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A Nickel‐Containing Model System of Acireductone Dioxygenases that Utilizes a C(1)‐H Acireductone Substrate
Author(s) -
Allpress Caleb J.,
Berreau Lisa M.
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402254
Subject(s) - chemistry , reactivity (psychology) , nickel , ligand (biochemistry) , medicinal chemistry , methanol , regioselectivity , oxidative addition , amine gas treating , substrate (aquarium) , stereochemistry , nuclear magnetic resonance spectroscopy , organic chemistry , catalysis , medicine , biochemistry , oceanography , alternative medicine , receptor , pathology , geology
A mononuclear Ni II complex bearing the monoanion of 1‐acetoxy‐3‐phenylpropane‐2,3‐dione ( 4 ) as a ligand has been prepared {[(6‐Ph 2 TPA)Ni{PhC(O)C(O)CHOC(O)CH 3 )]ClO 4 , 5 ; 6‐Ph 2 TPA = N , N ‐bis[(6‐phenyl‐2‐pyridyl)methyl]‐ N ‐(2‐pyridylmethyl)amine}. This complex was characterized by 1 H NMR, UV/Vis and IR spectroscopy, mass spectrometry, and elemental analysis. Exposure of solutions of 5 to O 2 did not result in any reaction over the course of hours. Deprotection of 5 by the addition of NaOCH 3 in methanol generated a Ni II species ( 6 ) that contains a coordinated dianionic C(1)‐H acireductone. Exposure of 6 to O 2 led to regioselective oxidative cleavage reactivity akin to that found for the Ni II ‐containing acireductone dioxygenase enzyme. The strategy outlined herein is the first synthetic approach that enables examination of the oxidative reactivity of a synthetic Ni II species containing a dianionic C(1)‐H acireductone ligand.