Secondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach

نویسندگان

  • Sumit Sahu
  • Leland R. Widger
  • Matthew G. Quesne
  • Sam P. de Visser
  • Hirotoshi Matsumura
  • Pierre Moënne-Loccoz
  • Maxime A. Siegler
  • David P. Goldberg
چکیده

The new biomimetic ligands N4Py(2Ph) (1) and N4Py(2Ph,amide) (2) were synthesized and yield the iron(II) complexes [Fe(II)(N4Py(2Ph))(NCCH3)](BF4)2 (3) and [Fe(II)(N4Py(2Ph,amide))](BF4)2 (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative Fe(IV)(O) intermediate, resulting in rapid arene hydroxylation. Addition of a peripheral amide substituent within hydrogen-bond distance of the iron first coordination sphere leads to stabilization of a high-spin Fe(III)OOR species which decays without arene hydroxylation. These results provide new insights regarding the impact of secondary coordination sphere effects at nonheme iron centers.

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عنوان ژورنال:

دوره 135  شماره 

صفحات  -

تاریخ انتشار 2013