On the Extreme Oxidation States of Iridium

被引：24

作者：

Pyykko, Pekka ^{[1
]}

Xu, Wen-Hua ^{[1
,2
,3
]}

机构：

[1] Univ Helsinki, Dept Chem, FIN-00014 Helsinki, Finland

[2] Northwest Univ, Coll Chem, Key Lab Synthet & Nat Funct Mol Chem, Minist Educ, Xian 710127, Peoples R China

[3] Northwest Univ, Dept Mat Sci, Xian 710127, Peoples R China

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2015年 / 21卷 / 26期

基金：

芬兰科学院;

关键词：

ab initio calculations; density functional calculations; iridium; IR spectroscopy; oxidation states; MOSSBAUER ISOMER-SHIFTS; INFRARED-SPECTROSCOPY; CARBONYL CATIONS; SPECTRA; APPROXIMATION; COMPLEXES; PALLADIUM; PLATINUM; METALS; MODEL;

D O I：

10.1002/chem.201500902

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

It has recently been suggested that the oxidation states of Ir run from the putative -III in the synthesized solid Na-3[Ir(CO)(3)] to the well-documented +IX in the species IrO4+. Furthermore, [Ir(CO)(3)](3-) was identified as an 18-electron species. A closer DFT study now finds support for this picture: The orbitals spanned by the 6s,6p,5d orbitals of the iridium are all occupied. Although some have considerable ligand character, the deviations from 18e leave the orbital symmetries unchanged. The isoelectronic systems from Os-IV to Au-I behave similarly, suggesting further possible species. To paraphrase RichardP. Feynmann there is plenty of room at the bottom.

引用

页码：9468 / 9473

页数：6

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