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Plasticity of the coordination sphere of Ag 2+
Author(s) -
Grochala Wojciech
Publication year - 2006
Publication title -
physica status solidi (b)
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.51
H-Index - 109
eISSN - 1521-3951
pISSN - 0370-1972
DOI - 10.1002/pssb.200642366
Subject(s) - octahedron , coordination sphere , crystallography , chemistry , bond length , ligand (biochemistry) , valence (chemistry) , jahn–teller effect , stereochemistry , ion , crystal structure , receptor , organic chemistry , biochemistry
The geometric distortions of the ligand environment around Ag 2+ cations have been examined for over 20 structurally characterized fluorides of Ag 2+ . Divalent silver is subject to a strong Jahn–Teller effect and it is most frequently found in an elongated or a compressed octahedral site. Typical Ag–F bond lengths vary from 2.34 to 2.60 Å (axial, R ax ) and from 2.01 to 2.11 Å (equatorial, R eq ) for the elongated octahedral site. The corresponding values for the compressed octahedral coordination are 2.00–2.09 Å ( R ax ) and 2.20–2.42 Å ( R eq ). The ellipsoidal Ag 2+ cation exhibits significant plasticity of its coordination sphere, similar to its lighter d 9 congener, Cu 2+ : the dependence of R eq vs. R ax is inverse and monotonic. The Jahn–Teller distortion parameter D (= R ax / R eq ) takes values from 0.83 to 1.29, with the forbidden range from 0.94 to 1.11 (close to ideal octahedron). Novel parametrization and subsequent analysis of the valence bond sums reveal that selected compounds of Ag 2+ require careful structural re‐examination. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)