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Octaammine Eu II and Yb II Azides and Their Thermal Decompositions to the Nitrides
Author(s) -
Müller Thomas G.,
Mogk Jochen,
Conrad Matthias,
Kraus Florian
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600709
Subject(s) - chemistry , homoleptic , europium , nitride , lanthanide , inorganic chemistry , ytterbium , metal , thermal decomposition , crystallography , organic chemistry , ion , layer (electronics) , physics , optoelectronics , doping
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 Eu II and Yb II complexes, as well as that the coordination number of these divalent cations can go beyond six with NH 3 ligands. In one of the cases presented here the observed coordination polyhedron is better described as a bicapped trigonal prism ( C 2 v ), in one case better as square‐antiprismatic ( D 4 d ). 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.