High spin d5 complexes of tris(6-hydroxymethyl-2-pyridylmethyl)amine (H3L): hepta-coordinated [Mn(H3L)]Cl2 and linear trinuclear [Fe3L2](ClO4)3

Dalton Transactions : an International Journal of Inorganic Chemistry
Gregorio Guisado-BarriosEuan K Brechin

Abstract

Reaction of MnCl(2).4H(2)O with H(3)L (H(3)L = tris(6-hydroxymethyl-2-pyridylmethyl)amine) in methanol gives hepta-coordinated [Mn(H(3)L)]Cl(2) involving attachment of Mn(II) to all four nitrogens and three hydroxymethyl arms. Reaction of H(3)L with Fe(ClO(4))(2).6H(2)O in CH(3)CN in the presence of NaO(2)CC(6)H(5) in an attempt to make [Fe(III)OH(H(3)L)(O(2)CC(6)H(5))](ClO(4)), a putative model for soybean lipoxygenase-1, instead gave rise to the linear triiron(III) complex [Fe(3)L(2)](ClO(4))(3) with all three hydroxymethyl arms deprotonated and forming three alkoxide bridges between each Fe(III) centre. The central Fe(III) is hexa-coordinated to only the alkoxide bridges and flanked by two hepta-coordinated iron(III) centres analogous to the Mn(ii) complex. [Fe(3)L(2)](ClO(4))(3) exhibits two reversible 1e(-) reductions to mixed-valence [Fe(3)L(2)](2+) and [Fe(3)L(2)](+) forms. Structure data and magnetochemistry on [Fe(3)L(2)](ClO(4))(3) reveals the tightest Fe-O-Fe angle (87.4 degrees ) and shortest Fe...Fe distance (2.834 A) yet found for any weakly antiferromagnetically-coupled high spin alkoxide-bridged di- or triiron(iii) system and challenges current theories involved in correlating the extent/nature of magnetic inter...Continue Reading

References

May 5, 1999·Current Opinion in Chemical Biology·H C LiangK D Karlin
May 21, 1997·Inorganic Chemistry·Peter CombaKenneth D. Karlin
Nov 7, 1996·Chemical Reviews·Lawrence Que, Raymond Y. N. Ho
Aug 3, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·David G LonnonStephen B Colbran

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Citations

Apr 16, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Gavin A CraigGuillem Aromí
Mar 1, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Fawaz A SaadBenson M Kariuki

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