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Cyclopalladated complexes containing 2-CRPPhligands (R = H, F): one-electron electrochemical reduction leading to metal–carbon σ-bond cleavage via palladium()

Version 2 2024-06-03, 15:28
Version 1 2015-08-27, 07:51
journal contribution
posted on 2024-06-03, 15:28 authored by G Kar, SH Privér, LA Jones, S-X Guo, Angel TorrieroAngel Torriero, AM Bond, MA Bennett, SK Bhargava
Three new ortho -metallated palladium complexes, [Pd(O,O’-hfacac)(κ2-2-C6F4PPh2)] (11), [Pd2(O,O’hfacac)2(μ-2-C6F4PPh2)2](12) and [Pd(O,O’-hfacac)(κC-2-C6F4PPh2)(PPh3)] (13) (hfacac = hexafluoroace-tylacetonate), have been prepared and fully characterised. The electrochemical reductions of complexes 11–13, together with those of other cyclopalladated complexes containing 2C6R4PPh2 ligands (R = H, F) were studied by cyclic, rotating disk and microelectrode voltammetry. Evidence for the one-electron reduction of [PdI(κ2-2-C6F4PPh2)(PPh2Fc)] (6) was obtained from coulometric analysis, although the product is unstable and undergoes further chemical processes. Preparative electro-reduction of [Pd2(μ-Br)2(κ2-2-C6F4PPh2)2] (7) in CH2Cl2 causes reductive cleavage of its Pd–C σ-bonds and formation of the complex [PdBr2{PPh2(2-C6F4H)}2](14); possible mechanisms are discussed.

History

Journal

Dalton transactions: an international journal of inorganic chemistry

Volume

44

Pagination

3367-3377

Location

Cambridge, Eng.

ISSN

1477-9226

eISSN

1477-9234

Language

eng

Publication classification

C Journal article, C1 Refereed article in a scholarly journal

Copyright notice

2015, Royal Society of Chemistry

Issue

7

Publisher

Royal Society of Chemistry