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Crystal Structures of Ag 2 ZrF 6 ·8NH 3 and Ag 2 HfF 6 ·8NH 3 and Their Synthesis by the “Reactive Fluoride Route” in Liquid Ammonia
Author(s) -
Meng Weizhe,
Kraus Florian
Publication year - 2008
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.200800230
Subject(s) - chemistry , ammonia , oxidizing agent , dissolution , fluoride , ternary operation , fluorine , ionic bonding , inorganic chemistry , lattice energy , ionic liquid , stoichiometry , crystal structure , transition metal , metal , crystallography , ion , catalysis , organic chemistry , computer science , programming language
Starting from the ternary transition‐metal fluorides Ag 3 M 2 F 14 (M = Zr, Hf) and dry liquid ammonia, [Ag(NH 3 ) 4 (μ‐NH 3 )Ag(NH 3 ) 3 ]ZrF 6 ( 1 ) and [Ag(NH 3 ) 4 (μ‐NH 3 )Ag(NH 3 ) 3 ]HfF 6 ( 2 ) have been prepared as colorless single crystals crystallizing isotypically in the space group Pnma ‐ D 2 h 16 (No. 62). The compounds feature weak Ag ··· Ag interactions known as argentophilicity, which is yet unknown in fluorides. It is also shown that ionic silver(II) fluorides are suitable starting materials for fluorine chemistry in liquid ammonia and are easily reduced to Ag I by oxidizing ammonia. This driving force bypasses the generally high lattice energy of ionic fluorides, so that they can be dissolved easily. We would like to introduce the term “reactive fluoride route” for this method of dissolving reactive ionic fluorides in liquid ammonia. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)