Dechlorination of diphenyl chlorophosphate with tin and sodium 3,6-di-tert-butyl-ortho-semiquinones

Rakhimov, R.R.; Prokof’ev, A.I.; Bah, R.; Pegram, S.A.; Hwang, J.S.; Khodak, A.A.; Alexandrov, I.A.; Aleksandrov, A.I.

Авторы: Rakhimov Rakhim R., Prokof’ev Alexander I., Bah Ramatoulie, Pegram Shannel A., Hwang Jimmy S., Khodak Alexander A., Alexandrov Ivan A., Aleksandrov Aleksey I.
Журнал: Inorganica Chimica Acta
Том: 360
Номер: 9
Год издания: 2007
Издательство: Elsevier BV
Местоположение издательства: Netherlands
Первая страница: 3033
Последняя страница: 3039
DOI: 10.1016/j.ica.2007.02.036
Аннотация: Dechlorination reactions of diphenyl chlorophosphate (PhO)2P(O)Cl with 3,6-di-tert-butyl-ortho-semiquinone complexes of triphenyl tin, SQSn(Ph)3 and sodium, SQNa have been investigated by electron spin resonance (ESR) both in solutions at 300 K and insolid phase at 77 K using mechanochemical activation. Paramagnetic 3,6-di-tert-butyl-ortho-semiquinone ligand (SQ) was used asspin probe to monitor changes in the Sn coordination sphere during the dechlorination reaction of (PhO)2P(O)Cl and consecutiveformation of tin chloride derivatives SQSnCl(Ph)2, SQSnCl2Ph, and SQSnCl3. Their structure was revealed based on the analysisof hyperfine interaction constants due to 1H nuclei in the 4,5-positions of the aromatic ring of the SQ ligand, hyperfine interactionconstants due to 35Cl and 37Cl nuclei of chlorine atoms in the Sn coordination sphere, and hyperfine interaction constants due to 117Sn and 119Sn nuclei of the central metal ion. Interaction of SQSnCl3 with (PhO)2P(O)Cl leads to the formation of a meta-stableradical–anion complex [SQSnCl4] P+(O)(OPh)2, which transforms to SQSnCl3P(O)R3, a stable adduct of SQSnCl3 with dechlorinated phosphate of a general formula P(O)R3. Analysis of solution dechlorination reaction products suggests the formation ofdiphenyl-phosphoryl radical (PhO)2P(O), which was not observed in solutions. Dechlorination of (PhO)2P(O)Cl with sodium 3,6-di-tert-butyl-ortho-semiquinone SQNa can proceed in solid phase in liquid nitrogen at 77 K via mechanochemical activation usinga ball mill. ESR analysis of the cryo-mechanochemical reaction showed the formation of the adduct of (PhO)2P(O) radical with3,6-di-tert-butyl-ortho-quinone.
Добавил в систему: Александров Алексей Иванович

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Dechlorination of diphenyl chlorophosphate with tin and sodium 3,6-di-tert-butyl-ortho-semiquinonesстатья

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