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DFT studies of isomerization in palladium(IV) chemistry and alkyl halide transfer from palladium(IV) to palladium(II)
Citation
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
Abstract
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 |
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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 |
Downloads: | 0 |
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