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Nitrene Insertion into CC and CH Bonds of Diamide Diimine Ligands Ligated to Chromium and Iron
Author(s) -
Heins Spencer P.,
Morris Wesley D.,
Wolczanski Peter T.,
Lobkovsky Emil B.,
Cundari Thomas R.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201507463
Subject(s) - diimine , chemistry , chromium , ligand (biochemistry) , medicinal chemistry , reactivity (psychology) , stereochemistry , organic chemistry , catalysis , biochemistry , receptor , medicine , alternative medicine , pathology
The impact of redox non‐innocence (RNI) on chemical reactivity is a forefront theme in coordination chemistry. A diamide diimine ligand, [{‐CHN(1,2‐C 6 H 4 )NH(2,6‐ i Pr 2 C 6 H 3 )} 2 ] n ( n =0 to −4), (dadi) n , chelates Cr and Fe to give [(dadi)M] ([ 1 Cr(thf)] and [ 1 Fe]). Calculations show [ 1 Cr(thf)] (and [ 1 Cr]) to have a d 4 Cr configuration antiferromagnetically coupled to (dadi) 2− *, and [ 1 Fe] to be S =2. Treatment with RN 3 provides products where RN is formally inserted into the CC bond of the diimine or into a CH bond of the diimine. Calculations on the process support a mechanism in which a transient imide (imidyl) aziridinates the diimine, which subsequently ring opens.