Post Tagged with: "Christopher A. Reed"

When is a Proton not a Proton?

A recent article in Accounts of Chemical research discusses this very topic as well as some other interesting facts revolving around protons, their structure and their generation. What does H+ signify? Well it means different things to different disciplines. If you are a physicist it refers to one of the fundamental elementary particles, if you are a chemist it refers to a hydrogen ion. So what is it exactly? Well it is a very strong acid about 1056 times stronger than 100% sulphuric acid! Its place in chemistry is well documented even although you can only add H+ to a molecule in the gas phase whereas only a solvated proton can be added in less gaseous media. This has great implications for biology especially where proton pumping is an important function, thus the structure H(H2O)+turns out to be a very important structure. This is especially so because the degree of solvation affects the rate of protonation particularly in proton/electron transfer.

According to Professor Reed, the author of this article a self – ionising acid, HA is very unlikely to form a H2A+ cation, the structure is better represented by the following equation:

proton

In the last few years it has emerged that the H+ is a 2-coordinate species, however, even this may extend to multi-coordinate when hydrogen bonding is involved. So what is the structure of H+ in water? This turns out to be a very difficult question to answer, and several instrumental methods have been applied to solve this problem, including IR and x-ray crystallography. These two methods and lots of hours have turned up H13O6+ ions as the structure. The experimental evidence backing up this claim can be found in this paper, which is open access!

Talking about protons leads to the strongest acids known H(CHB11Cl11) or H(CHB11F11), however the latter species is very difficult to obtain due to the ease with which it gives up its proton. These acids can easily protonate benzene or better alkanes! They are very useful in the study of protonation due to the complete inertness of the anions that do not undergo the usual corrosive reactions associated with other types of super acids. The acid H(CHB11F11) protonates butane to give the t-butyl cation at room temperature. Ethyl chloride is also protonated by H(CHB11Cl11) with concomitant loss of HCl to give the diethyl chloronium salts which can be isolated.

Oxatriquinanes are tricyclic analogues of the H3O+ ion. These very strong acids can H-bond to the last lone pair of oxatriquinane, which is a tetravalent oxygen species with a 2+ charge and is an analogue of the H4O2+ ion.

The Oxatriquinane oxonium cation.

ion

 

So if you are searching for a proton source not accompanied by the usual destructive counter ions try one of these carborane acids.

By August 8, 2013 6 comments science news

Most Popular Chemistry Paper for March 2012

Like January 2012, the most accessed paper for March 2012 on ChemFeeds was a small feature in Angewandte highlighting winners receiving recognition for their work, in this case the ACS 2012 National award. The winners in no particular order were David O’Hagan, Arnold L. Rheingold, Philip P. Power, Jonathan A. Ellman, Christopher A. Reed, Stephen Hanessian, Mitsuo Kira, Enrique Iglesia (not to be confused with the famous singer), and Raymond E. Schaak.

However, the honor of being the most highly accessed original science article was shared by two different JACS papers:

Reisman graphical abstract
Aiwen Lei graphical abstract

The paper with the most eye-catching graphical abstract goes to Young-Jae Oh and Ki-Hun Jeong for their Advanced Materials paper titled, “Glass Nanopillar Arrays with Nanogap-Rich Silver Nanoislands for Highly Intense Surface Enhanced Raman Scattering“.

Mitch
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By April 4, 2012 2 comments ChemFeeds