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Central Cation (central + cation)
Selected AbstractsOxidation of CH3NH2 and (CH3)2NH by NiIII(cyclam)(H2O)23+ in Aqueous SolutionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2004Dror Shamir Abstract NiII(1,4,8,11-tetraazacyclotetradecane)2+, NiIIL2+, is a good electrocatalyst for the oxidation of CH3NH2 and (CH3)2NH but not of (CH3)3N. The oxidation kinetics of the amines by NiIIIL(H2O)23+ indicate that the amines are good axial ligands to the tervalent nickel complex. The complexes NiIIIL[N(CH3)iH3,i](H2O)3+ are stronger oxidants than the complexes NiIIIL[N(CH3)iH3,i]23+. The oxidation is base-catalyzed and obeys a second-order rate law in NiIIILX2. It is proposed that the key step is NiIII,L(H2O)[N(CH3)iH2,i]2+ + NiIIILX2 , LNiII,N(=CH2)(CH3)i,1H2,i + NiIIL2+ + H3O+ + 2 X. Naturally, N(CH3)3 is not oxidized by this mechanism. Of special interest is the observation that the axial ligands CH3NH2 and (CH3)2NH are oxidized by the central cation, while the cyclam ligand, which has four secondary amine groups bound to the nickel(III) ion, and axially bound pendant primary amine groups, which are covalently linked to the macrocyclic ligand, are relatively stable. This difference in the behavior of axially bound amine groups is attributed to the free rotation of the axially bound N(CH3)iH3,i ligands that is required for the oxidation to proceed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Theoretical study of adsorption of methyl tert -butyl ether on broken clay minerals surfacesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2005A. Michalkova Abstract The interactions between methyl tert -butyl ether (MTBE) and differently defected tetrahedral and octahedral fragments of clay minerals containing Si4+, Al3+, and Mg2+ central cations have been studied at the B3LYP and MP2 levels of theory in conjunction with the 6-31G(d) basis set. MTBE interacts with defect clay structures due to the formation of multiple CH,O and OH,O hydrogen bonds. Interactions of MTBE with systems containing different types of defected mineral fragments were found to vary. Systems containing the same type of defected mineral fragment with different central cation interact almost the same way with MTBE. The formation of hydrogen bonds leads to changes in the geometrical parameters and to the polarization of MTBE. The values of the interaction energies depend on the charge of the mineral fragment. They amount to 5 kcal/mol,35 kcal/mol. MTBE interacts more preferably with octahedral fragments than with tetrahedral fragments that contain an Al3+ central cation. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Entropy considerations in kinetic method experimentsJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 9 2004Chrys WesdemiotisArticle first published online: 7 SEP 200 Abstract In extended kinetic method experiments, relative binding enthalpies (,affinities') and relative entropies are obtained based on unimolecular dissociation kinetics. A series of ion-bound dimers AXBi is formed, in which the sample (A) and structurally similar reference molecules (Bi) are bridged by a central cation or anion (X). The branching ratios of the AXBi set to AX and BiX are determined at different internal energies, usually by subjecting AXBi to collisionally activated dissociation at various collision energies. The dependence of the natural logarithm of the branching ratios on the corresponding BiX bond enthalpies (X affinities of Bi) is evaluated as a function of internal energy to thereby deduce the AX bond enthalpy (X affinity of A) as well as an apparent relative entropy of the competitive dissociation channels, ,(,Sapp). Experiments with proton- and Na+ -bound dimers show that this approach can yield accurate binding enthalpies. In contrast, the derived ,(,Sapp) values do not correlate with the corresponding thermodynamic entropy differences between the channels leading to AX and BiX, even after scaling. The observed trends are reconciled by the transition state switching model. According to this model, the kinetics of barrierless dissociations, such as those encountered in kinetic method studies, are dominated by a family of tight transition states (,entropy bottlenecks') lying lower in energy than the corresponding dissociation thresholds. In general, the relative energies of these tight transition states approximately match those of the dissociation products, but their relative entropies tend to be much smaller, as observed experimentally. Copyright © 2004 John Wiley & Sons, Ltd. [source] Theoretical study of adsorption of methyl tert -butyl ether on broken clay minerals surfacesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2005A. Michalkova Abstract The interactions between methyl tert -butyl ether (MTBE) and differently defected tetrahedral and octahedral fragments of clay minerals containing Si4+, Al3+, and Mg2+ central cations have been studied at the B3LYP and MP2 levels of theory in conjunction with the 6-31G(d) basis set. MTBE interacts with defect clay structures due to the formation of multiple CH,O and OH,O hydrogen bonds. Interactions of MTBE with systems containing different types of defected mineral fragments were found to vary. Systems containing the same type of defected mineral fragment with different central cation interact almost the same way with MTBE. The formation of hydrogen bonds leads to changes in the geometrical parameters and to the polarization of MTBE. The values of the interaction energies depend on the charge of the mineral fragment. They amount to 5 kcal/mol,35 kcal/mol. MTBE interacts more preferably with octahedral fragments than with tetrahedral fragments that contain an Al3+ central cation. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] | ||||||||||