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

Bontempelli, Gino; Fiorani, Mario; Daniele, Salvatore; Schiavon, Gilberto

doi:10.1016/0304-5102(87)80002-0

Cited by 10 publications

(5 citation statements)

References 16 publications

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Section: Transition Metal-mediated Isomerizations Of Allylbenzenesmentioning

confidence: 99%

“…The cationic nickel hydride-promoted isomerization of olefinic bonds, where the nickel species was obtained by electrogeneration, has been demonstrated by the Bontempelli group. 827 These researchers carried out the isomerization of allylbenzene 3 using the cationic nickel hydrides [NiHL 4 ] + [where L = 1/2 dppe, PPh 3 , or P(OEt) 3 ] [dppe = 1,2bis(diphenylphosphine)ethane]. Of particular interest is the fact that these nickel species were formed in situ by electrogeneration of the corresponding Ni(0) complexes in the presence of hydrogen ions.…”

Section: Nickel-catalyzed Reactionsmentioning

confidence: 99%

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Isomerization of Allylbenzenes

et al. 2015

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Section: Transition Metal-mediated Isomerizations Of Allylbenzenesmentioning

confidence: 99%

Section: Nickel-catalyzed Reactionsmentioning

confidence: 99%

Isomerization of Allylbenzenes

et al. 2015

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“…An analogous electrocatalytic cycle was suggested for the synthesis of hexa-1,5-diene from allyl bromide in the presence of nickel complexes with 2,2 H -bipyridyl 298 chloride under the action of the electrochemically generated cobalt complex with 2,2 H -bipyridyl. 305 However, the numbers of the catalytic cycles in these processes were rather low due to rapid decomposition of the catalyst.…”

Section: Mechanisms Of Reactions Catalysed By Nickel and Palladium Co...mentioning

confidence: 90%

“…One of the first studied processes is catalytic coupling of allyl halides, which proceeds with a very high rate according to the following scheme: 298 In this case, the catalyst, viz., the highly reactive nickel(0) triphenylphosphine complex A, is generated in situ by electrochemical reduction of the corresponding Ni(II) complex, which is stable and can be prepared by anodic oxidation of nickel in the presence of PPh 3 . 48, 297 ± 299 The Ni(0)(PPh 3 ) 4 complex (A) is involved in oxidative addition with allyl halide resulting in functionalisation of the C7Hal bond to form the allylnickel p-complex B.…”

Section: Mechanisms Of Reactions Catalysed By Nickel and Palladium Co...mentioning

confidence: 99%

Metal complex catalysis in organic electrosynthesis

Budnikova¹

2002

Russ. Chem. Rev.

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Data on the use of electrochemically generated metal Data on the use of electrochemically generated metal complex catalysts in organic synthesis are analysed, systematised complex catalysts in organic synthesis are analysed, systematised and generalised. The considerable potential of organic electro-and generalised. The considerable potential of organic electrochemistry is shown. Some electrochemical methods provide chemistry is shown. Some electrochemical methods provide advantages in the synthesis of compounds where conventional advantages in the synthesis of compounds where conventional chemical methods fail, are experimentally complicated or have chemical methods fail, are experimentally complicated or have environmental limitations. Particular attention is given to the environmental limitations. Particular attention is given to the mechanisms of electrocatalytic reactions. The bibliography mechanisms of electrocatalytic reactions. The bibliography includes 333 references includes 333 references. .

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“…Unlike the electrochemical behaviour of tris(2,2 -bipyridyl) ruthenium(II), iron(II), and osmium(II) complexes which exhibits two successive mono-electronic transfers [14], the reduction of the nickel(II) compound involves a two-electron process leading to the formation of a nickel(0) complex [20][21][22]. It was shown that the electrochemical reduction of [Ni II (bpy) 3 ] 2+ to [Ni 0 (bpy) 3 ] is followed by a fast loss of a bpy ligand to give [Ni 0 (bpy) 2 ] [19,20], the latter species being in equilibrium with a solvent molecule to give [Ni 0 (bpy)(MeCN)] [22]. These equilibria explain the presence of a second small oxidation wave on the reverse scan.…”

Section: Ion-exchange Voltammetry Of Ni(bpy) 3 (Bf 4 )mentioning

confidence: 99%

Ion-exchange voltammetry of tris(2,2′-bipyridine) nickel(II), cobalt(II), and Co(salen) at polyestersulfonated ionomer coated electrodes in acetonitrile: Reactivity of the electrogenerated low-valent complexes

Buriez

Moretto²,

Ugo³

2006

Electrochimica Acta

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The electrochemical behaviour of [Ni(bpy) 3 (BF 4 ) 2 ], [Co(bpy) 3 (BF 4 ) 2 ], and Co(salen) (where bpy = 2,2 -bipyridine, and salen = N,Nbis(salicylidene)ethylenediamine) is studied at a glassy carbon electrode modified with the poly(estersulfonate) ionomer Eastman AQ 55 in acetonitrile (MeCN). It is shown that the nickel complex is strongly incorporated into the polymer. The reduction of the divalent nickel compound features a two-electron process leading to a nickel(0) species which is released from the coating because of the lack of electrostatic attraction with the ionomer. Yet, the neutral zerovalent nickel-bipyridine complex is reactive towards ethyl 4-iodobenzoate and di-bromocyclohexane despite the presence of the polymer. The activation of the aryl halide occurs through an oxidative addition, whereas, an electron transfer is involved in the presence of the alkyl halide making the catalyst regeneration much faster in the latter case. The electrochemical study of [Co(bpy) 3 (BF 4 ) 2 ] shows that incorporation of the cobalt complex into the polymer is efficient, provided excess bpy is used. This excess bpy does not interfere with the electrocatalytic activity of the cobalt complex incorporated in the AQ coating and efficient electrocatalysis is observed towards di-bromocyclohexane and benzyl-bromide as substrates. Finally, replacement of the bpy ligand with the macrocycle N,N -bis(salicylidene)ethylenediamine, salen, leads to the incorporation of the non-charged Co II (salen) complex into the AQ 55 polymer showing the relevancy of hydrophobic interactions. The reaction between the electrogenerated [Co I (salen)] − with 1,2-dibromocyclohexane exhibits a fast inner sphere electron transfer.

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

Cited by 10 publications

References 16 publications

Isomerization of Allylbenzenes

Isomerization of Allylbenzenes

Metal complex catalysis in organic electrosynthesis

Ion-exchange voltammetry of tris(2,2′-bipyridine) nickel(II), cobalt(II), and Co(salen) at polyestersulfonated ionomer coated electrodes in acetonitrile: Reactivity of the electrogenerated low-valent complexes

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