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High and low spin mononuclear and dinuclear iron(II) complexes of 4-amino and 4-pyrrolyl-3,5-di(2-pyridyl)-4H-1,2,4-triazoles

High and low spin mononuclear and dinuclear iron(II) complexes of 4-amino and 4-pyrrolyl-3,5-di(2-pyridyl)-4H-1,2,4-triazoles
High and low spin mononuclear and dinuclear iron(II) complexes of 4-amino and 4-pyrrolyl-3,5-di(2-pyridyl)-4H-1,2,4-triazoles
The first dinuclear iron(II) complexes of any 4-substituted 3,5-di(2-pyridyl)-4H-1,2,4-triazole ligands, [Fe(II)2(adpt)2(H2O)1.5(CH3CN)2.5](BF4)4 and [Fe(II)2(pldpt)2(H2O)2(CH3CN)2](BF4)4, are presented [where adpt is 4-amino-3,5-di(2-pyridyl)-4H-1,2,4-triazole and pldpt is 4-pyrrolyl-3,5-di(2-pyridyl)-4H-1,2,4-triazole]. Both dinuclear complexes feature doubly triazole bridged iron(II) centers that are found to be [high spin-high spin] at all temperatures, 4-300 K, and to exhibit weak antiferromagnetic coupling. In the analogous monometallic complexes, [Fe(II)(Rdpt)2(X)2](n+), the spin state of the iron(II) center was controlled by appropriate selection of the axial ligands X. Specifically, both of the chloride complexes, [Fe(II)(adpt)2(Cl)2] x 2 MeOH and [Fe(II)(pldpt)2(Cl)2] x 2 MeOH x H2O, were found to be high spin whereas the pyridine adduct [Fe(II)(adpt)2(py)2](BF4)2 was low spin. Attempts to prepare [Fe(II)(pldpt)2(py)2](BF4)2 and the dinuclear analogues [Fe(II)2(Rdpt)2(py)4](BF4)4 failed, illustrating the significant challenges faced in attempts to develop control over the nature of the product obtained from reactions of iron(II) and these bis-bidentate ligands.
0020-1669
9450-9458
Kitchen, Jonathan A.
3999f5cb-d53e-4c51-b750-627bd2a1b9b6
Noble, Andy
cd64dac8-bb8a-479d-ab90-dad34c1d5f58
Brandt, Carsten D.
46a6cd37-fb4e-4c75-af7e-66850f46cd3a
Moubaraki, Boujemaa
eb24a914-5451-4870-8615-cd853a46b864
Murray, Keith S.
091a4624-9b14-4413-923b-7330444e64b2
Brooker, Sally
2ee9681a-3ff7-41be-88c5-681f66b953ef
Kitchen, Jonathan A.
3999f5cb-d53e-4c51-b750-627bd2a1b9b6
Noble, Andy
cd64dac8-bb8a-479d-ab90-dad34c1d5f58
Brandt, Carsten D.
46a6cd37-fb4e-4c75-af7e-66850f46cd3a
Moubaraki, Boujemaa
eb24a914-5451-4870-8615-cd853a46b864
Murray, Keith S.
091a4624-9b14-4413-923b-7330444e64b2
Brooker, Sally
2ee9681a-3ff7-41be-88c5-681f66b953ef

Kitchen, Jonathan A., Noble, Andy, Brandt, Carsten D., Moubaraki, Boujemaa, Murray, Keith S. and Brooker, Sally (2008) High and low spin mononuclear and dinuclear iron(II) complexes of 4-amino and 4-pyrrolyl-3,5-di(2-pyridyl)-4H-1,2,4-triazoles. Inorganic Chemistry, 47 (20), 9450-9458. (doi:10.1021/ic801039j). (PMID:18808113)

Record type: Article

Abstract

The first dinuclear iron(II) complexes of any 4-substituted 3,5-di(2-pyridyl)-4H-1,2,4-triazole ligands, [Fe(II)2(adpt)2(H2O)1.5(CH3CN)2.5](BF4)4 and [Fe(II)2(pldpt)2(H2O)2(CH3CN)2](BF4)4, are presented [where adpt is 4-amino-3,5-di(2-pyridyl)-4H-1,2,4-triazole and pldpt is 4-pyrrolyl-3,5-di(2-pyridyl)-4H-1,2,4-triazole]. Both dinuclear complexes feature doubly triazole bridged iron(II) centers that are found to be [high spin-high spin] at all temperatures, 4-300 K, and to exhibit weak antiferromagnetic coupling. In the analogous monometallic complexes, [Fe(II)(Rdpt)2(X)2](n+), the spin state of the iron(II) center was controlled by appropriate selection of the axial ligands X. Specifically, both of the chloride complexes, [Fe(II)(adpt)2(Cl)2] x 2 MeOH and [Fe(II)(pldpt)2(Cl)2] x 2 MeOH x H2O, were found to be high spin whereas the pyridine adduct [Fe(II)(adpt)2(py)2](BF4)2 was low spin. Attempts to prepare [Fe(II)(pldpt)2(py)2](BF4)2 and the dinuclear analogues [Fe(II)2(Rdpt)2(py)4](BF4)4 failed, illustrating the significant challenges faced in attempts to develop control over the nature of the product obtained from reactions of iron(II) and these bis-bidentate ligands.

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Published date: 23 September 2008
Organisations: Chemistry

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Local EPrints ID: 343594
URI: http://eprints.soton.ac.uk/id/eprint/343594
ISSN: 0020-1669
PURE UUID: 937eed09-9216-4e09-8381-57345e09b790
ORCID for Jonathan A. Kitchen: ORCID iD orcid.org/0000-0002-7139-5666

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Date deposited: 09 Oct 2012 09:13
Last modified: 16 Sep 2019 18:38

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