The isomerization of allylbenzene has been carried out by the cationic nickel hydrides [NHiL4]+ (L = 1 2dppe; PPh3; P(OEt)3) directly prepared in situ by electrogenerating the corresponding Ni(0) complexes in the presence of hydrogen ions. Such a procedure allows one also to take advantage of the catalytic activity of the poorly stable hydrides obtained when L = PPh3 or P(OEt)3. In these cases, a small but finite steady-state concentration of the promoter can be maintained in the solution by the occurrence of an electrocatalytic process cyclically renewing this species, thus making possible its interaction with olefin molecules in spite of its instability. The results obtained point out that high stability for the cationic nickel hydrides is accompanied by quite a low promoting activity, while hydrides which decay quickly also exhibit high reactivity. The information collected concerning the reaction pathway through which the catalyzed isomerization reactions occur, has then been exploited for devising an electrocatalytic process in which the coupling of allyl bromide and the isomerization of the diolefin product can occur simultaneously. © 1987.

An electroanalytical investigation on the olefin isomerization reaction promoted by electrogenerated cationic nickel hydrides

DANIELE, Salvatore;
1987-01-01

Abstract

The isomerization of allylbenzene has been carried out by the cationic nickel hydrides [NHiL4]+ (L = 1 2dppe; PPh3; P(OEt)3) directly prepared in situ by electrogenerating the corresponding Ni(0) complexes in the presence of hydrogen ions. Such a procedure allows one also to take advantage of the catalytic activity of the poorly stable hydrides obtained when L = PPh3 or P(OEt)3. In these cases, a small but finite steady-state concentration of the promoter can be maintained in the solution by the occurrence of an electrocatalytic process cyclically renewing this species, thus making possible its interaction with olefin molecules in spite of its instability. The results obtained point out that high stability for the cationic nickel hydrides is accompanied by quite a low promoting activity, while hydrides which decay quickly also exhibit high reactivity. The information collected concerning the reaction pathway through which the catalyzed isomerization reactions occur, has then been exploited for devising an electrocatalytic process in which the coupling of allyl bromide and the isomerization of the diolefin product can occur simultaneously. © 1987.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10278/32894
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