Cyclopalladated complexes containing 2-C6R4PPh2 ligands (R = H, F): one-electron electrochemical reduction leading to metal-carbon σ-bond cleavage via palladium(I).

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.

Synthesis, X-ray structure and electrochemical oxidation of palladium(II) complexes of ferrocenyldiphenylphosphine.

Four new complexes, [PdX(κ(2)-2-C(6)R(4)PPh(2))(PPh(2)Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh(2)Fc) have been prepared and fully characterised. The X-ray structures of complexes trans-1, cis-2 and cis-4, and that of a decomposition product of 4, [Pd(κ(2)-2-C(6)F(4)PPh(2))(μ-I)(μ-2-C(6)F(4)PPh(2))PdI(PPh(2)Fc)] (5), have been determined. These complexes show a distorted square planar geometry about the metal atom, the bite angles of the chelate ligands being about 69°, as expected.

Gold nanoparticle formation during bromoaurate reduction by amino acids.

The synthesis and characterization of water-soluble dispersions of gold nanoparticles by the reduction of a potassium tetrabromoaurate precursor solution using the amino acids L-tyrosine, glycyl-L-tyrosine, and L-arginine using alkaline synthesis conditions are reported. The particle sizes determined by small-angle X-ray scattering (SAXS) and high-resolution transmission electron microscopy (HRTEM) measurements are found to be inversely proportional to the rate of particle formation, which was determined by time-resolved UV-visible spectrophotometry measurements, and vary very slowly at intermediate gold concentrations and rapidly at the extremes. Dispersions produced with a mixture of the two amino acids glycyl-L-tyrosine and L-tyrosine showed particle sizes and particle size distributions which were directly proportional to the ratio of the two L-amino acids, thus offering the possibility for control over the properties of the gold nanoparticle dispersions.