Oxidative Spaltung von Poly( o 1‐phenylendiselenid)

Oxidative Cleavage of Poly( o 1‐phenylenediselenide) Poly( o 1‐phenylenediselenide) is cleaved at the Se–Se bond by treatment with SOCl 2 to give benzene‐1,2‐bis(selenenyl chloride) ( 2 ) and benzene‐1,2‐bis(selenium trichloride) ( 3 ), respectively. In the solid state 2 is dimerized by Se…Se bonds whereas 3 is monomeric having terminal as well as intramolecular bridging Cl atoms. Treatment of 2 with SbCl 5 gives an ionic compound ( 4 ) with a dimeric cation exhibiting a weak SeSe bond and SbCl 6 – as a counterion 3 reacts with W(CO) 6 to give trigonal prismatic dicarbonyl bis( o 1‐phenylenediselenolato)tungsten ( 5 ).