TY - JOUR
T1 - Synthesis, X-ray structure and electrochemical oxidation of palladium(II) complexes of ferrocenyldiphenylphosphine
AU - Bennett, Martin A.
AU - Bhargava, Suresh K.
AU - Bond, Alan M.
AU - Burgar, Iko M.
AU - Guo, Si Xuan
AU - Kar, Gopa
AU - Privér, Steven H.
AU - Wagler, Jörg
AU - Willis, Anthony C.
AU - Torriero, Angel A.J.
PY - 2010/10/14
Y1 - 2010/10/14
N2 - Four new complexes, [PdX(κ2-2-C6R 4PPh2)(PPh2Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh 2Fc) 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(κ2-2-C6F4PPh2)(μ-I) (μ-2-C6F4PPh2)PdI(PPh2Fc)] (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 PPh2Fc 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 PPh2Fc; subsequently, the metal-phosphorus bond is cleaved, leading to free PPh2Fc+, which undergoes further chemical and electrochemical reactions.
AB - Four new complexes, [PdX(κ2-2-C6R 4PPh2)(PPh2Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh 2Fc) 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(κ2-2-C6F4PPh2)(μ-I) (μ-2-C6F4PPh2)PdI(PPh2Fc)] (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 PPh2Fc 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 PPh2Fc; subsequently, the metal-phosphorus bond is cleaved, leading to free PPh2Fc+, which undergoes further chemical and electrochemical reactions.
UR - http://www.scopus.com/inward/record.url?scp=77956926539&partnerID=8YFLogxK
U2 - 10.1039/c0dt00016g
DO - 10.1039/c0dt00016g
M3 - Article
SN - 1477-9226
VL - 39
SP - 9079
EP - 9090
JO - Dalton Transactions
JF - Dalton Transactions
IS - 38
ER -