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• W2017129497 abstract "A theoretical study has been carried out for the mechanism of the reactions of allylammonium and -iminium substrates with Ni(0) complexes using the B3LYP density functional method. The main findings are as follows: (1) The actual active catalyst in the oxidative addition of ammonium and iminium salts is the bisphosphine−nickel complex. (2) For allylammonium salts the reaction is found to proceed via an associative mechanism (rather than a dissociative path) which involves (i) coordination of the allylammonium cation to the active metal catalyst, (ii) oxidative addition of the C−N bond to the Ni(0) complex, (iii) coordination of NH3 to yield a pentacoordinated intermediate, and (iv) loss of a phosphine ligand. The analogous reaction involving allyliminium salts does not follow the same mechanistic pattern; once the allyliminium cation is coordinated to the metal, the reaction prefers to proceed in a dissociative fashion. This preference is likely to be enhanced in solution. (3) The main difference between allylammonium and -iminium reaction mechanisms lies in the relative barriers corresponding to the insertion of the catalyst into the C−N bond leading to the pentacoordinated intermediate. For allylammonium cations, such a step is calculated to be less energy demanding than phosphine loss, whereas for allyliminium, the situation is reversed. (4) Finally the observed preference of allyliminium substrates to undergo C−N cleavage rather than N−H cleavage has been also investigated. The reason that allyl salt does not yield hydrido complexes is the kinetic impairment found for the N−H bond cleavage as compared to C−N. Intramolecular N−H activation is not allowed because of the high barriers corresponding to the three-centered transition states involved in the reaction. The structural rearrangements required for the coordinated iminium to form an η2-NH complex make the process prohibitive." @default.
• W2017129497 created "2016-06-24" @default.
• W2017129497 creator A5012743614 @default.
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• W2017129497 date "2000-09-20" @default.
• W2017129497 modified "2023-10-17" @default.
• W2017129497 title "Theoretical Study of the Mechanism of Oxidative Addition of Allyl−Ammonium and −Iminium Salts to Low-Valent Metal Complexes. Rationalization of Selective C−N and N−H Bond Activation" @default.
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• W2017129497 doi "https://doi.org/10.1021/om000468a" @default.
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