Jump to main content
Jump to site search

Issue 11, 2017
Previous Article Next Article

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

Author affiliations


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.

Graphical abstract: Computational study of C(sp3)–O bond formation at a PdIV centre

Back to tab navigation

Supplementary files

Publication details

The article was received on 11 Jan 2017, accepted on 23 Feb 2017 and first published on 27 Feb 2017

Article type: Paper
DOI: 10.1039/C7DT00096K
Citation: Dalton Trans., 2017,46, 3742-3748
  •   Request permissions

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

    A. J. Canty, A. Ariafard, N. M. Camasso, A. T. Higgs, B. F. Yates and M. S. Sanford, Dalton Trans., 2017, 46, 3742
    DOI: 10.1039/C7DT00096K

Search articles by author