Epoxy compounds usually have stronger nucleophilic ability, because the alkyl group on the oxygen atom makes the bond angle smaller, which makes the lone pair of electrons react more dissimilarly with the electron-deficient system. Compound: Bromoferrocene, is researched, Molecular C10BrFe, CAS is 1273-73-0, about Electron- and Hydride-Transfer Reactivity of an Isolable Manganese(V)-Oxo Complex.Product Details of 1273-73-0.
The electron-transfer and hydride-transfer properties of an isolated manganese(V)-oxo complex, (TBP8Cz)MnV(O) (1) (TBP8Cz = octa-tert-corrolazinato) were determined by spectroscopic and kinetic methods. The manganese(V)-oxo complex 1 reacts rapidly with a series of ferrocene derivatives ([Fe(C5H4Me)2], [Fe(C5HMe4)2], and [Fe(C5Me5)2] = Fc*) to give the direct formation of [(TBP8Cz)MnIII(OH)]- ([2-OH]-), a two-electron-reduced product. The stoichiometry of these electron-transfer reactions was found to be (Fc derivative)/1 = 2:1 by spectral titration The rate constants of electron transfer from ferrocene derivatives to 1 at room temperature in benzonitrile were obtained, and the successful application of Marcus theory allowed for the determination of the reorganization energies (λ) of electron transfer. The λ values of electron transfer from the ferrocene derivatives to 1 are lower than those reported for a manganese(IV)-oxo porphyrin. The presumed one-electron-reduced intermediate, a MnIV complex, was not observed during the reduction of 1. However, a MnIV complex was successfully generated via one-electron oxidation of the MnIII precursor complex 2 to give [(TBP8Cz)MnIV]+ (3). Complex 3 exhibits a characteristic absorption band at λmax = 722 nm and an EPR spectrum at 15 K with g’max = 4.68, g’mid = 3.28, and g’min = 1.94, with well-resolved 55Mn hyperfine coupling, indicative of a d3 MnIVS = 3/2 ground state. Although electron transfer from [Fe(C5H4Me)2] to 1 is endergonic (uphill), two-electron reduction of 1 is made possible in the presence of proton donors (e.g., CH3CO2H, CF3CH2OH, and CH3OH). In the case of CH3CO2H, saturation behavior for the rate constants of electron transfer (ket) vs. acid concentration was observed, providing insight into the critical involvement of H+ in the mechanism of electron transfer. Complex 1 was also shown to be competent to oxidize a series of dihydronicotinamide adenine dinucleotide (NADH) analogs via formal hydride transfer to produce the corresponding NAD+ analogs and [2-OH]-. The logarithms of the observed second-order rate constants of hydride transfer (kH) from NADH analogs to 1 are linearly correlated with those of hydride transfer from the same series of NADH analogs to p-chloranil.
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Reference:
Thiazolidine – Wikipedia,
Thiazolidine – ScienceDirect.com