Lanthanide Clusters with Azide Capping Ligands

Moore, Brian; Emge, Thomas J.; Brennan, John G.

doi:10.1021/ic400359x

Cited by 9 publications

(2 citation statements)

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“…Bulky ligands on lanthanoid atoms have been frequently employed to lend lanthanoid azides more stability towards mechanical shock or temperature changes, and also to increase the solubility in organic and unipolar solvents. Targets of these works are the preparation of phosphors or of molecular nitrides of the lanthanoids, which still seem to be elusive …”

Section: Introductionmentioning

confidence: 99%

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Octaammine Eu^II and Yb^II Azides and Their Thermal Decompositions to the Nitrides

et al. 2016

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The common preparation for many nitrides is the synthesis from the corresponding metals and nitrogen at quite high temperatures and/or high pressures. Here we present a route to metal nitrides by the use of ammine metal azides under relatively mild conditions. Europium(II) and ytterbium(II) azides are prepared in liquid ammonia at –36 °C in form of their temperature‐sensitive octaammine complexes. These were investigated by single‐crystal X‐ray diffraction at low temperatures, and their structures seem to be the first evidence for the existence of homoleptic ammine EuII and YbII complexes, as well as that the coordination number of these divalent cations can go beyond six with NH3 ligands. In one of the cases presented here the observed coordination polyhedron is better described as a bicapped trigonal prism (C2v), in one case better as square‐antiprismatic (D4d). Warming of these compounds to room temperature leads to the lanthanoid metal azides still containing approximately 1 equiv. of ammonia. The behaviour of these azides towards further heating was investigated: By very careful and slow decomposition, the nitrides of europium(III) and ytterbium(III) are obtained at only 230 °C at ambient pressure. This method may be suitable to obtain other metal nitrides at remarkably low temperatures and pressures.

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Section: Introductionmentioning

confidence: 99%

“…Targets of these works are the preparation of phosphors or of molecular nitrides of the lanthanoids, which still seem to be elusive. [39][40][41][42][43][44][45] Metal azides can be synthesized by several routes. The most important one is the pathway along metal fluorides and trimethylsilyl azide.…”

Section: Introductionmentioning

confidence: 99%