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Henry Rzepa's Blog

Henry Rzepa's Blog
Chemistry with a twist
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HypervalencyInteresting ChemistryBondQuadrupleCiencias QuímicasInglés
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So ingrained is the habit to think of a bond as a simple straight line connecting two atoms, that we rarely ask ourselves if they are bent, and if so, by how much (and indeed, does it matter?). Well Hursthouse, Malik, and Sales, as long ago as 1978, asked just such a question about the […]

Interesting ChemistryAnimationCatalytic SystemsChemical IntimacyEnergyCiencias QuímicasInglés
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The scheme below illustrates one of the iconic reactions in organic chemistry. It is a modern representation of Meerwein’s famous experiment from which he inferred a carbocation intermediate, deduced from studying the rate of enantiomerization of isobornyl chloride when treated with the Lewis acid SnCl4.

HypervalencyInteresting ChemistryAromaticityPericyclicSouth CarolinaCiencias QuímicasInglés
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In the previous post, the molecule F 3 S-C≡SF 3 was found to exhibit a valence bond isomerism, one of the S-C bonds being single, the other triple, and with a large barrier (~31 kcal/mol, ν 284 i cm -1 ) to interconversion of the two valence-bond forms. So an interesting extension of this phenomenon is shown below: A cyclic form of the SCS Motif.

HypervalencyInteresting ChemistryAnimationCalculated Free Energy BarrierInorganic ChemistCiencias QuímicasInglés
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A previous post posed the question; during the transformation of one molecule to another, what is the maximum number of electron pairs that can simultaneously move either to or from any one atom-pair bond as part of the reaction?

Interesting ChemistryAromaticityClarClar IslandsCloud Clar IslandsCiencias QuímicasInglés
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Clar islands are found not so much in an ocean, but in a type of molecule known as polycyclic aromatic hydrocarbons (PAH). One member of this class, graphene, is attracting a lot of attention recently as a potential material for use in computer chips.

HypervalencyInteresting ChemistryLarge Interaction EnergyCiencias QuímicasInglés
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In my first post on this theme, an ELF (Electron localization function) analysis of the bonding in the molecule HO-S≡C-H (DOI: 10.1002/anie.200903969) was presented. This analysis identified a lone pair of electrons localized on the carbon (integrating in fact to almost exactly 2.0) in addition to electrons in the CC region.