Bromoallene is a pretty simple molecule, with two non-equivalent double bonds. How might it react with an electrophile, say dimethyldioxirane (DMDO) to form an epoxide?[cite]10.1039/C6CC06395K[/cite] Here I explore the difference between two different and very simple approaches to predicting its reactivity. 
Posts Tagged ‘lowest energy’
Molecule orbitals as indicators of reactivity: bromoallene.
Thursday, September 1st, 2016A molecular balance for dispersion energy?
Sunday, February 7th, 2016The geometry of cyclo-octatetraenes differs fundamentally from the lower homologue benzene in exhibiting slow (nuclear) valence bond isomerism rather than rapid (electronic) bond-equalising resonance. In 1992 Anderson and Kirsch[cite]10.1039/P29920001951[/cite] exploited this property to describe a simple molecular balance for estimating how two alkyl substituents on the ring might interact via the (currently very topical) mechanism of dispersion (induced-dipole-induced-dipole) attractions. These electron correlation effects are exceptionally difficult to model using formal quantum mechanics and are nowadays normally replaced by more empirical functions such as Grimme's D3BJ correction.[cite]10.1002/jcc.21759[/cite] Here I explore aspects of how the small molecule below might be used to investigate the accuracy of such estimates of dispersion energies.
How to predict the regioselectivity of epoxide ring opening.
Sunday, April 28th, 2013I recently got an email from a student asking about the best way of rationalising epoxide ring opening using some form of molecule orbitals. This reminded me of the famous experiment involving propene epoxide.[cite]10.1021/ja01208a047[/cite]