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Issue 12, 2015
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The approach to 4d/4f-polyphosphides

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The first 4d/4f polyphosphides were obtained by reaction of the divalent metallocenes [Cp*2Ln(thf)2] (Ln = Sm, Yb) with [{CpMo(CO)2}2(μ,η2:2-P2)] or [Cp*Mo(CO)23-P3)]. Treatment of [Cp*2Ln(thf)2] (Ln = Sm, Yb) with [{CpMo(CO)2}2(μ,η2:2-P2)] gave the 16-membered bicyclic compounds [(Cp2*Ln)2P2(CpMo(CO)2)4] (Ln = Sm, Yb) as the major products. From the reaction involving samarocene, the cyclic P4 complex [(Cp*2Sm)2P4(CpMo(CO)2)2] and the cyclic P5 complex [(Cp*2Sm)3P5(CpMo(CO)2)3] were also obtained as minor products. In each reaction, the P2 unit is reduced and a rearrangement occurred. In dedicated cases, a P–P bond formation takes place, which results in a new aggregation of the central phosphorus scaffold. In the reactions of [Cp*2Ln(thf)2] (Ln = Sm, Yb) with [Cp*Mo(CO)2P3] a new P–P bond is formed by reductive dimerization and the 4d/4f hexaphosphides [(Cp*2Ln)2P6(Cp*Mo(CO)2)2] (Ln = Sm, Yb) were obtained.

Graphical abstract: The approach to 4d/4f-polyphosphides

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The article was received on 22 Jun 2015, accepted on 07 Sep 2015 and first published on 29 Sep 2015

Article type: Edge Article
DOI: 10.1039/C5SC02252E
Citation: Chem. Sci., 2015,6, 7179-7184
  • Open access: Creative Commons BY-NC license
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    The approach to 4d/4f-polyphosphides

    N. Arleth, M. T. Gamer, R. Köppe, N. A. Pushkarevsky, S. N. Konchenko, M. Fleischmann, M. Bodensteiner, M. Scheer and P. W. Roesky, Chem. Sci., 2015, 6, 7179
    DOI: 10.1039/C5SC02252E

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