title: Synthesis, X-ray structure and electrochemical oxidation of palladium(II) complexes of ferrocenyldiphenylphosphine.
abstract: 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. The cis/trans ratio of 1-4 in solution is strongly dependent on solvent. The new complexes and the uncoordinated PPh(2)Fc ligand were electrochemically characterised by cyclic and rotating disk voltammetry, UV-visible spectroelectrochemistry, and bulk electrolysis in dichloromethane and acetonitrile. In both cases, oxidation occurs at both the ferrocene and phosphine centres, but the complexes oxidise at more positive potentials than uncoordinated PPh(2)Fc; subsequently, the metal-phosphorus bond is cleaved, leading to free PPh(2)Fc(+), which undergoes further chemical and electrochemical reactions.
authors: Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
authors: Martin A
authors: MA
authors: Bennett
authors: Suresh K
authors: SK
authors: Bhargava
authors: Alan M
authors: AM
authors: Bond
authors: Iko M
authors: IM
authors: Burgar
authors: Si-Xuan
authors: SX
authors: Guo
authors: Gopa
authors: G
authors: Kar
authors: Steven H
authors: SH
authors: Privér
authors: Jörg
authors: J
authors: Wagler
authors: Anthony C
authors: AC
authors: Willis
authors: Angel A J
authors: AA
authors: Torriero