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Henry Rzepa's Blog

Henry Rzepa's Blog
Chemistry with a twist
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Chemical ITAcademic PublishingAmerican Chemical SocietyAuthorBusiness IntelligenceChimicaInglese
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The conventional procedures for reporting analysis or new results in science is to compose an “article”, augment that perhaps with “supporting information” or “SI”, submit to a journal which undertakes peer review, with revision as necessary for acceptance and finally publication.

Reaction MechanismAnimationCarbenium IonCationsChemical ElementsChimicaInglese
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Previously, I explored the Graham reaction to form a diazirine. The second phase of the reaction involved an Sn2′ displacement of N-Cl forming C-Cl. Here I ask how facile the simpler displacement of C-Cl by another chlorine might be and whether the mechanism is Sn2 or the alternative Sn1.

Chemical ITAmerican National Science FoundationBond LengthChemDrawChemicalChimicaInglese
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Members of the chemical FAIR data community have just met in Orlando (with help from the NSF, the American National Science Foundation) to discuss how such data is progressing in chemistry. There are a lot of themes converging at the moment.

Curly ArrowsInteresting Chemistry/RTActivation EnergyActivation Free EnergyChimicaInglese
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Students learning organic chemistry are often asked in examinations and tutorials to devise the mechanisms (as represented by curly arrows) for the core corpus of important reactions, with the purpose of learning skills that allow them to go on to improvise mechanisms for new reactions.

Interesting ChemistryAntiaromaticityAromaticityBaird's RuleConjugated SystemChimicaInglese
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There is emerging interest in cyclic conjugated molecules that happen to have triplet spin states and which might be expected to follow a 4n rule for aromaticity. The simplest such system would be the triplet state of cyclobutadiene, for which a non or anti-aromatic singlet state is always found to be lower in energy.

Chemical ITAcademic PublishingAcrobatArticlesChemical DiscoveriesChimicaInglese
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The traditional structure of the research article has been honed and perfected for over 350 years by its custodians, the publishers of scientific journals. Nowadays, for some journals at least, it might be viewed as much as a profit centre as the perfected mechanism for scientific communication.

Interesting ChemistryChemical KineticsChemical ReactionChemistryDeuteriumChimicaInglese
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Five years back, I speculated about the mechanism of the epoxidation of ethene by a peracid, concluding that kinetic isotope effects provided interesting evidence that this mechanism is highly asynchronous and involves a so-called “hidden intermediate”. Here I revisit this reaction in which a small change is applied to the atoms involved.