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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, DFT studies of isomerization in palladium(IV) chemistry and alkyl halide transfer from palladium(IV) to palladium(II), Journal of Organometallic Chemistry, 872 pp. 110-113. ISSN 0022-328X (2018) [Refereed Article]

Copyright Statement

Copyright 2018 Elsevier B.V.

DOI: doi:10.1016/j.jorganchem.2018.07.036


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 Details

Item Type:Refereed Article
Keywords:organopalladium, palladium(IV), DFT, exchange reactions, redox transmetallation, octahedral isomerism, isomerization
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:128212
Year Published:2018
Web of Science® Times Cited:1
Deposited By:Chemistry
Deposited On:2018-09-10
Last Modified:2019-03-07

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