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The impact of redox non-innocence (RNI) on chemical reactivity is a forefront theme in coordination chemistry. A diamide diimine ligand, [{-CH=N(1,2- C6H4)NH(2,6-iPr2C6H3)}2]n (n=0 to -4), (dadi)n, chelates Cr and Fe to give [(dadi)M] ([1Cr(thf)] and [1Fe]). Calculations show [1Cr(thf)] (and [1Cr]) to have a d4 Cr configuration antiferromagnetically coupled to (dadi)2-*, and [1Fe] to be S= 2. Treatment with RN3 provides products where RN is formally inserted into the C-C bond of the diimine or into a C-H bond of the diimine. Calculations on the process support a mechanism in which a transient imide (imidyl) aziridinates the diimine, which subsequently ring opens. [ABSTRACT FROM AUTHOR]

The impact of redox non‐innocence (RNI) on chemical reactivity is a forefront theme in coordination chemistry. A diamide diimine ligand, [{‐CHN(1,2‐C6H4)NH(2,6‐iPr2C6H3)}2]n (n=0 to −4), (dadi)n, chelates Cr and Fe to give [(dadi)M] ([1Cr(thf)] and [1Fe]). Calculations show [1Cr(thf)] (and [1Cr]) to have a d4 Cr configuration antiferromagnetically coupled to (dadi)2−*, and [1Fe] to be S=2. Treatment with RN3 provides products where RN is formally inserted into the CC bond of the diimine or into a CH bond of the diimine. Calculations on the process support a mechanism in which a transient imide (imidyl) aziridinates the diimine, which subsequently ring opens.Who’s your dadi? The implementation of a redox non‐innocent diamide diimine (dadi)n chelate enables intramolecular CC and CH nitrene insertion reactions. The reaction depends on the type of azide precursor used. [ABSTRACT FROM AUTHOR]