eCite Digital Repository

Computational study of C(sp3)-O bond formation at a PdIV centre


Canty, AJ and Ariafard, A and Camasso, NM and Higgs, AT and Yates, BF and Sanford, MS, Computational study of C(sp3)-O bond formation at a PdIV centre, Dalton Transactions, 46, (11) pp. 3742-3748. ISSN 1477-9226 (2017) [Refereed Article]

Copyright Statement

Copyright 2017 The Royal Society of Chemistry

DOI: doi:10.1039/c7dt00096k


This report describes a computational study of C(sp3)OR bond formation from PdIV complexes of general structure PdIV(CH2CMe2-o-C6H4-C,C′)(F)(OR)(bpy-N,N′) (bpy = 2,2′-bipyridine). Dissociation of OR from the different octahedral PdIV starting materials results in a common square-pyramidal PdIV cation. An SN2-type attack by OR (OR = phenoxide, acetate, difluoroacetate, and nitrate) then leads to C(sp3)OR bond formation. In contrast, when OR = triflate, concerted C(sp3)C(sp2) bond-forming reductive elimination takes place, and the calculations indicate this outcome is the result of thermodynamic rather than kinetic control. The energy requirements for the dissociation and SN2 steps with different OR follow opposing trends. The SN2 transition states exhibit "Pd⋯C⋯O" angles in a tight range of 151.5 to 153.0, resulting from steric interactions between the oxygen atom and the gem-dimethyl group of the ligand. Conformational effects for various OR ligands and isomerisation of the complexes were also examined as components of the solution dynamics in these systems. In all cases, the trends observed computationally agree with those observed experimentally.

Abstract Image

Item Details

Item Type:Refereed Article
Keywords:palladium, organopalladium, palladium(IV), SN2 mechanism, DFT
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:119885
Year Published:2017
Web of Science® Times Cited:15
Deposited By:Chemistry
Deposited On:2017-08-07
Last Modified:2018-03-26

Repository Staff Only: item control page