7 research outputs found
An efficient approach to calculation of zero-flux atomic surfaces and generation of atomic integration data
No full textThe charge distribution and the electric field gradient at the nuclei of two-coordinated N atoms
No full textComputational study of iminium ion formation: effects of amine structure
No full textD. functional calcns. are used to explore the formation of iminium ions from secondary amines and acrolein and the subsequent reactivity of the resulting iminium ions. After establishing a feasible profile for this reaction in simulated exptl. conditions, we focus on the effect of variation in amine structure on calcd. barriers. This anal. shows that incorporation of a heteroatom (N or O) in the α-position to the reactive amine results in significantly reduced energy barriers, as does an electron-withdrawing group (carbonyl or thiocarbonyl) in the β-position. Electron d. anal. is used to monitor reactions at a detailed level, and to identify important intermol. interactions at both min. and transition states. Barriers to reaction are linked to calcd. proton affinities of secondary amines, suggesting that the relative ease of protonation-deprotonation of the amine is a key property of effective catalysts. Moreover, barriers for subsequent Diels-Alder reaction of iminium ions with cyclopentadiene are lower than for their formation, suggesting that formation may be the rate detg. step in the catalytic cycle
Electronic structure of the benzene-tetracyanoethylene complex: A synthesis of molecular orbital and density functional descriptions
No full textThe X-Ray Molecular Structure of 1-(2′,4′-Dinitrophenyl)-1,2,3-triazole and the Problem of the Orthogonal Interaction Between a 'Pyridine-Like' Nitrogen and a Nitro Group
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