Lanthanide Complexes: Electronic Structure and H—H, C—H, and Si—H Bond Activation from a DFT Perspective

2004 ◽  
pp. 116-133 ◽  
Author(s):  
Lionel Perrin ◽  
Laurent Maron ◽  
Odile Eisenstein
Keyword(s):  
Electronic Structure ◽  
Lanthanide Complexes ◽  
Bond Activation

scholarly journals Imido Cobalt Complexes with Imidyl Character

2021 ◽  
Author(s):  
alexander Reckziegel ◽  
Manjinder Kour ◽  
Beatrice Battistella ◽  
Stefan Mebs ◽  
Katrin Beuthert ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Spin Density ◽  
High Spin ◽  
Bond Activation ◽  
High Spin State ◽  
Cobalt Complexes ◽  
Spectroscopic Methods ◽  
Computational Studies ◽  
Ancillary Ligand ◽  
Unpaired Spin

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L<sub>2</sub>)<sup>–</sup>, (L = N(Dipp)SiMe<sub>3</sub>), Dipp = 2,6-diisopropylphenyl) bearing very long Co–NAryl bonds of around 1.75 Å. The electronic structure was interrogated using a variety of physical and spectroscopic methods indicating the first authenticated examples of cobalt bound imidyl species. Computational studies corroborate these findings and reveal that the high-spin state of these complexes gives rise to unpaired spin-density on the imide nitrogen and leads to its imidyl character. Obtained complexes are capable of intermolecular H atom abstraction from C–H bonds that yields the corresponding cobalt amides. Exchange of the Dipp-substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me<sub>3</sub>Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.<br>

scholarly journals Imido Cobalt Complexes with Imidyl Character

2021 ◽  
Author(s):  
alexander Reckziegel ◽  
Manjinder Kour ◽  
Beatrice Battistella ◽  
Stefan Mebs ◽  
Katrin Beuthert ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Spin Density ◽  
High Spin ◽  
Bond Activation ◽  
High Spin State ◽  
Cobalt Complexes ◽  
Spectroscopic Methods ◽  
Computational Studies ◽  
Ancillary Ligand ◽  
Unpaired Spin

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L<sub>2</sub>)<sup>–</sup>, (L = N(Dipp)SiMe<sub>3</sub>), Dipp = 2,6-diisopropylphenyl) bearing very long Co–NAryl bonds of around 1.75 Å. The electronic structure was interrogated using a variety of physical and spectroscopic methods indicating the first authenticated examples of cobalt bound imidyl species. Computational studies corroborate these findings and reveal that the high-spin state of these complexes gives rise to unpaired spin-density on the imide nitrogen and leads to its imidyl character. Obtained complexes are capable of intermolecular H atom abstraction from C–H bonds that yields the corresponding cobalt amides. Exchange of the Dipp-substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me<sub>3</sub>Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.<br>

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