Coordinative flexibility of the 2-amino-2-(hydroxymethyl)propane-1,3-diol ligand in the synthesis of polynuclear Fe(III) complexes

Alan Ferguson, Lynne H. Thomas, Mark Murrie

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

The synthesis, structure and magnetic properties of four polynuclear iron(III)-containing polynuclear complexes are reported, [Fe 6NaO 2(HL) 2(H 2L) 2(PhCO 2) 9]·2MeCN (1·2MeCN), [Fe 6NaO 2(HL) 2(H 2L) 2(O 2CCMe 3) 9]·2MeCN (2·2MeCN), [Fe 8O 4(HL) 2(O 2CC 6H 4OPh) 10(NO 3) 2]·6MeCN (3·6MeCN) and [Fe 12O 6(OH) 2(HL) 2(H 2L) 2(PhCO 2) 16(PhCO 2H) 2]·6MeCN (4·6MeCN) {H 3L = 2-amino-2-(hydroxymethyl)propane-1,3-diol, H 2NC(CH 2OH) 3 or Tris}. The flexibility of the ligand, in both binding mode and level of deprotonation, has allowed isolation of complexes with a range of core topologies. All four complexes were prepared using iron oxo-centred carboxylate (pivalate, benzoate or 2-phenoxybenzoate) triangles {Fe 3O(O 2CR) 6} 0/+1 as starting materials and combining these with the Tris ligand or the trisodium salt of the ligand. The cores of complexes 1 and 2 are composed of {Fe 3O} units; 3 of {Fe 4O 2} units and 4 of fused {Fe 3O} units. Complexes 1 and 2 display a previously unseen core topology in iron-oxo chemistry. The magnetic properties of the complexes are dominated by antiferromagnetic exchange interactions. Magnetic characterization reveals small non-zero spin ground states for 1, 2 and 4 that are not well isolated, while 3 has a spin ground state of zero.
Original languageEnglish
Pages (from-to)227-233
JournalPolyhedron
Volume52
Early online date4 Oct 2012
DOIs
Publication statusPublished - 22 Mar 2013

Fingerprint

Propane
propane
flexibility
Iron
Ligands
iron
Ground state
ligands
Magnetic properties
synthesis
topology
Topology
magnetic properties
Deprotonation
ground state
Benzoates
Exchange interactions
triangles
carboxylates
isolation

Cite this

Coordinative flexibility of the 2-amino-2-(hydroxymethyl)propane-1,3-diol ligand in the synthesis of polynuclear Fe(III) complexes. / Ferguson, Alan; Thomas, Lynne H.; Murrie, Mark.

In: Polyhedron, Vol. 52, 22.03.2013, p. 227-233.

Research output: Contribution to journalArticle

@article{f4cf7d3255874ae8b3f8f032515b630b,
title = "Coordinative flexibility of the 2-amino-2-(hydroxymethyl)propane-1,3-diol ligand in the synthesis of polynuclear Fe(III) complexes",
abstract = "The synthesis, structure and magnetic properties of four polynuclear iron(III)-containing polynuclear complexes are reported, [Fe 6NaO 2(HL) 2(H 2L) 2(PhCO 2) 9]·2MeCN (1·2MeCN), [Fe 6NaO 2(HL) 2(H 2L) 2(O 2CCMe 3) 9]·2MeCN (2·2MeCN), [Fe 8O 4(HL) 2(O 2CC 6H 4OPh) 10(NO 3) 2]·6MeCN (3·6MeCN) and [Fe 12O 6(OH) 2(HL) 2(H 2L) 2(PhCO 2) 16(PhCO 2H) 2]·6MeCN (4·6MeCN) {H 3L = 2-amino-2-(hydroxymethyl)propane-1,3-diol, H 2NC(CH 2OH) 3 or Tris}. The flexibility of the ligand, in both binding mode and level of deprotonation, has allowed isolation of complexes with a range of core topologies. All four complexes were prepared using iron oxo-centred carboxylate (pivalate, benzoate or 2-phenoxybenzoate) triangles {Fe 3O(O 2CR) 6} 0/+1 as starting materials and combining these with the Tris ligand or the trisodium salt of the ligand. The cores of complexes 1 and 2 are composed of {Fe 3O} units; 3 of {Fe 4O 2} units and 4 of fused {Fe 3O} units. Complexes 1 and 2 display a previously unseen core topology in iron-oxo chemistry. The magnetic properties of the complexes are dominated by antiferromagnetic exchange interactions. Magnetic characterization reveals small non-zero spin ground states for 1, 2 and 4 that are not well isolated, while 3 has a spin ground state of zero.",
author = "Alan Ferguson and Thomas, {Lynne H.} and Mark Murrie",
year = "2013",
month = "3",
day = "22",
doi = "10.1016/j.poly.2012.09.043",
language = "English",
volume = "52",
pages = "227--233",
journal = "Polyhedron",
issn = "0277-5387",
publisher = "Elsevier",

}

TY - JOUR

T1 - Coordinative flexibility of the 2-amino-2-(hydroxymethyl)propane-1,3-diol ligand in the synthesis of polynuclear Fe(III) complexes

AU - Ferguson, Alan

AU - Thomas, Lynne H.

AU - Murrie, Mark

PY - 2013/3/22

Y1 - 2013/3/22

N2 - The synthesis, structure and magnetic properties of four polynuclear iron(III)-containing polynuclear complexes are reported, [Fe 6NaO 2(HL) 2(H 2L) 2(PhCO 2) 9]·2MeCN (1·2MeCN), [Fe 6NaO 2(HL) 2(H 2L) 2(O 2CCMe 3) 9]·2MeCN (2·2MeCN), [Fe 8O 4(HL) 2(O 2CC 6H 4OPh) 10(NO 3) 2]·6MeCN (3·6MeCN) and [Fe 12O 6(OH) 2(HL) 2(H 2L) 2(PhCO 2) 16(PhCO 2H) 2]·6MeCN (4·6MeCN) {H 3L = 2-amino-2-(hydroxymethyl)propane-1,3-diol, H 2NC(CH 2OH) 3 or Tris}. The flexibility of the ligand, in both binding mode and level of deprotonation, has allowed isolation of complexes with a range of core topologies. All four complexes were prepared using iron oxo-centred carboxylate (pivalate, benzoate or 2-phenoxybenzoate) triangles {Fe 3O(O 2CR) 6} 0/+1 as starting materials and combining these with the Tris ligand or the trisodium salt of the ligand. The cores of complexes 1 and 2 are composed of {Fe 3O} units; 3 of {Fe 4O 2} units and 4 of fused {Fe 3O} units. Complexes 1 and 2 display a previously unseen core topology in iron-oxo chemistry. The magnetic properties of the complexes are dominated by antiferromagnetic exchange interactions. Magnetic characterization reveals small non-zero spin ground states for 1, 2 and 4 that are not well isolated, while 3 has a spin ground state of zero.

AB - The synthesis, structure and magnetic properties of four polynuclear iron(III)-containing polynuclear complexes are reported, [Fe 6NaO 2(HL) 2(H 2L) 2(PhCO 2) 9]·2MeCN (1·2MeCN), [Fe 6NaO 2(HL) 2(H 2L) 2(O 2CCMe 3) 9]·2MeCN (2·2MeCN), [Fe 8O 4(HL) 2(O 2CC 6H 4OPh) 10(NO 3) 2]·6MeCN (3·6MeCN) and [Fe 12O 6(OH) 2(HL) 2(H 2L) 2(PhCO 2) 16(PhCO 2H) 2]·6MeCN (4·6MeCN) {H 3L = 2-amino-2-(hydroxymethyl)propane-1,3-diol, H 2NC(CH 2OH) 3 or Tris}. The flexibility of the ligand, in both binding mode and level of deprotonation, has allowed isolation of complexes with a range of core topologies. All four complexes were prepared using iron oxo-centred carboxylate (pivalate, benzoate or 2-phenoxybenzoate) triangles {Fe 3O(O 2CR) 6} 0/+1 as starting materials and combining these with the Tris ligand or the trisodium salt of the ligand. The cores of complexes 1 and 2 are composed of {Fe 3O} units; 3 of {Fe 4O 2} units and 4 of fused {Fe 3O} units. Complexes 1 and 2 display a previously unseen core topology in iron-oxo chemistry. The magnetic properties of the complexes are dominated by antiferromagnetic exchange interactions. Magnetic characterization reveals small non-zero spin ground states for 1, 2 and 4 that are not well isolated, while 3 has a spin ground state of zero.

UR - http://www.scopus.com/inward/record.url?scp=84875464767&partnerID=8YFLogxK

UR - http://dx.doi.org/10.1016/j.poly.2012.09.043

U2 - 10.1016/j.poly.2012.09.043

DO - 10.1016/j.poly.2012.09.043

M3 - Article

VL - 52

SP - 227

EP - 233

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

ER -