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Computational study of intramolecular arene palladation at a palladium(IV) center


Canty, AJ and Ariafard, A and Yates, BF and Sanford, MS, Computational study of intramolecular arene palladation at a palladium(IV) center, Organometallics, 34, (6) pp. 1085-1090. ISSN 0276-7333 (2015) [Refereed Article]

Copyright Statement

Copyright 2015 American Chemical Society

DOI: doi:10.1021/om5013049


A computational study of the palladation of a pendant phenyl group in the PdIV complex PdCl2(CF3)(biH)(But2bpy) to form PdCl(CF3)(bi)(But2bpy) (bi = biphenylenediyl) indicates that this reaction occurs via an SEAr mechanism after dissociation of a chloride ion from the Pd center. Chloride dissociation occurs trans to the PdC(biH) bond. This dissociation is followed by rate-limiting isomerization of the square-pyramidal five-coordinate cation to place the remaining chloride ligand trans to the pendant phenyl group, with concomitant formation of a Pd-arenonium species. The free chloride ion then assists the departure of the Cipso proton from the arenonium complex as HCl. Key findings of this study include the occurrence of facile ligand dissociation and isomerization at this PdIVcenter as well as the participation of a classical SEAr mechanistic pathway in this transformation.

Item Details

Item Type:Refereed Article
Keywords:palladium, metallation, palladation, C-H activation,palladium(IV), computational chemistry
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)
UTAS Author:Yates, BF (Professor Brian Yates)
ID Code:104950
Year Published:2015
Web of Science® Times Cited:21
Deposited By:Chemistry
Deposited On:2015-11-30
Last Modified:2018-03-14

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