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Chemical Hardness and the Adaptive Coordination Behavior of the d 0 Transition Metal Oxide Fluoride Anions
Author(s) -
Marvel Michael R.,
Pinlac Rachelle Ann F.,
Lesage Julien,
Stern Charlotte L.,
Poeppelmeier Kenneth R.
Publication year - 2009
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.200900019
Subject(s) - fluoride , chemistry , inorganic chemistry , oxide , isostructural , ion , alkali metal , polarizability , transition metal , crystallography , metal , crystal structure , molecule , organic chemistry , catalysis
Five new isostructural d 0 transition metal oxide fluoride compounds Rb 3 Na(NbOF 5 ) 2 · H 2 O and A 3 Na( M O 2 F 4 ) 2 · H 2 O ( A = K, Rb and M = Mo, W) have been synthesized by hydrothermal methods and their original structures determined by single‐crystal X‐ray diffraction. In these compounds, the sodium ions preferentially engage in strong electrostatic interactions with the least polarizable fluoride ions and concurrently the Nb 5+ , M 6+ ( M = Mo, W) metal centers displace toward the oxide ion(s) located trans to the fluorides in order to maintain atomic valences. Consequently, the oxide and fluoride sites retain unequal charge and the most negatively charged ions form the most/strongest interactions with the cations. The electrostatic potentials and the chemical hardness differences of the oxide and fluoride ions thus determine the anion connectivities: the cis ‐oxo M O 2 F 4 2– anions ( M = Mo, W) engage in the most/strongest electrostatic interactions with the alkali counter‐cations through the two fluorides trans to the cis oxides. The NbOF 5 2– anion forms its most/strongest electrostatic interactions with the cations through the one fluoride position trans to the oxide.