Following my conformational exploration of enols, here is one about a much more common molecule, a carboxylic acid. The components of the search are shown as four queries below, which will be combined in various Boolean senses (DOI: 10.14469/hpc/2462). Query one defines the carboxylic acid, with 3-coordinate carbon specified at the carbonyl along with 1-coordinate for the carbonyl oxygen.

Both the cyclopropenium cation and the cyclopentadienide anion are well-known 4n+2-type aromatic ions, but could the two together form an ion-pair? A search of the Cambridge structure database reveals 52 instances of the cyclopropenium cation with a variety of counter-anions, 77 cyclopentadienide anions with a variety of counter-cations and one (SOWMOG, private communication to CSD) where the two sub-structures are common.

Enols are simple compounds with an OH group as a substituent on a C=C double bond and with a very distinct conformational preference for the OH group. Here I take a look at this preference as revealed by crystal structures, with the theoretical explanation.

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.

Nowadays, data supporting most publications relating to the synthesis of organic compounds is more likely than not to be found in associated “supporting information “ rather than the (often page limited) article itself. For example, this article[cite]10.1021/jacs.6b13229[/cite] has an SI which is paginated at 907;

Occasionally one comes across a web site that manages to combine being unusual, interesting and also useful. Thus www.molinsight.net is I think a unique chemistry resource for blind and visually impaired students. If you think perhaps that it might be a little too specialised to be useful for you, go visit it first.

In an era when alternative facts and fake news afflict us, the provenance of scientific data becomes ever more important. Especially if that data is available as open access and exploitable by others for both valid scientific reasons but potentially also by those with other motives.

The previous post demonstrated the simple iso-electronic progression from six-coordinate carbon to five coordinate nitrogen. Here, a further progression to oxygen is investigated computationally. The systems are formally constructed from a cyclobutadienyl di-anion and firstly the HO ⁵⁺ cation, giving a tri-cationic complex. There are no examples of the resulting motif in the Cambridge structure database.

A few years back I followed a train of thought here which ended with hexacoordinate carbon, then a hypothesis rather than a demonstrated reality. That reality was recently confirmed via a crystal structure, DOI:10.5517/CCDC.CSD.CC1M71QM[cite]10.1002/anie.201608795[/cite]. Here is a similar proposal for penta-coordinate nitrogen. First, a search of the CSD (Cambridge structure database) for such nitrogen.

It is not only the non-classical norbornyl cation that has proved controversial in the past. A colleague mentioned at lunch (thanks Paul!) that tri-coordinate group 14 cations such as R ₃ Si ⁺ have also had an interesting history.[cite]10.1021/ja990389u[/cite] Here I take a brief look at some of these systems. Their initial characterisations, as with the carbon analogues, was by ²⁹ Si NMR.

The example a few posts back of how methane might invert its configuration by transposing two hydrogen atoms illustrated the reaction mechanism by locating a transition state and following it down in energy using an intrinsic reaction coordinate (IRC). Here I explore an alternative method based instead on computing a molecular dynamics trajectory (MD). I have used ethane instead of methane, since it is now possible to