Iron in a Trigonal Tris(alkoxide) Ligand Environment

被引：31

作者：

Chambers, Matthew B. ^{[1
]}

Groysman, Stanislav ^{[1
]}

Villagran, Dino ^{[1
]}

Nocera, Daniel G. ^{[1
,2
]}

机构：

[1] MIT, Dept Chem, Cambridge, MA 02139 USA

[2] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 06期

关键词：

SPIN OXOIRON(IV) COMPLEX; CORRELATED MOLECULAR CALCULATIONS; NONHEME IRON(IV)-OXO COMPLEX; EFFECTIVE CORE POTENTIALS; OXYGEN-ATOM TRANSFER; GAUSSIAN-BASIS SETS; C-H ACTIVATION; AB-INITIO; SPECTROSCOPIC CHARACTERIZATION; 2-STATE REACTIVITY;

D O I：

10.1021/ic302634q

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Mononuclear Fe(II) and Fe(III) complexes residing in a trigonal tris(ditox) (ditox = Bu-t(2)(Me)CO-) ligand environment have been synthesized and characterized. The Fe(III) ditox complex does not react with oxidants such as PhIO, whereas NMe3O substitutes a coordinated tetrahydrofuran (THF) in the apical position without undergoing oxo transfer. In contrast, the Fe(II) ditox complex reacts rapidly with PhIO or Me3NO in THF or cyclohexadiene to furnish a highly reactive intermediate, which cleaves C-H bonds to afford the Fe(III)-hydroxide complex. When generated in 1,2-difluorobenze, this intermediate can be intercepted to oxidize phosphines to phosphine oxide. The fast rates at which these reactions occur is attributed to a particularly weak ligand field imparted by the tris(alkoxide) ancillary ligand environment.

引用

页码：3159 / 3169

页数：11

共 66 条

[41] High-valent nonheme iron-oxo complexes: Synthesis, structure, and spectroscopy [J].