ChemInform Abstract: DIASTEREOMERIC ORGANOPHOSPHORUS COMPOUNDS, I. SYNTHESIS AND PROPERTIES OF CH3(TERT‐C4H9)P(X)‐Y‐(Z)P(TERT‐C4H9)CH3

Abstract

Die Umsetzung des Phosphinchlorids (II) mit H2S führt abhängig von den Reaktionsbedingungen zu dem Diastereomerengemisch des Diphosphinmonosulfids (Ia)/(Ib) und dem Phosphinsulfid (Ic) oder nur zu (Ic).

Understanding Reactive Sulfur Species through P/S Synergy

“…15 Although R 3 P motifs, such as tris(2carboxylethyl)phosphine (TCEP), 16 are commonly used to generate P=S bonds from S 0 -containing species, even H 2 S can be converted into a P=S bond in the presence of a chlorophosphine and base (Figure 1b). 17 As another example of activation, the diphosphine disulfide species [Ph 2 P(S)] 2 can insert S into a P−P bond to form mixed P(V)/P(III) species when irradiated with >300 nm light (Figure 1c). 18 Although P=S species are generally thermodynamically stable, 19 the electrochemical reduction of diphenyl dithiophosphinic acid (S=PPh 2 SH) can afford bis(diphenylphosphanyl)tetrasulfide (Figure 1d).…”

“…Considering the prevalence of P­(V) species in biology, P­(III) represents an excellent potential reaction partner with sulfur because P=S bonds are also extremely stable and thermodynamically favorable to form from highly reducing P­(III) starting materials . Although R 3 P motifs, such as tris­(2-carboxylethyl)­phosphine (TCEP), are commonly used to generate P=S bonds from S 0 -containing species, even H 2 S can be converted into a P=S bond in the presence of a chlorophosphine and base (Figure b) . As another example of activation, the diphosphine disulfide species [Ph 2 P­(S)] 2 can insert S into a P–P bond to form mixed P­(V)/P­(III) species when irradiated with >300 nm light (Figure c) .…”