Issue 12, 2015

The approach to 4d/4f-polyphosphides


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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Article information

Article type
Edge Article
22 Jun 2015
07 Sep 2015
First published
29 Sep 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 7179-7184

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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