English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Umpolung in a Pair of Cobalt(III) Terminal Imido/Imidyl Complexes

Mao, W., Fehn, D., Heinemann, F. W., Scheurer, A., van Gastel, M., Jannuzzi, S. A. V., et al. (2022). Umpolung in a Pair of Cobalt(III) Terminal Imido/Imidyl Complexes. Angewandte Chemie International Edition, 61(36): e202206848. doi:10.1002/anie.202206848.

Item is

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Mao, Weiqing1, Author
Fehn, Dominik1, Author
Heinemann, Frank W.1, Author
Scheurer, Andreas1, Author
van Gastel, Maurice2, Author           
Jannuzzi, Sergio A. V.3, Author
DeBeer, Serena3, Author
Munz, Dominik1, Author
Meyer, Karsten1, Author
Affiliations:
1Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Inorganic Chemistry, Egerlandstrasse 1, 91058 Erlangen, Germany, ou_persistent22              
2Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541713              
3Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34–36, 45470 Mülheim an der Ruhr, Germany, ou_persistent22              

Content

show
hide
Free keywords: Cobalt; Imidyl Radical; N-Heterocyclic Carbene; Terminal Imido; Umpolung
 Abstract: Reaction of the CoI complex [(TIMMNmes)CoI](PF6) (1) (TIMMNmes=tris-[2-(3-mesityl-imidazolin-2-ylidene)-methyl]amine) with mesityl azide yields the CoIII imide [(TIMMNmes)CoIII(NMes)](PF6) (2). Oxidation of 2 with [FeCp2](PF6) provides access to a rare CoIII imidyl [(TIMMNmes)Co(NMes)](PF6)2 (3). Single-crystal X-ray diffractometry and EPR spectroscopy confirm the molecular structure of 3 and its S=1/2 ground state. ENDOR, X-ray absorption spectroscopy and computational analyses indicate a ligand-based oxidation; thus, an imidyl-radical electronic structure for 3. Migratory insertion of one ancillary NHC to the imido ligand in 2 gives the CoI N-heterocyclic imine (4) within 12 h. Conversely, it takes merely 0.5 h for 3 to transform to the CoII congener (5). The migratory insertion in 2 occurs via a nucleophilic attack of the imido ligand at the NHC to give 4, whereas in 3, a nucleophilic attack of the NHC at the electrophilic imidyl ligand yields 5. The reactivity shunt upon oxidation of 2 to 3 confirms an umpolung of the imido ligand.

Details

show
hide
Language(s): eng - English
 Dates: 2022-05-102022-06-082022-09-05
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/anie.202206848
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Angewandte Chemie International Edition
  Abbreviation : Angew. Chem., Int. Ed.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 61 (36) Sequence Number: e202206848 Start / End Page: - Identifier: ISSN: 1433-7851
CoNE: https://pure.mpg.de/cone/journals/resource/1433-7851