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
✍ Scribed by Rituparna Biswas; Michael G. B. Drew; Carolina Estarellas; Antonio Frontera; Ashutosh Ghosh
- Publisher
- John Wiley and Sons
- Year
- 2011
- Tongue
- English
- Weight
- 763 KB
- Volume
- 2011
- Category
- Article
- ISSN
- 1434-1948
No coin nor oath required. For personal study only.
✦ Synopsis
Abstract
The synthesis and crystal structures of three nonheme diiron(III) complexes with a tridentate N,N,O Schiff‐baseligand, 2‐({[2‐(dimethylamino)ethyl]imino}methyl)phenol (HL), are reported. Complexes [Fe~2~OL~2~(NCO)~2~] (1a) and [Fe~2~OL~2~(SAL)~2~]·H~2~O [SAL = o‐(CHO)C~6~H~4~O^–^] (1b) are unsupported μ‐oxido‐bridged dimers, and [Fe~2~(OH)L~2~(HCOO)~2~(Cl)] (2) is a μ‐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)°], whereas in 2 the metal centers are hexacoordinate with a normal Fe–OH–Fe bridging angle [137.9(2)°]. The Fe–O–Fe angles in complexes 1a and 1b differ significantly to those usually shown by (μ‐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.