Oxoiron(IV) complexes of the tris(2-pyridylmethyl)amine ligand family: effect of pyridine alpha-substituents.
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 alpha-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.
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA.
Tapan K
TK
Paine
Miquel
M
Costas
József
J
Kaizer
Lawrence
L
Que
D058085:Iron Compounds / Q000737:chemistry*; D008024:Ligands; D011725:Pyridines / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet
D058085:Iron Compounds; D008024:Ligands; D011725:Pyridines; C431843:tris(2-pyridylmethyl)amine; C023666:pyridine