27205-99-8Relevant articles and documents
On the reaction of bis(phosphothioyl)disulfanes with hydroxamic acids, part I: Ionic versus radical reaction pathways
Przychodzen, Witold,Chojnacki, Jaroslaw
, p. 271 - 282 (2008/09/19)
Among sodium N-alkyl-4-chlorobenzohydroxamates treated with bis(phosphothioyl)disulfanes >P(S)SSP(S)P(S) is phosphorothioyl, phosphonothioyl, and phosphinothioyl), only the N-methyl one yields quantitatively the respective O-phosphothioyl derivatives exhibiting complete inversion of configuration at phosphorus in a reaction whose products are inert toward dithiophosphate arising in the reaction. For branched N-alkyl benzohydroxamates, products of a SET process predominated. The mechanism of the title reaction is discussed.
Effect of solute-co-ordinating solvent interactions and temperature on the EPR and electronic spectra of bis(dithiophosphato)copper(II)
Yordanov, Nicola D.,Ranguelova, Kalina
, p. 1171 - 1180 (2007/10/03)
The self-redox reaction proceeding between two molecules of the complex bis(disubstituted-dithiophosphato)copper(II), CuII(R2-dtp)2, is studied by EPR and UV-VIS spectroscopy in DMFA, DMSO and pyridine. The effect of temperature and disulphide concentration in the solutions is also evaluated. The EPR spectra show that the g-values of CuII(R2-dtp)2 increase when it is dissolved in co-ordinating solvents, whereas the copper hyperfine splitting decreases compared to the corresponding values in non-co-ordinating solvents. Under the same conditions, a hypsochromic shift is observed in the maximal absorption at 420 nm of the electronic spectra which corresponds to the ligand-to-metal charge-transfer (LMCT) transition of the complex. The results are explained with the formation of axial or equatorial adducts between CuII(R2-dtp)2 and the co-ordinating solvents used. On the other hand, the molar absorptivity of the LMCT band and the intensity of the EPR spectrum increase strongly with the nature of the used co-ordinating solvent, the time after dissolution and the quantity of added disulphide. Both also depend on the size and shape of remote ligand substituents and they increase in the order Me2P(S)S-S(S)P(RO)2] to the CuII(R2-dtp)2 solution. As a result, the molar absorptivity value at the maximum of the LMCT band of Cu[(i-PrO)2-dtp]2 increases from 7.9×103 m-1dm3cm-1 immediately after dissolution to 2.9×104 m-1dm3cm-1. In DMSO and pyridine, the intensity of both the EPR signal and LMCT band of CuII(R2-dtp)2 continuously decrease after the preparation of the solutions. A small increase is only observed immediately after the addition of the corresponding disulphide of dithiophosphate. While DMFA forms stable adducts with Cu[(i-PrO)2-dtp]2, adduct formation with DMSO and pyridine destroys the initial complex.
NUCLEOPHILIC SUBSTITUTION REACTIONS ON ANTIMONY(III) 0,0-DISUBSTITUTED PHOSPHORODITHIOATES
McEwen, W. E.,Woo, E. J.,Kalbacher, B. J.
, p. 35 - 40 (2007/10/02)
Antimony(III) tris(O,O-diisobutyl phosphorodithioate), 1 (R=i-Bu) has been found to undergo a nucleophilic displacement reaction with sodium 1-propanethiolate to give antimony(III) tris-(1-propanethiolate), 4, and sodium O,O-diisobutyl phosphorodithioate (8, R=i-Bu).Reaction of 1 (R=i-Bu) with phenyllithium gave triphenylstibine and lithium O,O-diisobutyl phosphorodithioate.Similar reactions of various compounds of type 1 with the sodium salts of carboxylic acids and with the sodium salt of pyrrole were also found to occur.Furthermore, antimony tris(O,O-diisobutyl phosphorodithioate), 1 (R=i-Bu), was found to undergo solvolysis with n- propyl mercaptan to give 4 and O,O-diisobutyl phosphorodithioic acid 5.Compounds of type 1 are used as passivating agents in petroleum refining, and reactions of the types described for 1 with n-propyl mercaptan and with the salts of carboxylic acids probably occur when "Phil-Ad CA" is added to the feedstock of a fluid catalytic cracking unit.
