Out-of-center distortions in d0 transition metal oxide fluoride anions

Margaret E. Welk, Alexander J. Norquist, Frederick P. Arnold, Charlotte L. Stern, Kenneth R Poeppelmeier

Research output: Contribution to journalArticle

106 Citations (Scopus)

Abstract

Electronic effects and the bond network are the two factors that cause out-of-center distortions in octahedral d0 transition metal oxide fluoride anions. Overlap between filled oxide p orbitals and vacant cation d orbitals results in strong, short metal-oxide bonds causing the metal ion to distort toward the oxide ligand. This primary, electronic distortion is not dependent on the extended structure. Smaller, secondary distortions of the anionic octahedra are caused by interactions with the bond network. [HNC6H6OH]2[Cu(NC5 H5)4(NbOF5)2], prepared with 5-hydroxy-2-methylpyridine that provides two coordination contact sites to the anion when protonated, exhibits distortions in the anion reflecting both factors. Crystal data for [HNC6H6OH]2[Cu(NC5 H5)4(NbOF5)2]: monoclinic, space group C2/c (No. 15), with a = 10.9427(8) Å, b = 16.204(1) Å, c = 21.396(2), Å, β = 93.263(1)°, and Z = 4. Conditions for detection of both distortion types are discussed with five additional examples.

Original languageEnglish
Pages (from-to)5119-5125
Number of pages7
JournalInorganic Chemistry
Volume41
Issue number20
DOIs
Publication statusPublished - Oct 7 2002

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Fluorides
Oxides
Transition metals
Anions
metal oxides
fluorides
transition metals
anions
orbitals
oxides
electronics
Metal ions
Cations
metal ions
Metals
Ligands
cations
Crystals
ligands
causes

ASJC Scopus subject areas

  • Inorganic Chemistry

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Out-of-center distortions in d0 transition metal oxide fluoride anions. / Welk, Margaret E.; Norquist, Alexander J.; Arnold, Frederick P.; Stern, Charlotte L.; Poeppelmeier, Kenneth R.

In: Inorganic Chemistry, Vol. 41, No. 20, 07.10.2002, p. 5119-5125.

Research output: Contribution to journalArticle

Welk, Margaret E. ; Norquist, Alexander J. ; Arnold, Frederick P. ; Stern, Charlotte L. ; Poeppelmeier, Kenneth R. / Out-of-center distortions in d0 transition metal oxide fluoride anions. In: Inorganic Chemistry. 2002 ; Vol. 41, No. 20. pp. 5119-5125.
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