Synthesis and Crystal Structures of μ-Oxido- and μ-Hydroxido-Bridged Dinuclear Iron(III) Complexes with an N2O Donor Ligand - A Theoretical Study on the Influence of Weak Forces on the Fe-O-Fe Bridging Angle

被引：27

作者：

Biswas, Rituparna ^{[2
]}

Drew, Michael G. B. ^{[3
]}

Estarellas, Carolina ^{[1
]}

Frontera, Antonio ^{[1
]}

Ghosh, Ashutosh ^{[2
]}

机构：

[1] Univ Illes Balears, Dept Quim, Palma De Mallorca 07122, Baleares, Spain

[2] Univ Calcutta, Dept Chem, Univ Coll Sci, Kolkata 700009, India

[3] Univ Reading, Sch Chem, Reading RG6 6AD, Berks, England

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2011年 / 16期

基金：

英国工程与自然科学研究理事会;

关键词：

Iron; Schiff bases; N; O ligands; Crystal structures; Density functional calculations; TRANSITION-METAL-COMPLEXES; X-RAY STRUCTURES; MOLECULAR-STRUCTURE; ELECTRONIC-STRUCTURE; EXCHANGE INTERACTION; DIIRON COMPLEX; ACTIVE-SITE; OXO; OXYGEN; IRON;

D O I：

10.1002/ejic.201100032

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis and crystal structures of three nonheme di-iron(III) complexes with a tridentate N,N,O Schiff-base ligand, 2-({[2-(dimethylamino) ethyl] imino} methyl) phenol (HL), are reported. Complexes [Fe2OL2(NCO)(2)] (1a) and [Fe2OL2(SAL)(2)]center dot H2O [SAL = o-(CHO)C6H4O-] (1b) are unsupported mu-oxido-bridged dimers, and [Fe-2(OH)L-2(HCOO)(2)-(Cl)] (2) is a mu-hydroxido-bridged dimer supported by a formato bridging ligand. All complexes have been characterized by X-ray crystallography and spectroscopic analysis. Complex 1b has been reported previously; however, it has been reinvestigated to confirm the presence of a crucial water molecule in the solid state. Structural analyses show that in 1a the iron atoms are pentacoordinate with a bent Fe-O-Fe angle [142.7(2)degrees], whereas in 2 the metal centers are hexacoordinate with a normal Fe-OH-Fe bridging angle [137.9(2)degrees]. The Fe-O-Fe angles in complexes 1a and 1b differ significantly to those usually shown by (mu-oxido) Fe-III complexes. A theoretical study has been performed in order to rationalize this deviation. Moreover, the influence of the water molecule observed in the solid-state structure of 1b on the Fe-O-Fe angle is also analyzed theoretically.

引用

页码：2558 / 2566

页数：9

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