X-ray structures and oxidative electrochemistry of phosphine sulfides and phosphine selenides

作者：Tiedemann Margaret A; Mandell Chelsea L; Chan Benny C; Nataro Chip^*

来源：Inorganica Chimica Acta, 2014, 422: 193-201.

DOI：10.1016/j.ica.2014.06.004

• Cyclic voltammetry
• Electrochemistry
• X-ray crystal structures
• Phosphine sulfide
• Phosphine selenide

A variety of mono- and bisphosphine sulfides and selenides were synthesized and structurally characterized by NMR spectroscopy. In addition, the X-ray crystal structures were determined for eleven of these compounds. The percent buried volume was determined from the X-ray structures and the use of this measurement in estimating the steric bulk in phosphine sulfides and selenides was further developed. The oxidation of the mono-and bisphosphine chalcogenides was examined using cyclic voltammetry in methylene chloride and acetonitrile. The solvent had little effect on the observed trends in the potentials at which oxidation occurred. Both the mono-and bisphosphine chalcogenides display an irreversible oxidative wave. Many of the phosphine selenides also display a follow-up, irreversible reductive wave indicative of the formation of a Se-Se bond upon oxidation. However, the products for the oxidation of the phosphine selenides could not be isolated by chemical oxidation. The potential at which oxidation of the phosphine sulfides occurs is more positive than the analogous phosphine selenides.

• 出版日期2014-10-1