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Issue 48, 2008
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The reduction of platinum(IV) and palladium(IV) ions by 2,6-pyridinedihydroxamic acid

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Abstract

Reaction of K2[PtIVCl6] and K2[PdIVCl6] with 2,6-pyridinedihydroxamic acid (2,6-pyha) and its disodium salt, 2,6-pyhaNa2, yielded not the desired Pt(IV) and Pd(IV) 2,6-pyridinedihydroxamato complexes, but rather the Pt(II) and Pd(II) 2,6-pyridinedicarboxylato complexes, trans-[PtII(2,6-pycaH−1)2]·2H2O and trans-[PdII(2,6-pycaH−1)2]·2H2O respectively (2,6-pyca = 2,6-pyridinedicarboxylic acid). Thus in the presence of Pt(IV) and Pd(IV), the dihydroxamic acid was adventitiously hydrolysed to the corresponding dicarboxylic acid and Pt(IV) and Pd(IV) reduced to Pt(II) and Pd(II)in situ. The X-ray crystal structures of 2,6-pyha, 2,6-pyhaNa2·8H2O, trans-[PtII(2,6-pycaH−1)2]·2H2O and trans-[PdII(2,6-pycaH−1)2]·2H2O are reported, together with a possible mechanism for the metal-assisted hydrolysis of the dihydroxamic acid and reduction of Pt(IV) and Pd(IV) to Pt(II) and Pd(II) respectively.

Graphical abstract: The reduction of platinum(IV) and palladium(IV) ions by 2,6-pyridinedihydroxamic acid

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Publication details

The article was received on 06 Jun 2008, accepted on 22 Aug 2008 and first published on 23 Oct 2008


Article type: Paper
DOI: 10.1039/B809584A
Citation: Dalton Trans., 2008,0, 6933-6939

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    The reduction of platinum(IV) and palladium(IV) ions by 2,6-pyridinedihydroxamic acid

    D. Griffith, A. Chopra, H. Müller-Bunz and C. J. Marmion, Dalton Trans., 2008, 0, 6933
    DOI: 10.1039/B809584A

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