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Henry Rzepa's Blog

Henry Rzepa's Blog
Chemistry with a twist
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Bond SlamCrystal_structure_miningHypervalencyInteresting ChemistryAromatic SystemsChemical Sciences
Published

A few years back I followed a train of thought here which ended with hexacoordinate carbon, then a hypothesis rather than a demonstrated reality. That reality was recently confirmed via a crystal structure, DOI:10.5517/CCDC.CSD.CC1M71QM. Here is a similar proposal for penta-coordinate nitrogen.

Crystal_structure_mining2-Norbornyl CationCarbocationsChemical BondingChemistryChemical Sciences
Published

It is not only the non-classical norbornyl cation that has proved controversial in the past. A colleague mentioned at lunch (thanks Paul!) that tri-coordinate group 14 cations such as R3Si+ have also had an interesting history. Here I take a brief look at some of these systems.

Reaction MechanismAnimationChemical ReactionChemistryComputational ChemistryChemical Sciences
Published

The example a few posts back of how methane might invert its configuration by transposing two hydrogen atoms illustrated the reaction mechanism by locating a transition state and following it down in energy using an intrinsic reaction coordinate (IRC). Here I explore an alternative method based instead on computing a molecular dynamics trajectory (MD).

Reaction MechanismChemistryMethaneMolecular GeometryOrbital HybridisationChemical Sciences
Published

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. NiH4 for which the square planar motif is its minimum.

Chemical ITAPIChemical DatabasesCity: LondonCompany: TfLChemical Sciences
Published

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.