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

journal contribution
posted on 2023-05-19, 09:25 authored by Allan CantyAllan Canty, Alireza AriafardAlireza Ariafard, Camasso, NM, Higgs, AT, Brian YatesBrian Yates, Sanford, MS

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.

History

Publication title

Dalton Transactions

Volume

46

Issue

11

Pagination

3742-3748

ISSN

1477-9226

Department/School

School of Natural Sciences

Publisher

Royal Soc Chemistry

Place of publication

Thomas Graham House, Science Park, Milton Rd, Cambridge, England, Cambs, Cb4 0Wf

Rights statement

Copyright 2017 The Royal Society of Chemistry

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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