Metal-Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands

被引：50

作者：

Kuppuswamy, Subramaniam ^{[1
]}

Powers, Tamara M. ^{[2
]}

Johnson, Bruce M. ^{[3
]}

Bezpalko, Mark W. ^{[1
]}

Brozek, Carl K. ^{[4
]}

Foxman, Bruce M. ^{[1
]}

Berben, Louise A. ^{[3
]}

Thomas, Christine M. ^{[1
]}

机构：

[1] Brandeis Univ, Dept Chem, Waltham, MA 02454 USA

[2] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02139 USA

[3] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

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

来源：

INORGANIC CHEMISTRY | 2013年 / 52卷 / 09期

关键词：

ELECTRONIC-STRUCTURE; BASIS-SETS; ATOM-TRANSFER; IRON; FE; SUSCEPTIBILITY; APPROXIMATION; ENVIRONMENTS; AMINATION; ENERGY;

D O I：

10.1021/ic302108k

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The tris(phosphinoamide)-bridged (FeFeII)-Fe-II diiron complex Fe(mu-PrNPPh2)(3)Fe(eta(2)-(PrNPPh2)-Pr-i) (1) can be reduced in the absence or presence of PMe3 to generate the mixed valence (FeFeI)-Fe-II complexes Fe(mu-(PrNPPh2)-Pr-i)(3)Fe((PPh2NHPr)-Pr-i) (2) or Fe(mu-(PrNPPh2)-Pr-i)(3)Fe(PMe3) (3), respectively. Following a typical oxidative group transfer procedure, treatment of 2 or 3 with organic azides generates the mixed-valent (FeFeIII)-Fe-II imido complexes Fe((PrNPPh2)-Pr-i)(3)Fe NR (R = Bu-t (4), Ad (5), 2,4,6-trimethylphenyl (6)). These complexes represent the first examples of first-row bimetallic complexes featuring both metal-ligand multiple bonds and metal-metal bonds. The reduced complexes 2 and 3 and imido complexes 4-6 have been characterized via X-ray crystallography, Mossbauer spectroscopy, cyclic voltammetry, and SQUID magnetometry, and a theoretical description of the bonding within these diiron complexes has been obtained using computational methods. The effect of the metal-metal interaction on the electronic structure and bonding in diiron imido complexes 4-6 is discussed in the context of similar monometallic iron imido complexes.

引用

页码：4802 / 4811

页数：10

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