SF and SC Activation of SF₆ and SF₅ Derivatives at Rhodium: Conversion of SF₆ into H₂S

Abstract

The degradation of SF 6 and SF 5 organyls by S À F and S À C bond-activation reactions at [{Rh(m-H)(dippp)} 2 ] under mild conditions is reported. Fluorido and thiolato species were identified as products or intermediates, and were characterized by X-ray diffraction analysis and multinuclear NMR spectroscopy. An unprecedented cyclic process for the conversion of the potent greenhouse gas SF 6 into H 2 S was developed.

The Activation of Sulfur Hexafluoride at Highly Reduced Low‐Coordinate Nickel Dinitrogen Complexes

“…[10] Angewandte Chemie Subsequently, I reacts further with SF x and unconsumed SF 6 , respectively, to give 1 and 2 in a 2:1 ratio. [6,13] Herein we showed that SF 6 (as well as SF 5 Ph) can be converted within the coordination sphere of a reduced nickel atom bound by bdiketiminato ligands. Attempts to identify the SF x species were unsuccessful.…”

“…Still, reports on successful SF 6 activation at transition-metal centers are scarce. [6,13] Herein we showed that SF 6 (as well as SF 5 Ph) can be converted within the coordination sphere of a reduced nickel atom bound by bdiketiminato ligands. Additionally, we have successfully identified the resulting fluoride and sulfide products, which are very interesting complexes in their own rights: 1 is the first structurally characterized three-coordinate nickel fluoride complex, while 2 is a rare example of a transition-metal complex exhibiting an almost linear [Ni(m-S)Ni] 2+ arrangement.…”

Aktivierung von Schwefelhexafluorid an hoch reduzierten niedrig koordinierten Nickel‐Distickstoff‐Komplexen

“…Dennoch sind Beispiele für eine erfolgreiche SF 6 -Aktivierung an Übergangsmetallzentren rar. [6,13] Hier berichten wir, dass das inerte SF 6 -Molekül (ebenso wie dessen Derivat SF 5 Ph) bereits unter Standardbedingungen in der Koordinationssphäre von reduzierten, mit b-Diketiminato-Liganden versehenen Nickelatomen aktiviert werden kann. Zudem konnten wir die entstehenden fluor-und schwefelhaltigen Reaktionsprodukte identifizieren, die selbst außergewçhnliche Komplexe darstellen: Bei 1 handelt es sich um den ersten strukturell charakterisierten dreifach koordinierten Nickel-Fluorido-Komplex, während 2 ein seltenes Beispiel für einen Übergangsmetallkomplex mit einer nahezu linearen [Ni(m-S)Ni] 2+ -Anordnung darstellt.…”