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Henry Rzepa's Blog

Henry Rzepa's Blog
Chemistry with a twist
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HypervalencyGas PhaseMt. EverestPenceChemieEnglisch
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Climbers scale Mt. Everest, because its there , and chemists have their own version of this. Ever since G. N. Lewis introduced the concept of the electron-pair bond in 1916, the idea of a bond as having a formal bond-order has been seen as a useful way of thinking about molecules. The initial menagerie of single, double and triple formal bond orders (with a few half sizes) was extended in the 1960s to four, and in 2005 to five.

Interesting ChemistryChairConformational AnalysisFinal Resting EnergyFree EnergyChemieEnglisch
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In an earlier post, I re-visited the conformational analysis of cyclohexane by looking at the vibrations of the entirely planar form (of D 6h symmetry). The method also gave interesting results for the larger cyclo-octane ring. How about a larger leap into the unknown? Let us proceed as follows. One fun game to play in chemistry is to invoke i so-electronic substitutions.

GeneralInteresting ChemistryAdolf Von BaeyerAnimationCChemieEnglisch
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Like benzene, its fully saturated version cyclohexane represents an icon of organic chemistry. By 1890, the structure of planar benzene was pretty much understood, but organic chemistry was still struggling somewhat to fully embrace three rather than two dimensions. A grand-old-man of organic chemistry at the time, Adolf von Baeyer, believed that cyclohexane too was flat, and what he said went.

HypervalencyInteresting ChemistryBondQuadrupleChemieEnglisch
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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 unlikeliest of bonds, a quadruple Cr-Cr bond, found in the compound di-μ-trimethylsilylmethyl-bis-[(tri-methylphosphine)

Chemical ITRDFSemanticChemieEnglisch
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A Semantic blog is one in which the system at least in part understands about (some of the) concepts and topics that are in the content. The idea is that this content can be more intelligently (is that the correct word?) and importantly, automatically searched, harvested, and connected to the same or similar concepts found elsewhere in other blogs and the Web as whole.

Chemical ITGeneric SolutionChemieEnglisch
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After around 40 posts here, I decided to take a look at the whole effort and ask some questions. For example Should (scientific) blogs be used to report new science, or merely opinion on existing science (see this blog also)? If the former, should they be abstracted in the manner of regular articles (e.g. by CAS etc). Unlike e.g. a journal, a blog is often (and certainly in this case) the effort of an individual.

HypervalencyInteresting ChemistryAromaticityPericyclicSouth CarolinaChemieEnglisch
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In the previous post, the molecule F3S-C≡SF3 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 284i cm-1) to interconversion of the two valence-bond forms.

HypervalencyInteresting ChemistryAnimationCalculated Free Energy BarrierInorganic ChemistChemieEnglisch
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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?