Mechanistic study on rhenium(V) dimer catalysis for the oxygen atom transfer from pyridine oxide to Ph3E (E = P, As): experiment and computational study

The rhenium(v)oxo dimer {MeReO(edt)}2 (edt = 1,2-ethanedithiolate) is an effective catalyst for the oxygen atom transfer (OAT) reaction from pyridine oxide and picoline oxide to triphenylarsine (Ph3As) as oxygen acceptor. Kinetics measurements were carried out by the initial rate method because of the monomerization reaction of the pyridine product with the {MeReO(edt)}2 catalysts. The derived rate is R = k[Re][NO] (where NO is picoline oxide or pyridine oxide) and independent of the Ph3As concentration. The rate constant at room temperature in chloroform is k(PicNO) = 268.1 ± 3.5 L mol−1 s−1 and k(PyNO) = 155.3 ± 2.3 L mol−1 s−1. The analogue rhenium(v)oxo dimer {MeReO(pdt)}2 (pdt = 1,3-propanedithiolate) does not monomerize with pyridine. However, {MeReO(edt)}2 rapidly monomerizes with pyridine. Density functional theory study of the enthalpy of the monomerization reaction shows that the {MeReO(edt)}2 reaction with pyridine is more thermodynamically favoured than {MeReO(pdt)}2 and this is attributed to the higher angle strain on the {MeReO(edt)}2 bridging sulfur. The computational study of the proposed slow step shows that enthalpy of activation (ΔH‡) of ReV oxidation to ReVII is unchanged by varying the substituent on the pyridine oxide.

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Mechanistic study on rhenium(V) dimer catalysis for the oxygen atom transfer from pyridine oxide to Ph3E (E = P, As): experiment and computational study

Cited by 2 publications

References 40 publications

Kinetics and mechanistic study on deoxygenation of pyridine oxide catalyzed by {MeRe V O(pdt)} 2 dimer

Kinetics and mechanistic study on deoxygenation of pyridine oxide catalyzed by {MeRe V O(pdt)} 2 dimer

Kinetic and Computational Studies of Rhenium Catalysis for Oxygen Atom Transfer Reactions

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