The Chemical and Physical Properties of Polychalcogens : Dialkoxydisulfides, Thionosulfites and Polysulfides

ISBN-13: 9783639148954 / Angielski / Miękka / 2009 / 500 str.

Eli Zysman-Colman

Opis

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.

O autorze

Eli Zysman-Colman received his BSc in physics from McGill. He
completed his doctorate with D.N. Harpp, also at McGill. In 2004,
he began a postdoc at the Universität Zürich with J.S. Siegel. In
2006 he began a postdoc at Princeton with S. Bernhard. In July,
2007 he began as an assistant professor at the Université de
Sherbrooke.