Synthesis of bis(trithio)phosphines by oxidative transfer of phosphorus(i)

Abstract

The synthesis of novel bis(trithio)phosphines is achieved by oxidative addition of tetrathiocins to the phosphorus(i) reagent [Pdppe][Br] in good yields under ambient conditions. These bis(trithio)phosphines and the related intermediate diphosphine species are characterized by X-ray diffraction and multinuclear NMR and a mechanism is proposed for the formation of these molecules. In contrast, the related reaction with diphenyldisulfide produces a mononuclear tris(phenylthio)phosphine.

Magnetic Bistability in Naphtho-1,3,2-dithiazolyl: Solid State Interconversion of a Thiazyl π-Radical and Its N–N σ-Bonded Dimer

“…The σ-bond parlance used here should be interpreted with caution. Unlike the localized P–P σ-bond in 1,3,2-dithiaphospholyl dimers, the net bonding orbital in the N–N σ-bonded DTA dimer (Figure S4), derived from the pairing of two radical SOMOs, remains delocalized with significant S–S π-overlap, in keeping with the short interannular S–S distance (3.23 Å).…”

Synthesis of Stable Potassium Phosphinophosphides and Reaction with Organosilyl Halides and Chlorophosphanes

“…Both symmetrically and asymmetrically substituted diphosphanes can be synthesized via dehydrocoupling, salt metathesis, and trimethylsilyl chloride (TMSCl or Me 3 SiCl) elimination reactions. A variety of symmetrically as well as asymmetrically substituted diphosphanes have been reported so far, containing B-substituted, , C-substituted, ,− Si-substituted, − N-substituted, ,,,,,,,− P-substituted, , O-substituted, S-substituted, − and H-substituted ,− P atoms. Despite this variety, the selective introduction of certain substituents to access diphosphanes with a defined substitution pattern remains challenging.…”