Dihydrophenanthrene Open-Shell Singlet Diradicals and Their Roles in the Mallory Photocyclization Reaction.

A computational study (ωB97X-D/6-31G(d)) of the Mallory photocyclization reaction has revealed that the well-established dihydrophenanthrene (DHP) intermediates can adopt either closed-shell (CS) or open-shell-diradical (OS) singlet ground states. A detailed study of the properties of DHPs allowed their classifications as OS, borderline-OS, borderline-CS, or CS intermediates. The triplet electronic state and higher energy CS* isomer of all the OS singlet diradicals were computationally located, and the expected relationship between the diradical index, , and the triplet energy and the OS-CS* energy gaps was established.

Structure-Activity Relationships for Psilocybin, Baeocystin, Aeruginascin, and Related Analogues to Produce Pharmacological Effects in Mice.

4-Phosphoryloxy-,-dimethyltryptamine (psilocybin) is a naturally occurring tertiary amine found in many mushroom species. Psilocybin is a prodrug for 4-hydroxy-,-dimethyltryptamine (psilocin), which induces psychedelic effects via agonist activity at the serotonin (5-HT) 2A receptor (5-HT). Several other 4-position ring-substituted tryptamines are present in psilocybin-containing mushrooms, including the secondary amine 4-phosphoryloxy--methyltryptamine (baeocystin) and the quaternary ammonium 4-phosphoryloxy-,,-trimethyltryptamine (aeruginascin), but these compounds are not well studied.

Self-assembly of an organometallic FeO cluster from aerobic oxidation of (tmeda)Fe(CHBu).

Aerobic oxidation of (tmeda)Fe(CHBu) in toluene or THF solution leads to the self-assembly of a magic-sized all-ferrous oxide cluster containing the FeO subunit and bearing organometallic and diamine ligands. Mössbauer studies of the cluster are consistent with an all-ferrous assignment and magnetometry reveals complex intracluster and intercluster magnetic interactions.

Electrostatic polarization of nonpolar substrates: a study of interactions between simple cations and Mo-bound N.

Although a great deal of catalytic studies have focused on covalent interactions between substrates and catalyst centers, recognition of the importance of noncovalent and ionic interactions is driving new approaches to catalyst design. Electrostatic interactions with simple cations (those with little covalency, such as alkali metals) play crucial roles in many catalytic processes, but these effects are challenging to study due to their complicated solvation and speciation behaviour. These effects are particularly difficult to study during cation-mediated reactions with weakly-polar or non-polar substrates.