Following on from discussing octet expansion in species such as SeMe ₆ , ClMe ₃ and ClMe ₅ , I felt impelled to return to SF ₆ , often used as an icon for hypervalence.

A few years back, I took a look at the valence-shell electron pair repulsion approach to the geometry of chlorine trifluoride, ClF ₃ using so-called ELF basins to locate centroids for both the covalent F-Cl bond electrons and the chlorine lone-pair electrons.

One thread that runs through this blog is that of hypervalency. It was therefore nice to come across a recent review of the concept[cite]10.1039/c5sc02076j[/cite] which revisits the topic, and where a helpful summary is given of the evolving meanings over time of the term hypervalent.

An N-B single bond is iso-electronic to a C-C single bond, as per below. So here is a simple question: what form does the distribution of the lengths of these two bonds take, as obtained from crystal structures?  The Conquest search query is very simple (no disorder, no errors). When applied to the Cambridge structure database (CSD) the following two distributions are obtained.

Mention carbon dioxide (CO ₂ ) to most chemists and its properties as a metal ligand are not the first aspect that springs to mind. Here thought I might take a look at how it might act as such.

Back in the early 1990s, we first discovered the delights of searching crystal structures for unusual bonding features.[cite]10.1039/P29940000703[/cite] One of the first cases was a search for hydrogen bonds formed to the π-faces of alkenes and alkynes. In those days the CSD database of crystal structures was a lot smaller (<80,000 structures; it’s now ten times larger) and the search software less powerful.

Layer stacking in structures such as graphite is well-studied. The separation between the π-π planes is ~3.35Å, which is close to twice the estimated van der Waals (vdW) radius of carbon (1.7Å). But how much closer could such layers get, given that many other types of relatively weak interaction such as hydrogen bonding can contract the vdW distance sum by up to ~0.8Å or even more?

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.

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.