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

journal contribution
posted on 2023-05-18, 14:50 authored by Allan CantyAllan Canty, Alireza AriafardAlireza Ariafard, Brian YatesBrian Yates, Sanford, MS
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 Pd–C(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.

History

Publication title

Organometallics

Volume

34

Issue

6

Pagination

1085-1090

ISSN

0276-7333

Department/School

School of Natural Sciences

Publisher

Amer Chemical Soc

Place of publication

1155 16Th St, Nw, Washington, USA, Dc, 20036

Rights statement

Copyright 2015 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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