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The Solid‐State Lanthanoid‐Assisted Hydrolysis of the Solvolytically “Inert” [AsF 6 ] − Ion
Author(s) -
Ponikvar Maja,
Sedej Borka,
Liebman Joel F.
Publication year - 2004
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.200300632
Subject(s) - chemistry , lanthanide , octahedron , hydrolysis , solid state , ligand (biochemistry) , catalysis , homogeneous , crystallography , inorganic chemistry , ion , solvent , coordination sphere , nuclear chemistry , crystal structure , organic chemistry , biochemistry , physics , receptor , thermodynamics
Results of elemental chemical analyses of the coordination compounds of the type LnF n (AsF 6 ) 3‐ n (Ln = Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) indicated unexpectedly low stability of the generally highly hydrolytically stable [AsF 6 ] − ion. Experiments conducted on model compounds of the type NdF n (AsF 6 ) 3‐ n have shown that hydrolysis proceeded instantaneously during the reaction of the solid compound with water. The ligand substitution catalysis of the compounds is explained in terms of the distortion of the [AsF 6 ] − octahedra earlier shown by vibrational spectroscopy. The study contrasts formally related reactions on the solid−solvent interface as opposed to those in homogeneous solution. A new look at some long studied and well‐known inorganic species is offered. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)