proceed through iodide catalysed radical initiation, radical addition and iodine promoted alkenyl functionality recovery. Catalytic HI elimination similar to the β-hydride elimination of transition metals was realized for the radic...

We study the electronic and optical properties of 39 small molecules containing transition metal atoms and 7 others related to quantum-dots for photovoltaics. We explore in particular the merits of the many-body GW formalism, as compared to the ΔSCF approach within density functional theory, in the description of the ionization energy and electronic affinity. Mean average errors of 0.2-0.3 eV w...

The quantum states in metal clusters bunch into supershells with associated orbitals having shapes resembling those in atoms, giving rise to the concept that selected clusters could mimic the characteristics of atoms and be classified as superatoms. Unlike atoms, the superatom orbitals span over multiple atoms and the filling of orbitals does not usually exhibit Hund's rule seen in atoms. Here,...

Identification of transient species is a necessary part of delineating the kinetics and mechanisms associated with chemical dynamics; when dealing with photo-induced processes, this can be an exceptionally challenging task due to the fact that spectra associated with excited state(s) sampled over the course of a photochemical event often cannot be uniquely identified nor readily calculated. Usi...