If H3N+-O– is viable compared with its tautomer H2N-OH when carrying water bridges, then why not try H2O+-O– vs HO-OH?
Posts Tagged ‘Hydrogen bond’
Oxane oxide: a tautomer of hydrogen peroxide.
Friday, April 15th, 2016Azane oxide, a tautomer of hydroxylamine.
Friday, April 15th, 2016In the previous post I described how hydronium hydroxide or H3O+…HO–, an intermolecular tautomer of water, has recently been observed captured inside an organic cage[cite]10.1002/chem.201406383[/cite] and how the free-standing species in water can be captured computationally with the help of solvating water bridges. Here I explore azane oxide or H3N+-O–,‡ a tautomer of the better known hydroxylamine (H2N-OH).
Hydronium hydroxide: the why of pH 7.
Thursday, April 14th, 2016Ammonium hydroxide (NH4+…OH–) can be characterised quantum mechanically when stabilised by water bridges connecting the ion-pairs. It is a small step from there to hydronium hydroxide, or H3O+…OH–. The measured concentrations [H3O+] ≡ [OH–] give rise of course to the well-known pH 7 of pure water, and converting this ionization constant to a free energy indicates that the solvated ion-pair must be some ~19.1 kcal/mol higher in free energy than water itself.♣ So can a quantum calculation reproduce pH7 for water?
Bond stretch isomerism. Did this idea first surface 100 years ago?
Tuesday, February 9th, 2016The phenomenon of bond stretch isomerism, two isomers of a compound differing predominantly in just one bond length, is one of those chemical concepts that wax and occasionally wane.[cite]10.1016/S1631-0748(02)01380-2[/cite] Here I explore such isomerism for the elements Ge, Sn and Pb.
I’ve started so I’ll finish. Kinetic isotope effect models for a general acid as a catalyst in the protiodecarboxylation of indoles.
Sunday, January 10th, 2016Earlier I explored models for the heteroaromatic electrophilic protiodecarboxylation of an 3-substituted indole, focusing on the role of water as the proton transfer and delivery agent. Next, came models for both water and the general base catalysed ionization of indolinones. Here I explore general acid catalysis by evaluating the properties of two possible models for decarboxylation of 3-indole carboxylic acid, one involving proton transfer (PT) from neutral water in the presence of covalent un-ionized HCl (1) and one with PT from a protonated water resulting from ionised HCl (2).
Interactions responsible for the lowest energy structure of the trimer of fluoroethanol.
Friday, October 23rd, 2015Steve Bachrach on his own blog has commented on a recent article[cite]10.1002/anie.201505934[/cite] discussing the structure of the trimer of fluoroethanol. Rather than the expected triangular form with three OH—O hydrogen bonds, the lowest energy form only had two such bonds, but it matched the microwave data much better. Here I explore this a bit more.
The mechanism of borohydride reductions. Part 1: ethanal.
Sunday, April 12th, 2015Sodium borohydride is the tamer cousin of lithium aluminium hydride (LAH). It is used in aqueous solution to e.g. reduce aldehydes and ketones, but it leaves acids, amides and esters alone. Here I start an exploration of why it is such a different reducing agent.
