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- W815200471 abstract "The new binuclear oxothiolatorhenium(V) compound, Re202(mtp)3 (Dl, mtpH2 = 2mercaptomethylthiophenol) was found to be an efficient catalyst for oxygen-transfer reactions. Electron donor ligands such as phosphines coordinate to one of the rhenium centers in Dl strongly, breaking up one of the Re-S bridges. Dialkylsulfides coordinate weakly. Alkylarj'lsulfides, diarylsulfides, triphenylarsine and triphenylstibine, dienes and alkenes do not coordinate to Di. Dl catalyzes the oxidation of phosphines, arsines, stilbenes, sulfides and dienes by pyridine N-oxides, and the oxidation of phosphines by dimethylsulfoxide. The kinetics and mechanism for the oxidation of triarylphosphines by pyridine N-oxides were investigated. The relative reactivities of all substrates were studied by competitive reactions. The order was found to be: phosphine > arsine > stilbene > sulfide > diene. The reaction is proposed to go through a Re(VII) intermediate with pyridine N-oxide as one of the ligands. The N-O bond was activated through coordination to rhenium and the oxygen atom was abstracted by a phosphine, forming a phosphine oxide. Introduction Oxygen atom transfer reactions are catalyzed by high-valent transition metal-oxo complexes, such as Re^^/Re^,^^^ Mo^/Mo^,^^'^^ and W^'/W^.Molybdenum and tungsten systems have received the most attention because of their roles in biological systems. In such pairs, the oxidation states differ by two units in keeping with their role as oxotransferases; the metals exist in their highest oxidation states to stabilize the metal-oxo n ^ Reproduced in part with permission from Inorganic Chemistry, submitted for publication. Unpublished work copyright 2000 American Chemical Society." @default.
- W815200471 created "2016-06-24" @default.
- W815200471 creator A5011366541 @default.
- W815200471 date "2018-08-13" @default.
- W815200471 modified "2023-09-23" @default.
- W815200471 title "Oxygen transfer reactions catalyzed by rhenium (VII) and rhenium (V) complexes" @default.
- W815200471 doi "https://doi.org/10.31274/rtd-180813-13600" @default.
- W815200471 hasPublicationYear "2018" @default.
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