title: Cyclopalladated complexes containing 2-C6R4PPh2 ligands (R = H, F): one-electron electrochemical reduction leading to metal-carbon σ-bond cleavage via palladium(I).
abstract: Three new ortho-metallated palladium complexes, [Pd(O,O'-hfacac)(κ(2)-2-C6F4PPh2)] (), [Pd2(O,O'-hfacac)2(μ-2-C6F4PPh2)2] () and [Pd(O,O'-hfacac)(κC-2-C6F4PPh2)(PPh3)] () (hfacac = hexafluoroacetylacetonate), have been prepared and fully characterised. The electrochemical reductions of complexes , together with those of other cyclopalladated complexes containing 2-C6R4PPh2 ligands (R = H, F) were studied by cyclic, rotating disk and microelectrode voltammetry. Evidence for the one-electron reduction of [PdI(κ(2)-2-C6F4PPh2)(PPh2Fc)] () was obtained from coulometric analysis, although the product is unstable and undergoes further chemical processes. Preparative electro-reduction of [Pd2(μ-Br)2(κ(2)-2-C6F4PPh2)2] () in CH2Cl2 causes reductive cleavage of its Pd-C σ-bonds and formation of the complex [PdBr2{PPh2(2-C6F4H)}2] (); possible mechanisms are discussed.
authors.affiliation: Centre for Advanced Materials and Industrial Chemistry (CAMIC), School of Applied Sciences (Applied Chemistry), RMIT University, GPO Box 2476, Melbourne, Victoria 3001, Australia. suresh.bhargava@rmit.edu.au.
authors.forename: Gopa
authors.initials: G
authors.lastname: Kar
authors.forename: Steven H
authors.initials: SH
authors.lastname: Privér
authors.forename: Lathe A
authors.initials: LA
authors.lastname: Jones
authors.forename: Si-Xuan
authors.initials: SX
authors.lastname: Guo
authors.forename: Angel A J
authors.initials: AA
authors.lastname: Torriero
authors.forename: Alan M
authors.initials: AM
authors.lastname: Bond
authors.forename: Martin A
authors.initials: MA
authors.lastname: Bennett
authors.forename: Suresh K
authors.initials: SK
authors.lastname: Bhargava