In a comment appended to an earlier post, I mused about the magnitude of the force constant relating to the interconversion between a classical and a non-classical structure for the norbornyl cation. Most calculations indicate the force constant for an “isolated” symmetrical cation is +ve, which means it is a true minimum and not a transition state for a [1,2] shift. The latter would have been required if the species equilibrated between two classical carbocations. I then pondered what might happen to both the magnitude and the sign of this force constant if various layers of solvation and eventually a counter-ion were to be applied to the molecule, so that a bridge of sorts between the different states of solid crystals, superacid and aqueous solutions might be built.
Posts Tagged ‘Paul Schleyer’
What is the (calculated) structure of a norbornyl cation anion-pair in water?
Saturday, April 1st, 2017Benzene: an oscillation or a vibration?
Wednesday, May 28th, 2014In the preceding post, a nice discussion broke out about Kekulé’s 1872 model for benzene.[cite]10.1002/jlac.18721620110[/cite] This model has become known as the oscillation hypothesis between two extreme forms of benzene (below). The discussion centered around the semantics of the term oscillation compared to vibration (a synonym or not?) and the timescale implied by each word. The original article is in german, but more significantly, obtainable only with difficulty. Thus I cannot access[cite]10.1002/jlac.18721620110[/cite] the article directly since my university does not have the appropriate “back-number” subscription.‡ So it was with delight that I tracked down an English translation in a journal that I could easily access.[cite]10.1039/JS8722500605[/cite] Here I discuss what I found (on pages 614-615, the translation does not have its own DOI).
Patterns of behaviour: serendipity in action for enantiomerisation of F-S-S-Cl
Thursday, September 19th, 2013Paul Schleyer sent me an email about a pattern he had spotted, between my post on F3SSF and some work he and Michael Mauksch had done 13 years ago with the intriguing title “Demonstration of Chiral Enantiomerization in a Four-Atom Molecule“.[cite]http://doi.org/d8g2nw[/cite] Let me explain the connection, but also to follow-up further on what I discovered in that post and how a new connection evolved.
Halogen bonds: Part 1.
Saturday, November 29th, 2014Halogen bonds are less familiar cousins to hydrogen bonds. They are defined as non-covalent interactions (NCI) between a halogen atom (X, acting as a Lewis acid, in accepting electrons) and a Lewis base D donating electrons; D….X-A vs D…H-A. They are superficially surprising, since both D and X look like electron rich species. In fact the electron distribution around X-X (A=X) is highly anisotropic, with the electron rich distribution (the "donor") being in a torus encircling the bond, and an electron deficient region (the "acceptor") lying along the axis of the bond.
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Tags:crystal structure search, D. Note, frequent commentator, Paul Schleyer
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