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Investigation of Counterion Influence on an Octahedral IrH6-Complex in the Solid State Hydrides AAeIrH6 (A = Na, K and Ae = Ca, Sr, Ba, and Eu) with a New Structure Type
journal contribution
posted on 2011-12-05, 00:00 authored by K. Kadir, D. Moser, M. Münzel, D. NoréusA number of new quaternary iridium based hydrides and
deuterides
AAeIrH/D6 (where A = Na and K; Ae = Ca, Ba, Sr, and Eu)
have been synthesized by direct combination of the alkali, alkaline
earth or europium binary hydrides/deuterides and iridium powder. The
crystal structures were determined by Guinier–Hägg X-ray
and neutron powder diffraction and a new cubic structure type was
found. The structure is described in space group F4̅3m, but related to the K2PtCl6 type structure. The new structure can be described as consisting
of cubes of A+ and Ae2+ ions, where the A+ and Ae2+ ions alternates so that they occupy opposite
corners in the cube. Every second cube contains a regular octahedral
[Ir(III)H6]−3-complex and the adjacent
is empty. Solid-state IR spectroscopy was used to determine the Ir-allowed
stretching and bending frequencies for the [Ir(III)H6]−3 complex with different counterions. These were also
compared with the corresponding stretching frequencies for Fe(II)H6, Ru(II)H6, Os(II)H6, and Ir(II)H5 complexes in similar solid state hydrides, which increased
when going from Fe through Ru, Os to Ir. The frequencies scaled almost
linearly with the inverse of size of the cube surrounding the complexes
but showed no significant dependence of the formal oxidation state
or the experimentally obtained Ir–D distances. However, this
was mainly because of difficulties in obtaining enough accurate atomic
positions. The ab initio DFT calculations could reproduce the stretching
frequencies within a few 10 cm–1, indicating that
experimental vibrational frequencies offer a sensitive test of DFT
results.
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Keywords
RuBairidium powdercomplexcubeK 2PtCl type structureneutron powder diffractionSolid State Hydrides AAeIrH 6frequencyCounterion Influenceab initio DFT calculationsvibrational frequencies offerstate hydridesEuNaFeSrquaternary iridiumDFT resultsstructure typecrystal structuresIRoxidation stateNew Structure TypeA number
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