Mechanistic study of styrene aziridination by iron(iv) nitrides.

A combined experimental and computational investigation was undertaken to investigate the mechanism of aziridination of styrene by the tris(carbene)borate iron(iv) nitride complex, PhB( BuIm)Fe[triple bond, length as m-dash]N. While mechanistic investigations suggest that aziridination occurs a reversible, stepwise pathway, it was not possible to confirm the mechanism using only experimental techniques. Density functional theory calculations support a stepwise radical addition mechanism, but suggest that a low-lying triplet ( = 1) state provides the lowest energy path for C-N bond formation (24.

Intramolecular Oxyl Radical Coupling Promotes O-O Bond Formation in a Homogeneous Mononuclear Mn-based Water Oxidation Catalyst: A Computational Mechanistic Investigation.

The mechanism of water oxidation performed by a recently discovered manganese pyridinophane catalyst [Mn(PyNBu)(HO)] is studied using density functional theory methods. A complete catalytic cycle is constructed and the catalytically active species is identified to consist of a Mn-bis(oxo) moiety that is generated from the resting state by a series of proton-coupled electron transfer reactions. Whereas the electronic ground state of this key intermediate is found to be a triplet, the most favorable pathway for O-O bond formation is found on the quintet potential energy surface and involves an intramolecular coupling of two oxyl radicals with opposite spins bound to the Mn-center that adopts an electronic structure most consistent formally with a high-spin Mn ion.

The mechanism of selective catalytic reduction of NO on Cu-SSZ-13 - a computational study.

The copper-exchanged aluminosilicate zeolite SSZ-13 is a leading catalyst for the selective catalytic reduction of NO. Density functional theory calculations are used to construct a complete catalytic cycle of this process paying special attention to the coordination geometries and redox states of copper. N can be produced in the reduction half-cycle via a nitrosamine intermediate generated from the reaction of the additive reductant NH with a NO intermediate stabilized by the zeolite lattice.

The origin of the ligand-controlled regioselectivity in Rh-catalyzed [(2 + 2) + 2] carbocyclizations: steric stereoelectronic effects.

Density functional theory calculations demonstrate that the reversal of regiochemical outcome of the addition for substituted methyl propiolates in the rhodium-catalyzed [(2 + 2) + 2] carbocyclization with PPh and ()-xyl-binap as ligands is both electronically and sterically controlled. For example, the ester functionality polarizes the alkyne π* orbital to favor overlap of the methyl-substituted terminus of the alkyne with the p-orbital of the alkenyl fragment of the rhodacycle during alkyne insertion with PPh as the ligand. In contrast, the sterically demanding xyl-binap ligand cannot accommodate the analogous alkyne orientation, thereby forcing insertion to occur at the sterically preferred ester terminus, overriding the electronically preferred orientation for alkyne insertion.

How a [Co(IV) a bond and a half O](2+) fragment oxidizes water: involvement of a biradicaloid [Co(II)-(⋅O⋅)](2+) species in forming the O-O bond.

The mechanism of water oxidation performed by a recently discovered cobalt complex [Co(Py5)(OH2)](ClO4)2 (1; Py5=2,6-(bis(bis-2-pyridyl)-methoxymethane)pyridine) was examined using quantum chemical models based on density functional theory. The computer models were first benchmarked against the experimental cyclic voltammetry data to identify the catalytically competent resting state of the catalyst, which was thought to contain a Co(IV) -oxyl complex. The electronic structure calculations suggest that the low-spin doublet state is energetically most favorable, but the catalytically most active species is the intermediate-spin quartet complex that is almost isoenergetic with the doublet state.

Switching the enantioselectivity in catalytic [4 + 1] cycloadditions by changing the metal center: principles of inverting the stereochemical preference of an asymmetric catalysis revealed by DFT calculations.

The mechanisms of the asymmetric [4 + 1] carbocyclization of vinylallenes with carbon monoxide catalyzed by Pt(0) and Rh(I) carrying the chiral support ligand (R,R)-Me-DuPHOS (Me-DuPHOS = 1,2-bis(2,5-dimethylphosphorano)benzene) were studied using density functional theoretical models. Previously, it was observed that the (R)-stereoisomer of the 5-substituted 2-alkylidene-3-cyclopentenone products was obtained with Pt(0), but the (S)-enantiomer was formed when Rh(I) metal was used to promote the reaction. Our calculations suggest that the rate-determining step in both cases consists of a C-C coupling between the vinyl end of the vinylallene substrate and carbon monoxide that is accompanied by charge transfer from the metal center to the organic substrate.

Stable-isotope probing of the polycyclic aromatic hydrocarbon-degrading bacterial guild in a contaminated soil.

The bacteria responsible for the degradation of naphthalene, phenanthrene, pyrene, fluoranthene or benz[a]anthracene in a polycyclic aromatic hydrocarbon (PAH)-contaminated soil were investigated by DNA-based stable-isotope probing (SIP). Clone libraries of 16S rRNA genes were generated from the (13) C-enriched ('heavy') DNA recovered from each SIP experiment, and quantitative PCR primers targeting the 16S rRNA gene were developed to measure the abundances of many of the SIP-identified sequences. Clone libraries from the SIP experiments with naphthalene, phenanthrene and fluoranthene primarily contained sequences related to bacteria previously associated with the degradation of those compounds.