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BIBTEX RIS

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

2013; American Chemical Society; Volume: 135; Issue: 29 Linguagem: Inglês

10.1021/ja402688t

ISSN

1943-2984

Autores

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

Tópico(s)

Magnetism in coordination complexes

Resumo

The new biomimetic ligands N4Py2Ph (1) and N4Py2Ph,amide (2) were synthesized and yield the iron(II) complexes [FeII(N4Py2Ph)(NCCH3)](BF4)2 (3) and [FeII(N4Py2Ph,amide)](BF4)2 (5). Controlled orientation of the Ph substituents in 3 leads to facile triplet spin reactivity for a putative FeIV(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 FeIIIOOR 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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