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DFT calculations were performed for the methyl group transfer reaction between CH3Co (dmgBF2)py and PPh3Ni(Triphos). The reaction mechanism and its energetics were investigated. This reaction is relevant to the catalytic mechanism of the enzyme acetyl coenzyme A synthase. BP86 and PBE functionals and dispersion corrections were used. It was found that intermolecular interactions are very important for this reaction. The influence of the solvent on the reaction was studied. [ABSTRACT FROM AUTHOR]

At 20, 25, 30, and 40 °C, the ultrasonic absorption spectra of the protic ionic liquid 3-(butoxymethyl)-1H-imidazol-3-ium salicylate have been measured between 0.6 and 900 MHz. Below 250 MHz, the absorption coefficient decreases with temperature, potentially indicating a major effect of the viscosity and/or a relaxation time. Essentially the broad spectra can be favorably represented by two relaxation terms in addition to an asymptotic high-frequency contribution. One term reflects an asymmetric relaxation time distribution. It is described by a model of noncritical fluctuations in the structure and thermodynamic parameters of the liquid in order to yield the fluctuation correlation length and the mutual diffusion coefficient. Applying the Stokes-Einstein-Kawasaki-Ferrell relation, these quantities can be used to show that the effective shear viscosity controlling the fluctuations is substantially smaller than the steady-state shear viscosity. This result is consistent with dispersion in the shear viscosity as revealed by viscosity measurements at 25, 55, and 81 MHz. The other term can be well described by a Debye-type relaxation function. It has been tentatively assigned to a structural isomerization of the butoxymethyl chain of the imidazole molecule. However, it cannot be completely excluded that this term reflects, at least in parts, a Brønstedt acid-base equilibrium or a specific association process. [ABSTRACT FROM AUTHOR]

The TDDFT method in the B3LYP version was used to calculate the electronic spectra of protonated and unprotonated metal-free corrins. Two low energy forms were found from geometry optimization for the protonated and unproton.

The photolysis of the methylcobalamin cofactor (MeCbl) in its base-off form was investigated by considering the extent of spin-orbit coupling (SOC). Triplet Co-C photodissociation pathways previously invoked at the density functional theory level using Landau-Zener theory were further validated with ab initio calculations that combine SOC based on multi-state second order perturbation theory. It was determined that SOC is feasible between singlet and triplet states at elongated Co-C distances, leading to photodissociation from the state having dominant σ(dz2) character, by either direct coupling with the lowest singlet states or by crossing with SOC mixed triplets. [ABSTRACT FROM AUTHOR]

Photolysis of methylcobalamin (MeCbl) in the presence of molecular oxygen (O2) has been investigated using density functional theory (DFT) and time-dependent DFT (TD-DFT). The key step involves the formation of the Cbl–O–O–CH3 intermediate as a result of triplet O2 insertion in the Co–C bond in the presence of light. Analysis of low-lying excited states shows that the presence of light is only needed to activate the Co–C bond via the formation of the ligand field (LF) state. The insertion of O2, as well as the change in the spin state, takes place in the ground state. The analysis of the structural and electronic properties of the Cbl–O–O–CH3 intermediate is presented and possible decomposition also discussed. [ABSTRACT FROM AUTHOR]

The analysis of the electronic spectra of adenosylcobalamin (AdoCbl) and its derivative in which the trans axial base was replaced by a water molecule (AdoCbi–H2O) has been performed by means of time-dependent density functional theory (TDDFT). The latter corresponds to the situation encountered in strongly acidic conditions. The TDDFT electronic transitions and oscillator strengths were calculated at the optimized B3LYP and BP86 ground state equilibrium geometries. A comparison of the orbital energy diagrams obtained with the B3LYP and BP86 functionals reveals a different orbital order and composition of the highest occupied and lowest unoccupied molecular orbitals. In B3LYP the lowest-energy transitions are of π/d→π*, π/d→σ*, and π/d→d characters while in the case of BP86 they are mainly d/π→π* and d→π*. The long range charge transfer transitions involving excitations from adenine π orbitals to antibonding corrin π* orbital can be observed at low energies, especially in BP86 results. Calculated electronic excitations were used to simulate the absorption spectra for a direct comparison with the absorption spectra recorded for AdoCbl at different pH values. As previously found for methylcobalamin [see Andruniów et al., J. Chem. Phys. 129, 085101 (2008)] also for AdoCbl the two-parameter scaling technique is required to obtain a satisfactory agreement between theoretical and experimental spectra. Both functionals correctly predict the shifting of the lowest intense transition toward blue by approximately 13 nm upon changing pH from 7 to 1. [ABSTRACT FROM AUTHOR]

Time-dependent density functional theory (TDDFT) has been applied to the analysis of the electronic spectra of methylcobalamin (MeCbl) and its derivative in which the trans axial base was replaced by a water molecule (MeCbi[Single_Bond]H2O). The latter corresponds to the situation encountered in strongly acidic solutions. The study primarily focuses on the accuracy of two functionals, the hybrid B3LYP and the gradient corrected BP86, in dealing with the electronic excitations. The high resolution crystal structure of MeCbl was the source of the initial coordinates. To generate the initial structures, the full MeCbl was simplified by replacing the corrin side chains by H atoms. The vertical excitation energies, together with the corresponding oscillator strengths, were calculated at the optimized BP86 and B3LYP structures of the ground electronic state of the complexes. The NBO analysis shows that the B3LYP functional gives a bonding description of the ground state as a more polarized covalent bond compared to that given by BP86. The latter functional has more covalent bonding and is thus more appropriate for modeling the axial bonding properties. To validate the accuracy of the present TDDFT analysis, the computed excitations were directly compared to the absorption spectra of MeCbl. In order to obtain a reliable agreement between experiment and theory, the two-parameter scaling technique was introduced, which compensates differently the low-energy and high-energy excitations. Electronic excitations strongly depend on the choice of the functional. Transitions involving corrin π→π* excitations are better described by the B3LYP functional while transitions associated with metal-to-ligand (d/π→π*/d) excitations are better described by BP86. These differences can be associated with the different bonding descriptions obtained by B3LYP and BP86. [ABSTRACT FROM AUTHOR]

Time dependent density functional theory (TD-DFT) is used to examine the relevant excited states involved in the photolysis of methylcobalamin (MeCbl). The low lying singlet and triplet excited states are calculated along the Co-C bond at the TD-DFT/BP86/6-31g(d) level of theory in order to investigate the dissociation process of MeCbl.