Nitrene Insertion into CC and CH Bonds of Diamide Diimine Ligands Ligated to Chromium and Iron. Issue 48 (6th October 2015)

• Record Type: Journal Article
• Authors: Heins, Spencer P.; Morris, Wesley D.; Wolczanski, Peter T.; Lobkovsky, Emil B.; Cundari, Thomas R.
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 48(2015)
• Page Start: 14407
• Page End: 14411
• Publication Date: 2015-10-06
• Subjects: chelates -- chromium -- iron -- nitrene -- redox chemistry; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201507463
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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‐C6 H4 )NH(2, 6‐ i Pr2 C6 H3 )}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 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 : 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.