Karmakar, Soma ; Chakravorty, Animesh (1996) Carboxyl-bonded low-spin iron(III). Chemistry of a family of coordination type cis-FeN4O2 Inorganic Chemistry, 35 (7). pp. 1935-1939. ISSN 0020-1669
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Official URL: http://pubs.acs.org/doi/abs/10.1021/ic950976q
Related URL: http://dx.doi.org/10.1021/ic950976q
Abstract
Three tridentate ligands H2PhL (Ar = Ph), H2ToL (Ar = p-tolyl), and H2NpL (Ar = α-naphthyl) of structural type HON=C(Ar)N=NC6H4CO2H have been synthesized. These (general abbreviation H2ArL) react with iron(III) chloride, affording the pink Et4N[Fe(ArL)2] (s = 1/2; μeff = 1.98-2.04 μ B) in which azo oxime chelation ensures spin-pairing while carboxylate coordination stabilizes the trivalent state. The EPR spectra of the complexes in frozen dimethylformamide-toluene glass (77 K) are rhombic with g values in the range 1.997-2.173. The X-ray structure of Et4N[Fe(NpL)2]·H2O·CH2Cl2 has been determined, revealing meridional binding of the two ligands affording cis-FeN4O2 geometry. The effect of spin-pairing is expressed in the relatively short (~1.90 Å) Fe-O and Fe-N lengths. The water of crystallization is hydrogen-bonded to carboxyl O atoms. The iron(III)-iron(II) reduction potentials lie near -0.1 V vs SCE. Crystal data for Et4N[Fe(NpL)2]·H2O·CH2Cl2: crystal system triclinic, space group P, a = 11.539(9) Å, b = 13.306(13) Å, c = 14.60(2) Å, α = 89.30(9)°, β = 82.65(9)°, γ = 79.90(8)°, V = 2189(4) Å3, Z = 2, R = 6.59%, Rw = 6.23%.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to American Chemical Society. |
| ID Code: | 6789 |
| Deposited On: | 26 Oct 2010 06:00 |
| Last Modified: | 31 Jan 2011 07:03 |
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