Nitrene Insertion into C-C and C-H Bonds of Diamide Diimine Ligands Ligated to Chromium and Iron.
Angew Chem Int Ed Engl
; 54(48): 14407-11, 2015 Nov 23.
Article
em En
| MEDLINE
| ID: mdl-26440694
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-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 d(4) 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.
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MEDLINE
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Ano de publicação:
2015
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Article