Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride)

Jiří Hanusek, Mark A. Russell, Andrew P. Laws, Petr Jansa, John H. Atherton, Kevin Fettes, Michael I. Page

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Contrary to a previous report, the sulfurisation of phosphorus(iii) derivatives by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products. The reaction of xanthane hydride with triphenyl phosphine or trimethyl phosphite yields triphenyl phosphine sulfide or trimethyl thiophosphate, respectively, and thiocarbamoyl isothiocyanate which has been trapped with nucleophiles. The reaction pathway involves initial nucleophilic attack of the phosphorus at sulfur next to the thiocarbonyl group of xanthane hydride followed by decomposition of the phosphonium intermediate formed to products. The Hammett ρ-values for the sulfurisation of substituted triphenyl phosphines and triphenyl phosphites in acetonitrile are ∼ -1.0. The entropies of activation are very negative (-114 ± 15 J mol-1 K-1) with little dependence on solvent which is consistent with a bimolecular association step leading to the transition state. The negative values of ΔS and ρ values indicate that the rate limiting step of the sulfurisation reaction is formation of the phosphonium ion intermediate which has an early transition state with little covalent bond formation. The site of nucleophilic attack has been also confirmed using computational calculations.

Original languageEnglish
Pages (from-to)478-484
Number of pages7
JournalOrganic and Biomolecular Chemistry
Volume5
Issue number3
Early online date18 Dec 2006
DOIs
Publication statusPublished - 7 Feb 2007

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Phosphines
Phosphites
phosphine
phosphines
hydrides
attack
trimethyl phosphite
phosphorus
cyanamides
Phosphorus
carbon disulfide
nucleophiles
Cyanamide
covalent bonds
Carbon Disulfide
reaction products
Nucleophiles
acetonitrile
Covalent bonds
sulfides

Cite this

Hanusek, Jiří ; Russell, Mark A. ; Laws, Andrew P. ; Jansa, Petr ; Atherton, John H. ; Fettes, Kevin ; Page, Michael I. / Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride). In: Organic and Biomolecular Chemistry. 2007 ; Vol. 5, No. 3. pp. 478-484.
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Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride). / Hanusek, Jiří; Russell, Mark A.; Laws, Andrew P.; Jansa, Petr; Atherton, John H.; Fettes, Kevin; Page, Michael I.

In: Organic and Biomolecular Chemistry, Vol. 5, No. 3, 07.02.2007, p. 478-484.

Research output: Contribution to journalArticle

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