Gregg A. Lane

The electron-transfer properties of alkyne-bridged dipalladium complexes: synthesis and reactions of [Pd2(µ-PhC2Ph)(η-C5Ph5)2][PF6], and comments on the mechanism of the oxidative cleavage of binuclear organotransition-metal complexes

Cyclic voltammetry shows that [Pd2(µ- PhC2Ph)(η-C5Ph5)2](1) undergoes one one-electron reduction and two one-electron oxidations at a platinum electrode. Chemical oxidation of (1) with AgPF6 in toluene gives the paramagnetic salt [Pd2(µ-PhC2Ph)(η-C5Ph5)2][PF5] which reacts with P-donor ligands or dienes to give [PdL2(η-C5Ph5)][PF5](2, L2= Ph2PCH2CH2PPh2, cyclo-octa-1,5–diene, cyclo-octatetraene, norbornadiene, or dibenzo[a,e]cyclo-octene) and (1). The mechanism of the cleavage of [Pd2(µ-PhC2Ph)(η-C5Ph5)2]+(1)+ has been probed by voltammetry at a rotating platinum electrode; the implications of this mechanism with respect to the oxidative cleavage of other binuclear organotransition-metal complexes is discussed.