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Oxoiron(IV) complexes of the tris(2-pyridylmethyl)amine ligand family: effect of pyridine α-substituents

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An Erratum to this article was published on 01 November 2006

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Abstract

The oxoiron(IV) complexes of two 6-substituted tris(2-pyridylmethyl)amine ligand derivatives have been generated and characterized with respect to their spectroscopic and reactivity properties. The introduction of an α-substituent maintains the low-spin nature of the oxoiron(IV) unit but weakens the ligand field, as evidenced by red shifts in its characteristic near-IR chromophore. While its hydrogen-atom abstraction ability is only slightly affected, the oxo-transfer reactivity of the oxoiron(IV) center is significantly enhanced relative to that of the parent complex. These results demonstrate that the ligand environment plays a key role in modulating the reactivity of this important biological oxidant.

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Fig. 1
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Change history

  • 01 November 2006

    Erratum to: J Biol Inorg Chem 11:272–276 DOI 10.1007/s00775-006-0089-6

Abbreviations

acac:

Pentane-2,4-dionate anion

BnOH:

Benzyl alcohol

ESI:

Electrospray ionization

6-Me–TPA:

(6-Methyl-2-pyridylmethyl)bis(2-pyridylmethyl)amine

N4Py:

Bis(2-pyridylmethyl)bis(2-pyridyl)methylamine

OTf:

Trifluoromethanesulfonate anion

PhSMe:

Thioanisole

Py:

Pyridine

PyO:

Pyridine-N-oxide

QBPA:

(2-Quinolylmethyl)bis(2-pyridylmethyl)amine

TauD:

Taurine/α-ketoglutarate dioxygenase

TMC:

1,4,8,11-Tetramethyl-1,4,8,11-tetraazacyclotetradecane

TPA:

Tris(2-pyridylmethyl)amine

TPM:

Triphenylmethane

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Acknowledgement

This work was supported by grant GM33162 from the National Institutes of Health to L.Q.

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Author notes

  1. Tapan K. Paine

    Present address: Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A&2B Raja S C Mullick Road, 700032, Calcutta, India

  2. Miquel Costas

    Present address: Departament de Quimica, Universitat de Girona, 17071, Girona, Spain

  3. József Kaizer

    Present address: Research Group for Petrochemistry, Hungarian Academy of Sciences, 8200, Veszprem, Hungary

Authors and Affiliations

  1. Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN, 55455, USA

    Tapan K. Paine, Miquel Costas, József Kaizer & Lawrence Que Jr

Authors
  1. Tapan K. Paine
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  2. Miquel Costas
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  3. József Kaizer
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  4. Lawrence Que Jr
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Correspondence to Lawrence Que Jr.

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Paine, T.K., Costas, M., Kaizer, J. et al. Oxoiron(IV) complexes of the tris(2-pyridylmethyl)amine ligand family: effect of pyridine α-substituents. J Biol Inorg Chem 11, 272–276 (2006). https://doi.org/10.1007/s00775-006-0089-6

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