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Oxidative Addition of C–X Bonds and H–H Activation Using PNNP‐Iron Complexes
Author(s) -
Gautam Monika,
Yatabe Takafumi,
Tanaka Shinji,
Satou Naoto,
Takeshita Tomohiro,
Yamaguchi Kazuya,
Nakajima Yumiko
Publication year - 2020
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201904616
Subject(s) - chemistry , ligand (biochemistry) , phenanthroline , deprotonation , bond cleavage , oxidative addition , stereochemistry , bromide , cleave , medicinal chemistry , photochemistry , crystallography , organic chemistry , receptor , catalysis , ion , biochemistry , enzyme
Iron(0) complex bearing a phenanthroline‐based meridional PNNP ligand [{Fe(PNNP)} 2 ( μ ‐N 2 )] ( 1 ) (PNNP=2,9‐bis((diphenylphosphino)methyl)‐1,10‐phenanthroline) smoothly reacted with CH 3 I at ambient temperature to cleave C–I bond, resulting in the formation of the corresponding oxidative addition product, [Fe(CH 3 )(I)(PNNP)] ( 2 ). Complex 2 was fully identified by NMR and its structure was determined by a single crystal X‐ray diffraction study. Mechanistic study using cyclopropylmethyl bromide as a radical clock supported a radical pathway for the C–I bond cleavage of CH 3 I. Complex 2 underwent deprotonation on treatment with NaO t Bu to form 4 , which possessed a dearomatized phenanthroline backbone. Complex 4 further reacted with H 2 to cleave H–H bond. The reaction was mediated by metal‐ligand cooperation process that involves re‐aromatization of the phenanthroline backbone of the PNNP ligand.