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Issue 6, 2014
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Addition of pnictogen atoms to chromium(II): synthesis, structure and magnetic properties of a chromium(IV) phosphide and a chromium(III) arsenide

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Abstract

Chromium(II) chloride reacts with lithium pentamethylcyclopentadienide (LiCp*, Cp* = C5Me5) and LiE(SiMe3)2 (E = P or As) to give the heterocubane chromium phosphide [(η5-Cp*Cr)(μ3-P)]4 (1) or the chromium arsenide cage [(η5-Cp*Cr)33-As)2] (2), respectively. The crystal and molecular structures of both compounds have been determined by X-ray crystallography. The reactions represent unusual oxidative additions of pnictogen atoms to chromium(II), which in the case of 1 results in the formation of the unusual chromium(IV) formal oxidation state, and in the case of 2 provides access to chromium(III). Compound 1 is also a rare example of a transition metal μ3-phosphide-ligated cubane. Magnetic susceptibility and magnetization measurements, with support from DFT calculations, indicate S = 2 and S = 9/2 ground states for 1 and 2, respectively, which can be rationalized by considering the electronic structure in terms of chromium–chromium bonding.

Graphical abstract: Addition of pnictogen atoms to chromium(ii): synthesis, structure and magnetic properties of a chromium(iv) phosphide and a chromium(iii) arsenide

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Publication details

The article was received on 04 Mar 2014, accepted on 27 Mar 2014 and first published on 28 Mar 2014


Article type: Edge Article
DOI: 10.1039/C4SC00666F
Citation: Chem. Sci., 2014,5, 2443-2448
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    Addition of pnictogen atoms to chromium(II): synthesis, structure and magnetic properties of a chromium(IV) phosphide and a chromium(III) arsenide

    S. Reisinger, M. Bodensteiner, E. M. Pineda, J. J. W. McDouall, M. Scheer and R. A. Layfield, Chem. Sci., 2014, 5, 2443
    DOI: 10.1039/C4SC00666F

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