5958-59-8Relevant academic research and scientific papers
Reactivity of X3P compounds with elemental sulfur, carbon disulfide or both, to yield X3PS, X3RCS2 or X3P.Sn.CS2 adducts
Demarcq, Michel C.
, p. 307 - 320 (1998)
Kinetic constants k2 have been obtained for the reaction of sulfur with 25 PIII compounds in toluene or hexane. In the series PhnMe3-nP (n = 1-3) or PhnBu3-nP (n = 0-3), log k2 decreases linearly with Σχi (χi=Tolman's electronic parameter of each ligand on P), taken as a gauge for the donor strength of P. Dramatic deviations from additivity are observed for the series PhnP(OEt)3-n, PhnP(OEt)3-n, and BunP(OEt)3-n(n = 0-3); the deviation is smaller for PhnPCl3-n, and even smaller for PhnP(NEt2)3-n . The results are discussed in terms of P-coordination (PIV vs. PV), stability and geometry of the intermediate X3P.S8 or of the transition state leading to this adduct, emphasis being laid on the donor/acceptor character of the P site. A similar dependence on X governs the reactivity of X3P with S8, CS2 or both, to give X3PS, X3P.CS2 (binary red adduct) or X3P.Sn.CS2 (ternary yellow adduct) respectively; an explanation for this parallelism is proposed.
Highly atom-economic one-pot formation of three different C-P bonds: General synthesis of acyclic tertiary phosphine sulfides
Baccolini, Graziano,Boga, Carla,Mazzacurati, Marzia
, p. 4774 - 4777 (2007/10/03)
The reaction of benzothiadiphosphole 1 with an equimolar mixture of R 1MgBr and R2MgBr gave intermediate A′, which, after only 4-5 min, was treated with an equimolar amount of R3MgBr, giving the asymmetric phosphine PR1R2R3 in 45% overall yield (75-80% yield when R1 = R2 and 85-90% yield when R1 = R2 = R3) and the byproduct 6 in 90% yield. The treatment of 6 with PCl3 quantitatively regenerates the starting reagent 1. Treatment of the phosphines with elemental sulfur gave the corresponding sulfides.
