Monitoring structural transformations in crystals. 6. The [4 + 4] photodimerization of 9-methylanthracene

The structural changes in a crystal of 9-methylanthracene (1) during the [4 + 4] photodimerization were monitored by means of X-ray diffraction. This is the first example in the literature of such a study of a [4 + 4] photodimerization. The results obtained were compared with data for the [2 + 2] photodimerization. The shape of the product molecules and their preferred packing can explain the crystal disintegration. This was the reason that the reaction was monitored only to 28% completion. As far as could be determined the reaction proceeds with a constant rate. The cell volume increases at the beginning of the transformation and decreases afterwards. The product molecules do not assume a fixed position in the crystal during the photo-reaction, but move in a smooth way that includes a rotational component. The movements of the reactant are much smaller. Movements of molecules characterized by a rotational component were also observed in the case of the [2 + 2] photodimerization of 5-benzylidene-2-benzylcyclopentanone and 5-benzylidene-2-(4-chlorobenzyl)-cyclopentanone. The distance between the reacting atoms of the adjacent monomer molecules of (1) decreases with the degree of reaction completion, but more slowly than in the case of the [2 + 2] photodimerizations cited above. The orientation of the neighbouring monomer molecules changes during the phototransformation so that the monomer pair resembles the dimer product.

Electrical conductivity of fused lead bromide + potassium bromide mixtures

Bridge-terminal exchange of methyl groups in trimethylaluminium dimer and the exchange of methyl groups between the dimer and trimethylgallium or dimethylzinc are all interpreted as proceeding by initial rate-determining dissociation of the trimethyl-aluminium dimer to liquid-caged monomer pair. Most exchange occurs before the monomers of the pair become separated. An alternative mechanism in which exchange follows separation is rejected. ��� The choice of mechanism is based on (a) p.m.r. kinetics of exchange between trimethylgallium and trimethylaluminium in cyclopentane; (b) p.m.r. kinetics of exchange between dimethylzinc and trimethylaluminium in cyclopentane; and (c) estimates of the rate of recombination of trimethylaluminium monomer.