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Henry Rzepa's Blog

Henry Rzepa's Blog
Chemistry with a twist
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HypervalencyWibergChemieEnglisch
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One approach to reporting science which is perhaps better suited to the medium of a blog than a conventional journal article is the opportunity to follow ideas in unexpected, even unconventional directions. Thus my third attempt, like a dog worrying a bone, to explore hypervalency.

HypervalencyPenceChemieEnglisch
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In the last post, IH 7 was examined to see if it might exhibit true hypervalency. The iodine, despite its high coordination, turned out not to be hypervalent, with its (s/p) valence shell not exceeding eight electrons (and its d-shell still with 10, and the 6s/6p shells largely unoccupied). Instead, the 14 valence electrons (7 from H, 7 from iodine) fled to the H…H regions.

Interesting ChemistryCambridgeChemical NameHistoricalMetalChemieEnglisch
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The molecule below was characterised in 1996 (DOI: 10.1246/cl.1996.489) and given the name tris(dithiolene)vanadium (IV). No attempt was made in the original article to give this molecule a Lewis structure using Lewis electron pair bonds. This blog will explore some of the issues that arise when this is attempted. 1 NAMPOG.

Interesting ChemistryEnergyFree EnergyTrimer EnergyChemieEnglisch
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Many university chemistry departments, and mine is no exception, like to invite applicants to our courses to show them around. Part of the activities on the day is an “interview” in which the candidate is given a chance to shine. Over the years, I have evolved questions about chemistry which can form the basis of discussion, and I thought I would share one such question here.

HypervalencyInteresting Chemistry13-dimethylcyclobutadieneBorboiuCambridgeChemieEnglisch
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Carbon dioxide is much in the news, not least because its atmospheric concentration is on the increase. How to sequester it and save the planet is a hot topic. Here I ponder its solid state structure, as a hint to its possible reactivity, and hence perhaps for clues as to how it might be captured. The structure was determined (DOI 10.1103/PhysRevB.65.104103) as shown below. The structure of solid carbon dioxide.

Interesting ChemistryAcetic AcidAnimationAromaticityChemicalChemieEnglisch
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Unravelling reaction mechanisms is thought to be a 20th century phenomenon, coincident more or less with the development of electronic theories of chemistry. Hence electronic arrow pushing as a term. But here I argue that the true origin of this immensely powerful technique in chemistry goes back to the 19th century.

GeneralInteresting Chemistry3gAnimationCatalysisChemieEnglisch
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Lactide is a small molecule made from lactic acid, which is itself available in large quantities by harvesting plants rather than drilling for oil. Lactide can be turned into polymers with remarkable properties, which in turn degrade down easily back to lactic acid. A perfect bio-renewable material!

HypervalencyInteresting ChemistryElectronic EnergyEnergyEnergy DensityChemieEnglisch
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In this post, I will take a look at what must be the most extraordinary small molecule ever made (especially given that it is merely a hydrocarbon). Its peculiarity is the region indicated by the dashed line below. Is it a bond? If so, what kind, given that it would exist sandwiched between two inverted carbon atoms?