In:
Angewandte Chemie, Wiley, Vol. 134, No. 22 ( 2022-05-23)
Abstract:
We disclose a new reactivity mode for electrophilic cyano λ 3 ‐iodanes as group transfer one‐electron oxidants to synthesize Fe III and Fe IV cyanide complexes. The inherent thermal instability of high‐valent Fe IV compounds without π‐donor ligands (such as oxido (O 2− ), imido (RN 2− ) or nitrido (N 3− )) makes their isolation and structural characterization a very challenging task. We report the synthesis of an Fe IV cyanide complex [(N 3 N′)FeCN] ( 4 ) by two consecutive single electron transfer (SET) processes from Fe II precursor [(N 3 N′)FeLi(THF)] ( 1 ) with cyanobenziodoxolone (CBX). The Fe IV complex can also be prepared by reaction of [(N 3 N′)Fe III ] ( 3 ) with CBX. In contrast, the oxidation of Fe II with 1‐cyano‐3,3‐dimethyl‐3‐(1H)‐1,2‐benziodoxole (CDBX) enables the preparation of Fe III cyanide complex [(N 3 N′)Fe III (CN)(Li)(THF) 3 ] ( 2‐Li THF ). Complexes 4 and 2‐Li THF have been structurally characterized by single crystal X‐ray diffraction and their electronic structure has been examined by Mössbauer, EPR spectroscopy, and computational analyses.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v134.22
DOI:
10.1002/ange.202201699
Language:
English
Publisher:
Wiley
Publication Date:
2022
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