Open AccessSecondary Coordination Sphere Influence on the Reactivity of Nonheme Iron(II) Complexes: An Experimental and DFT Approach
Author(s) -
Sumit Sahu,
Leland R. Widger,
Matthew G. Quesne,
Sam P. de Visser,
Hirotoshi Matsumura,
Pierre MoënneLoccoz,
Maxime A. Siegler,
David P. Goldberg
Publication year - 2013
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/ja402688t
Subject(s) - chemistry , amide , reactivity (psychology) , coordination sphere , hydroxylation , substituent , coordination complex , yield (engineering) , stereochemistry , medicinal chemistry , spin states , hydrogen bond , crystallography , molecule , organic chemistry , metal , inorganic chemistry , crystal structure , enzyme , medicine , alternative medicine , materials science , pathology , metallurgy
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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