Synthesis and characterization of homoleptic ruthenium(II) imidazole complexes, and a carbonyl species derived by CO abstraction from DMF

Article Abstract:

(Ru(II)(L)6)2+ complexes have been synthesized from (Ru(DMF)6)(CF3SO3)3. DMF is dimethylformamide, L is imidazole, N-methylimidazole, or 5-methylimidazole. Synthesis of the complex with 2-methylimidazole, trans (Ru(CO)(DMF)(2MeIm)4)(CF3SO3)2, was carried out using a reaction involving abstraction of CO from DMF. Complexes were characterized by several means including spectroscopies, elemental analysis and conductivity. Structures were studied using Patterson methods refined with full-matrix least-squares procedures.

Models, Observations, Isotopes, Molecules, Imidazole, Crystal lattices, Ruthenium

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Hydration of the carbonyl group: further evidence for a cooperative mechanism from experimental and theoretical studies of the hydrations of formaldehyde, acetaldehyde, acetone, and cyclohexanone

Article Abstract:

The hydration of the carbonyl group appears to proceed via a cooperative, nonionic mechanism between water molecules. The (super 18)O isotope shift was used to study the neutral hydration of acetone by H(sub2)(super18)O. The mechanism proceeded via different-sized water clusters during the hydration of acetone, formaldehyde, acetaldehyde and cyclohexanone. Free energies of activation reveal a cyclic mechanism containing four nonspectator water molecules.

Hydration, Rehydration solutions, Carbonyl compounds

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Transverse compression and the secondary H/D isotope effects in intramolecular S(sub N)2 methyl- transfer reactions

Article Abstract:

The intramolecular S(sub N)2 transfer of two oxygens proceeds by two different mechanisms depending on how many bonds separate the two oxygen atoms. Three or four bonds causes a high energy retention mechanism and six bonds cause a high energy inversion mechanism. Five bonds result in both mechanisms. During the retention mechanism, the CH3/CD3 kinetic isotope effects are normal, but are inverse during the inversion mechanism.

Methyl groups, Methyl compounds, Isotope shift

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