The Chemical and Physical Properties of Polychalcogens

The optimized synthesis of acyclic dialkoxy
disulfides and aromatic polysulfides is described and
their physical properties probed. In particular, the
origin of the high barrier to rotation in the
dialkoxy disulfides was determined to be due to a
generalized anomeric effect. The origin of the high
rotational barrier was also verified experimentally.
Complimentary to this thermal process, the
decomposition of dialkoxy disulfides was also
investigated.

Theoretical modeling on the relative ground state
energies of dialkoxy disulfides is also described.
It has been ascertained that the equilibrium position
between the two isomers can be influenced by the ring
size of the molecule; larger rings promote the
dialkoxy disulfide isomer. These modeling studies
were successfully corroborated experimentally.

The kinetics of desulfurization of acyclic aromatic
tri- and tetrasulfides is described. Tetrasulfides
were found to transfer a sulfur atom to
triphenylphosphine over ten times faster than their
trisulfide analogues.

Autorentext

Eli Zysman-Colman received his BSc in physics from McGill. Hecompleted his doctorate with D.N. Harpp, also at McGill. In 2004,he began a postdoc at the Universität Zürich with J.S. Siegel. In2006 he began a postdoc at Princeton with S. Bernhard. In July,2007 he began as an assistant professor at the Université deSherbrooke.

Klappentext

The optimized synthesis of acyclic dialkoxydisulfides and aromatic polysulfides is described andtheir physical properties probed. In particular, theorigin of the high barrier to rotation in thedialkoxy disulfides was determined to be due to ageneralized anomeric effect. The origin of the highrotational barrier was also verified experimentally. Complimentary to this thermal process, thedecomposition of dialkoxy disulfides was alsoinvestigated. Theoretical modeling on the relative ground stateenergies of dialkoxy disulfides is also described. It has been ascertained that the equilibrium positionbetween the two isomers can be influenced by the ringsize of the molecule; larger rings promote thedialkoxy disulfide isomer. These modeling studieswere successfully corroborated experimentally. The kinetics of desulfurization of acyclic aromatictri- and tetrasulfides is described. Tetrasulfideswere found to transfer a sulfur atom totriphenylphosphine over ten times faster than theirtrisulfide analogues.