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Issue 38, 2010
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Synthesis, X-ray structure and electrochemical oxidation of palladium(II) complexes of ferrocenyldiphenylphosphine

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Abstract

Four new complexes, [PdX(κ2-2-C6R4PPh2)(PPh2Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh2Fc) 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.

Graphical abstract: Synthesis, X-ray structure and electrochemical oxidation of palladium(ii) complexes of ferrocenyldiphenylphosphine

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Publication details

The article was received on 23 Feb 2010, accepted on 17 Jun 2010 and first published on 23 Aug 2010


Article type: Paper
DOI: 10.1039/C0DT00016G
Citation: Dalton Trans., 2010,39, 9079-9090
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    Synthesis, X-ray structure and electrochemical oxidation of palladium(II) complexes of ferrocenyldiphenylphosphine

    M. A. Bennett, S. K. Bhargava, A. M. Bond, I. M. Burgar, S. Guo, G. Kar, S. H. Privér, J. Wagler, A. C. Willis and A. A. J. Torriero, Dalton Trans., 2010, 39, 9079
    DOI: 10.1039/C0DT00016G

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