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

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High spin d5 complexes of tris(6-hydroxymethyl-2-pyridylmethyl)amine (H3L) : hepta-coordinated [Mn(H3L)]Cl2 and linear trinuclear [Fe3L2](ClO4)3. / Guisado-Barrios, Gregorio; Li, Yang; Slawin, Alexandra M Z; Richens, David T; Gass, Ian A; Murray, Paul R; Yellowlees, Lesley J; Brechin, Euan K.

In: Dalton Transactions, No. 4, 2008, p. 551-8.

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Guisado-Barrios, Gregorio ; Li, Yang ; Slawin, Alexandra M Z ; Richens, David T ; Gass, Ian A ; Murray, Paul R ; Yellowlees, Lesley J ; Brechin, Euan K. / High spin d5 complexes of tris(6-hydroxymethyl-2-pyridylmethyl)amine (H3L) : hepta-coordinated [Mn(H3L)]Cl2 and linear trinuclear [Fe3L2](ClO4)3. In: Dalton Transactions. 2008 ; No. 4. pp. 551-8.

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@article{2994072b7a57433eb13ef3733d86ee70,
title = "High spin d5 complexes of tris(6-hydroxymethyl-2-pyridylmethyl)amine (H3L): hepta-coordinated [Mn(H3L)]Cl2 and linear trinuclear [Fe3L2](ClO4)3",
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 interactions in such systems based on Fe-O(bridge) distances and Fe-O-Fe angles. The central hexa-alkoxide coordinated Fe(III) is novel and shows a remarkable resistance towards reduction to Fe(II).",
author = "Gregorio Guisado-Barrios and Yang Li and Slawin, {Alexandra M Z} and Richens, {David T} and Gass, {Ian A} and Murray, {Paul R} and Yellowlees, {Lesley J} and Brechin, {Euan K}",
year = "2008",
doi = "10.1039/b712188a",
language = "English",
pages = "551--8",
journal = "Dalton Transactions",
issn = "1477-9234",
publisher = "Royal Society of Chemistry",
number = "4",

}

RIS

TY - JOUR

T1 - High spin d5 complexes of tris(6-hydroxymethyl-2-pyridylmethyl)amine (H3L)

T2 - hepta-coordinated [Mn(H3L)]Cl2 and linear trinuclear [Fe3L2](ClO4)3

AU - Guisado-Barrios, Gregorio

AU - Li, Yang

AU - Slawin, Alexandra M Z

AU - Richens, David T

AU - Gass, Ian A

AU - Murray, Paul R

AU - Yellowlees, Lesley J

AU - Brechin, Euan K

PY - 2008

Y1 - 2008

N2 - 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 interactions in such systems based on Fe-O(bridge) distances and Fe-O-Fe angles. The central hexa-alkoxide coordinated Fe(III) is novel and shows a remarkable resistance towards reduction to Fe(II).

AB - 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 interactions in such systems based on Fe-O(bridge) distances and Fe-O-Fe angles. The central hexa-alkoxide coordinated Fe(III) is novel and shows a remarkable resistance towards reduction to Fe(II).

U2 - 10.1039/b712188a

DO - 10.1039/b712188a

M3 - Article

C2 - 18185873

SP - 551

EP - 558

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9234

IS - 4

ER -