In 1890, chemists had to work hard to find out what the structures of their molecules were, given they had no access to the plethora of modern techniques we are used to in 2010. For example, how could they be sure what the structure of naphthalene was? Well, two such chemists, William Henry Armstrong (1847-1937) and his student William Palmer Wynne (1861-1950;

Reactions in cavities can adopt quite different characteristics from those in solvents. Thus first example of the catalysis of the Diels-Alder reaction inside an organic scaffold was reported by Endo, Koike, Sawaki, Hayashida, Masuda, and Aoyama[cite]10.1021/ja964198s[/cite], where the reaction shown below is speeded up very greatly in the presence of a crystalline lattice of the anthracene derivative shown below. A Diels-Alder reaction.

Curly arrows are something most students of chemistry meet fairly early on. They rapidly become hard-wired into the chemists brain. They are also uncontroversial! Or are they? Consider the following very simple scheme. Curly arrow pushing It represents protonation of an alkene by an acid.

The rather presumptious title assumes the laws and fundamental constants of physics are the same everywhere (they may not be). With this constraint (and without yet defining what is meant by strongest), consider the three molecules: Property  (CCSD/aug-cc-pVTZ) N≡N (H-N≡N) ⁺ (H-N≡N-H) ²⁺ NN length, Å 1.0967 1.0915 1.0795 NN stretch, cm ^-1 2418.8 2356.4

One approach to reporting science which is perhaps better suited to the medium of a blog than a conventional journal article is the opportunity to follow ideas in unexpected, even unconventional directions. Thus my third attempt, like a dog worrying a bone, to explore hypervalency.

Chemistry as the inspiration for art! The inspiration was the previous post. As for whether its art, you decide for yourself.

In the last post, IH ₇ was examined to see if it might exhibit true hypervalency. The iodine, despite its high coordination, turned out not to be hypervalent, with its (s/p) valence shell not exceeding eight electrons (and its d-shell still with 10, and the 6s/6p shells largely unoccupied). Instead, the 14 valence electrons (7 from H, 7 from iodine) fled to the H…H regions.

The Wikipedia page on hypervalent compounds reveals that the concept is almost as old as that of normally valent compounds.

The molecule below was characterised in 1996 (DOI: 10.1246/cl.1996.489) and given the name tris(dithiolene)vanadium (IV). No attempt was made in the original article to give this molecule a Lewis structure using Lewis electron pair bonds. This blog will explore some of the issues that arise when this is attempted. ¹ NAMPOG.

Many university chemistry departments, and mine is no exception, like to invite applicants to our courses to show them around. Part of the activities on the day is an “interview” in which the candidate is given a chance to shine. Over the years, I have evolved questions about chemistry which can form the basis of discussion, and I thought I would share one such question here.