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The Dimeric [V 2 O 4 F 6 ] 4– Vanadium Oxide‐Fluoride Anion in Na 2 (M(H 2 O) 2 )(V 2 O 4 F 6 ) (M = Co 2+ , Ni 2+ , and Cu 2+ )
Author(s) -
Donakowski Martin D.,
Vinokur Anastasiya I.,
Poeppelmeier Kenneth R.
Publication year - 2012
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201200121
Subject(s) - fluoride , vanadium , hydrofluoric acid , inorganic chemistry , chemistry , transition metal , oxide , vanadium oxide , metal , ion , nucleophile , crystallography , catalysis , organic chemistry
Three new vanadium oxide‐fluoride phases, Na 2 (M(H 2 O) 2 )(V 2 O 4 F 6 ) (M = Co 2+ , Ni 2+ , and Cu 2+ ), were prepared by hydrothermal techniques in hydrofluoric acid. The compounds contain the dioxo vanadium fluoride dimeric anion: [V 2 O 4 F 6 ] 4– . The harder (Na + ) and softer (M = Co 2+ , Ni 2+ , and Cu 2+ ) cations coordinate to the harder fluoride and softer oxide anions, respectively. In contrast to monoxo vanadium fluorides, the dioxo vanadium fluoride exhibits an increased nucleophilicity of the oxide anions. This increased nucleophilicity allows the anion to bond covalently with late transition metals to form 2D layers that contain both an early transition metal (V 5+ ) and a late transition metal (Co 2+ , Ni 2+ , or Cu 2+ ).