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Henry Rzepa's Blog

Henry Rzepa's Blog
Chemistry with a twist
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Reaction MechanismChemistryMethaneMolecular GeometryOrbital HybridisationCiencias QuímicasInglés
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This is a spin-off from the table I constructed here for further chemical examples of the classical/non-classical norbornyl cation conundrum. One possible entry would include the transition state for inversion of methane via a square planar geometry as compared with e.g. NiH 4 for which the square planar motif is its minimum.

Interesting Chemistry2-Norbornyl CationAqueous SolutionsChemical BondChemical InstrumentationCiencias QuímicasInglés
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George Olah passed away on March 8th. He was part of the generation of scientists in the post-war 1950s who had access to chemical instrumentation that truly revolutionised chemistry.

Crystal_structure_miningAmmoniaAmmoniumAromaticityCationsCiencias QuímicasInglés
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A few years back, I did a post about the Pirkle reagent[cite]10.1039/c39910000765[/cite] and the unusual π-facial hydrogen bonding structure[cite]10.1039/P29940000703[/cite] it exhibits. For the Pirkle reagent, this bonding manifests as a close contact between the acidic OH hydrogen and the edge of a phenyl ring; the hydrogen bond is off-centre from the middle of the aryl ring.

Chemical ITAPIChemical DatabasesCity: LondonCompany: TfLCiencias QuímicasInglés
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Living in London, travelling using public transport is often the best way to get around. Before setting out on a journey one checks the status of the network. Doing so today I came across this page: our open data from Transport for London.  I learnt that by making TFL travel data openly available, some 11,000 developers (sic!) have registered for access, out of which some 600 travel apps have emerged.

Crystal_structure_miningAntiaromaticityChemistryCyclobutadieneInstabilityCiencias QuímicasInglés
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Cyclobutadiene is one of those small iconic molecules, the transience and instability of which was explained theoretically long before it was actually detected in 1965.[cite]10.1021/ja01092a049[/cite] Given that instability, I was intrigued as to how many crystal structures might have been reported for this ring system, along with the rather more stable congener cyclo-octatetraene. Here is what I found.

Interesting ChemistryChemical BondingChemistryElectrideFree EnergyCiencias QuímicasInglés
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The thread thus far. The post about Na 2 He introduced the electride anionic counter-ion to Na + as corresponding topologically to a rare feature known as a non-nuclear attractor. This prompted speculation about other systems with such a feature, and the focus shifted to a tetrahedral arrangement of four hydrogen atoms as a dication, sharing a total of two valence electrons. The story now continues here.

Interesting ChemistryAttractorBrief SearchChemistryElectronCiencias QuímicasInglés
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This post arose from a comment attached to the post on Na 2 He and relating to peculiar and rare topological features of the electron density in molecules called non-nuclear attractors. This set me thinking about other molecules that might exhibit this and one of these is shown below.

Interesting ChemistryBromineBromine TrifluorideChemical ElementsChemistryCiencias QuímicasInglés
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I analysed the bonding in chlorine trifluoride a few years back in terms of VSEPR theory. I noticed that several searches on this topic which led people to this post also included a query about the differences between it and the bromine analogue. For those who posed this question, here is an equivalent analysis.

Bond SlamCrystal_structure_miningInteresting Chemistry10.1038AtomCiencias QuímicasInglés
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On February 6th I was alerted to this intriguing article[cite]10.1038/nchem.2716[/cite] by a phone call, made 55 minutes before the article embargo was due to be released. Gizmodo wanted to know if I could provide an (almost) instant quote. After a few days, this report of a stable compound of helium and sodium still seems impressive to me and I now impart a few more thoughts here.

Historical2001-2050Alfred NobelBill GriffithCountry: United KingdomCiencias QuímicasInglés
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The book of the title has recently appeared giving a rich and detailed view over 417 pages, four appendices and 24 pages of photographs of how a university chemistry department in the UK came into being in 1845 and its subsequent history of discoveries, Nobel prizes and much more.