Metal Segregation in Bimetallic Co[BOND]Pd Carbide Carbonyl Clusters: Synthesis, Structure, Reactivity and Electrochemistry of [H6−nCo20Pd16C4(CO)48]n (n=3–6)

Authors

  • Iacopo Ciabatti,

    1. Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Viale Risorgimento 4, 40136 Bologna (Italy), Fax: (+39) 0512093690
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  • Dr. Fabrizia Fabrizi de Biani,

    1. Dipartimento di Chimica, Università di Siena, Via Aldo Moro 2, Siena (Italy)
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  • Dr. Cristina Femoni,

    1. Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Viale Risorgimento 4, 40136 Bologna (Italy), Fax: (+39) 0512093690
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  • Prof. Maria Carmela Iapalucci,

    1. Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Viale Risorgimento 4, 40136 Bologna (Italy), Fax: (+39) 0512093690
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  • Prof. Giuliano Longoni,

    1. Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Viale Risorgimento 4, 40136 Bologna (Italy), Fax: (+39) 0512093690
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  • Prof. Stefano Zacchini

    Corresponding author
    1. Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Viale Risorgimento 4, 40136 Bologna (Italy), Fax: (+39) 0512093690
    • Dipartimento di Chimica Industriale “Toso Montanari”, Università di Bologna, Viale Risorgimento 4, 40136 Bologna (Italy), Fax: (+39) 0512093690

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Abstract

Nanometric Co[BOND]Pd bimetallic [H6−nCo20Pd16C4(CO)48]n (n=3–6) tetracarbide carbonyl clusters have been prepared by redox condensation of [Co6C(CO)15]2− with [PdCl2(Et2S)2]. The crystal structures of both the dihydride tetra-anion and monohydride penta-anion have been determined as their [NEt4]4[H2Co20Pd16C4(CO)48]4 CH3COCH3 and [NMe3(CH2Ph)][NMe4]4[HCo20Pd16C4(CO)48]5 CH3COCH3 salts, respectively. The two species are isostructural and their structures display a perfect segregation of the two metals. They are composed of a cubic close-packed (ccp) Pd16 core stabilised on its surface by four {Co5C(CO)12} organometallic fragments. Their polyhydride nature has been corroborated by the study of their reactions with acids and bases, and confirmed by electrochemical studies. In addition, the reactions of [H2Co20Pd16C4(CO)48]4− with Na/naphthalene and PPh3/CO allowed the isolation of other lower nuclearity homoleptic and heteroleptic clusters, that is, [H6−nCo16Pd2C3(CO)28]n (n=5, 6), [Co4Pd2C(CO)11(PPh3)2], [Co2Pd5C(CO)8(PPh3)5], and [Co4Pd4C2(PPh3)4(CO)10Cl]. [H6−nCo16Pd2C3(CO)28]n (n=5, 6) represent the first homoleptic metal–carbonyl clusters containing three interstitial carbide atoms.

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