Reactivity of X3P compounds with elemental sulfur, carbon disulfide or both, to yield X3PS, X3RCS2 or X3P.Sn.CS2 adducts

Article abstract of DOI:10.1080/10426509808545471

Kinetic constants k₂ have been obtained for the reaction of sulfur with 25 P^III compounds in toluene or hexane. In the series Ph_nMe_3-nP (n = 1-3) or Ph_nBu_3-nP (n = 0-3), log k₂ decreases linearly with Σχ_i (χ_i=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 Ph_nP(OEt)_3-n, Ph_nP(OEt)3_-n, and Bu_nP(OEt)_3-n(n = 0-3); the deviation is smaller for Ph_nPCl_3-n, and even smaller for Ph_nP(NEt₂)_3-n . The results are discussed in terms of P-coordination (P^IV vs. P_V), 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.S_n.CS₂ (ternary yellow adduct) respectively; an explanation for this parallelism is proposed.

Full text of DOI:10.1080/10426509808545471

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Phosphorus, Sulfur, and
Silicon and the Related
Elements
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Reactivity of X3P
Compounds with
Elemental Sulfur, Carbon
Disulfide or Both, to Yield
X3PS, X3P.CS2 or X3P.Sn.CS2
Adducts
Michel C. Démarcq
a Institut National des Sciences Appliquées,
Laboratoire de Chimie Organique ,
20 Avenue Albert Einstein, F-69621
Villeurbanne Cedex, France
Published online: 17 Mar 2008.
To cite this article: Michel C. Démarcq (1998) Reactivity of X3P Compounds
with Elemental Sulfur, Carbon Disulfide or Both, to Yield X3PS, X3P.CS2 or
X3P.Sn.CS2 Adducts, Phosphorus, Sulfur, and Silicon and the Related Elements,
134:1, 307-320, DOI: 10.1080/10426509808545471
To link to this article: http://dx.doi.org/10.1080/10426509808545471
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