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C−H and C−N Activation at Redox‐Active Pyridine Complexes of Iron
Author(s) -
MacLeod K. Cory,
Lewis Richard A.,
DeRosha Daniel E.,
Mercado Brandon Q.,
Holland Patrick L.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201610679
Subject(s) - pyridine , chemistry , redox , regioselectivity , bond cleavage , cleavage (geology) , catalysis , photochemistry , medicinal chemistry , polymer chemistry , inorganic chemistry , organic chemistry , materials science , fracture (geology) , composite material
Pyridine activation by inexpensive iron catalysts has great utility, but the steps through which iron species can break the strong (105–111 kcal mol −1 ) C−H bonds of pyridine substrates are unknown. In this work, we report the rapid room‐temperature cleavage of C−H bonds in pyridine, 4‐tert‐butylpyridine, and 2‐phenylpyridine by an iron(I) species, to give well‐characterized iron(II) products. In addition, 4‐dimethylaminopyridine (DMAP) undergoes room‐temperature C−N bond cleavage, which forms a dimethylamidoiron(II) complex and a pyridyl‐bridged tetrairon(II) square. These facile bond‐cleaving reactions are proposed to occur through intermediates having a two‐electron reduced pyridine that bridges two iron centers. Thus, the redox non‐innocence of the pyridine can play a key role in enabling high regioselectivity for difficult reactions.