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

被引：120

作者：

Welk, ME ^{[1
]}

Norquist, AJ ^{[1
]}

Arnold, FP ^{[1
]}

Stern, CL ^{[1
]}

Poeppelmeier, KR ^{[1
]}

机构：

[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA

来源：

INORGANIC CHEMISTRY | 2002年 / 41卷 / 20期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1021/ic025622v

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Electronic effects and the bond network are the two factors that cause out-of-center distortions in octahedral d(0) 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(NC5H5)(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(NC5H5)(4)(NbOF5)(2)]: monoclinic, space group C2/c (No. 15), with a = 10.9427(8) Angstrom, b = 16.204(1) Angstrom, c = 21-396(2) Angstrom, beta = 93.263(1)degrees, and Z = 4. Conditions for detection of both distortion types are discussed with five additional examples.

引用

页码：5119 / 5125

页数：7

共 26 条

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