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DFT studies of isomerization in palladium(IV) chemistry and alkyl halide transfer from palladium(IV) to palladium(II)

Canty, AJ and Ariafard, A ORCID: 0000-0003-2383-6380 2018 , 'DFT studies of isomerization in palladium(IV) chemistry and alkyl halide transfer from palladium(IV) to palladium(II)' , Journal of Organometallic Chemistry, vol. 872 , pp. 110-113 , doi: 10.1016/j.jorganchem.2018.07.036.

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A DFT study of alkyl halide exchange from Pd(IV) to Pd(II) centers supports proposals for an SN2 process in which nucleophilic Pd(II) square-planar complexes attack the axial alkyl group in electrophilic squarepyramidal Pd(IV) centers, leading to transfer of R+ from Pd(IV) to Pd(II) involving a transition structure of the form [R2(bpy)··R··PdR2 (bpy)]+ (bpy = 2,20’ -bipyridine). Computation accounts for the selectivity in benzyl (Bn) over methyl transfer from PhMeBnPdIV(bpy)Br to Me2PdII(bpy), giving PhMePdII(bpy) and BnMe2PdIV(bpy). Transition structures are formed by the interaction of a dz2-like HOMO at the Pd(II) nucleophile and the Pd-C σ* LUMO at the cationic Pd(IV) electrophile. Isomerization of octahedral palladium(IV) complexes via halide loss followed by involvement of trigonal-bipyramidal transition structures to facilitate isomerization is also examined. A lower barrier for Bn+ than Me+ transfer is attributed to stabilisation of the transition structure by delocalisation of positive charge within the benzyl group, reflected in a higher total charge density for the benzyl group than found for the methyl group.

Item Type: Article
Authors/Creators:Canty, AJ and Ariafard, A
Keywords: organopalladium, palladium(IV), DFT, exchange reactions, redox transmetallation, octahedral isomerism, isomerization
Journal or Publication Title: Journal of Organometallic Chemistry
Publisher: Elsevier Science Sa
ISSN: 0022-328X
DOI / ID Number: 10.1016/j.jorganchem.2018.07.036
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Copyright 2018 Elsevier B.V.

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