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Issue 31, 2010
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Synthesis and characterization of neutral and anionic carbonyl derivatives of palladium(II)

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Abstract

The action of CO on the solvento-complexes cis-[PdR2(thf)2] [R = C6F5 (1), C6Cl5 (2)] at low temperature gives cis-[PdR2(CO)2] [R = C6F5 (3), C6Cl5 (4)] in good yield by simple replacement of the highly labile thf molecules. These are rare cases of PdII dicarbonyl compounds, whose characterization relies on spectroscopic and analytic data. The crystal structure of the square-planar platinum homologue cis-[Pt(C6Cl5)2(CO)2] is also presented. CO can split the double bridging-system in the dinuclear species [{PdR2}2(μ-X)2]2− giving the homologous series of anionic monocarbonyl PdII derivatives with formula [cis-PdR2X(CO)] (5–10: R = C6F5, C6Cl5; X = Cl, Br, I), which were isolated (except for the R = C6F5 and X = I) and suitably characterized. Characterization includes the crystal and molecular structure of [PPh3Me][cis-Pd(C6F5)2Br(CO)] (6′). The anionic species [NBu4][cis-Pd(C6F5)2Cl(CO)] (5) reacts with neutral cis-[Pd(C6F5)2(CO)2] (3) under CO extrusion, affording the dinuclear derivative [NBu4][{Pd(C6F5)2(CO)}2(μ-Cl)] (11), which contains a single unsupported halide bridge (X-ray diffraction). Complex 11 can be considered as modelling a possible intermediate step in intermolecular CO substitution reactions that are easily undergone by PdII halo carbonyl species.

Graphical abstract: Synthesis and characterization of neutral and anionic carbonyl derivatives of palladium(ii)

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Publication details

The article was received on 22 Feb 2010, accepted on 17 May 2010 and first published on 30 Jun 2010


Article type: Paper
DOI: 10.1039/C0DT00014K
Citation: Dalton Trans., 2010,39, 7301-7309
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    Synthesis and characterization of neutral and anionic carbonyl derivatives of palladium(II)

    I. Ara, J. Forniés, A. Martín, L. F. Martín, B. Menjón and H. Miedes, Dalton Trans., 2010, 39, 7301
    DOI: 10.1039/C0DT00014K

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