English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

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

Mao, W., Fehn, D., Heinemann, F. W., Scheurer, A., van Gastel, M., Venturinelli Jannuzzi, S. A., et al. (2022). Umpolung in a Pair of Cobalt(III) Terminal Imido/Imidyl Complexes. Angewandte Chemie International Edition, (61): e202206848, pp. 1-9. 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., Author           
Scheurer, Andreas1, Author
van Gastel, Maurice1, Author           
Venturinelli Jannuzzi, Sergio Augusto2, Author           
DeBeer, Serena2, Author           
Munz, Dominik1, Author
Meyer, Karsten, Author           
Affiliations:
1external, ou_persistent22              
2Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              

Content

show
hide
Free keywords: TRANSITION-METAL-COMPLEXES; H BOND AMINATION; IMIDO COMPLEXES; LIGATION SYNTHESIS; SPECIES RELEVANT; ORGANIC AZIDES; IRON; REACTIVITY; AZOARENES; LIGANDSChemistry; Cobalt; Imidyl Radical; N-Heterocyclic Carbene; Terminal Imido; Umpolung;
 Abstract: Reaction of the Co-I complex [(TIMMNmes)Co-I](PF6) (1) (TIMMNmes=tris-[2-(3-mesityl-imidazolin-2-ylidene)-methyl]amine) with mesityl azide yields the Co-III imide [(TIMMNmes)Co-III(NMes)](PF6) (2). Oxidation of 2 with [FeCp2](PF6) provides access to a rare Co-III 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 Co-I N-heterocyclic imine (4) within 12 h. Conversely, it takes merely 0.5 h for 3 to transform to the Co-II 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
 Publication Status: Issued
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: ISI: 000835455400001
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) Sequence Number: e202206848 Start / End Page: 1 - 9 Identifier: ISSN: 1433-7851
CoNE: https://pure.mpg.de/cone/journals/resource/1433-7851