ABSTRACT
Addition of formate on the dicationic cluster [Pd(3)(dppm)(3)(mu(3)-CO)](2+) (dppm=bis(diphenylphosphinomethane) affords quantitatively the hydride cluster [Pd(3)(dppm)(3)(mu(3)-CO)(mu(3)-H)](+). This new palladium-hydride cluster has been characterised by (1)H NMR, (31)P NMR and UV/Vis spectroscopy and MALDI-TOF mass spectrometry. The unambiguous identification of the capping hydride was made from (2)H NMR spectroscopy by using DCO(2) (-) as starting material. The mechanism of the hydride complex formation was investigated by UV/Vis stopped-flow methods. The kinetic data are consistent with a two-step process involving: 1) host-guest interactions between HCO(2) (-) and [Pd(3)(dppm)(3)(mu(3)-CO)](2+) and 2) a reductive elimination of CO(2). Two alternatives routes to the hydride complex were also examined : 1) hydride transfer from NaBH(4) to [Pd(3)(dppm)(3)(mu(3)-CO)](2+) and 2) electrochemical reduction of [Pd(3)(dppm)(3)(mu(3)-CO)](2+) to [Pd(3)(dppm)(3)(mu(3)-CO)](0) followed by an addition of one equivalent of H(+). Based on cyclic voltammetry, evidence for a dual mechanism (ECE and EEC; E=electrochemical (one-electron transfer), C=chemical (hydride dissociation)) for the two-electron reduction of [Pd(3)(dppm)(3)(mu(3)-CO)(mu(3)-H)](+) to [Pd(3)(dppm)(3)(mu(3)-CO)](0) is provided, corroborated by digital simulation of the experimental results. Geometry optimisations of the [Pd(3)(H(2)PCH(2)PH(2))(3)(mu(3)-CO)(mu(3)-H)](n) model clusters were performed by using DFT at the B3 LYP level. Upon one-electron reductions, the Pd--Pd distance increases from a formal single bond (n=+1), to partially bonding (n=0), to weak metal-metal interactions (n=-1), while the Pd--H bond length remains relatively the same.
ABSTRACT
The reduction mechanism of the title cluster has been investigated by means of cyclic voltammetry (CV), rotating disk electrode (RDE) voltammetry, and coulometry. The 2-electron reduction proceeds via two routes simultaneously. The first one involves two 1-electron reduction steps, followed by an iodide elimination to form the neutral Pd(3)(dppm)(3)(CO)(0) cluster (EEC mechanism). The second one is a 1-electron reduction process, followed by an iodide elimination, then by a second 1-electron step (ECE mechanism) to generate the same final product. Control over these two competitive mechanisms can be achieved by changing temperature, solvent polarity, iodide concentration, or sweep rate. The reoxidation of the Pd(3)(dppm)(3)(CO)(0) cluster in the presence of iodide proceeds via a pure ECE pathway. The overall results were interpreted with a six-member square scheme, and the cyclic and RDE voltammograms were simulated, in order to extract the reaction rate and equilibrium constants for iodide exchange for all three Pd(3)(dppm)(3)(CO)(I)(n)() (n = +1, 0, -1) adducts.
