Computational Studies of Intramolecular Carbon−Heteroatom Bond Activation of N-Aryl Heterocyclic Carbene Ligands

2008 ◽  
Vol 27 (5) ◽  
pp. 938-944 ◽  
Author(s):  
Richard A. Diggle ◽  
Andrew A. Kennedy ◽  
Stuart A. Macgregor ◽  
Michael K. Whittlesey
Keyword(s):  
Bond Activation ◽  
Computational Studies ◽  
Carbene Ligands

Computational studies on Ni-catalyzed amide C–N bond activation

2019 ◽  
Vol 55 (76) ◽  
pp. 11330-11341 ◽  
Author(s):  
Hongliang Wang ◽  
Shuo-Qing Zhang ◽  
Xin Hong
Keyword(s):  
Bond Activation ◽  
Bond Cleavage ◽  
Mechanistic Models ◽  
Computational Studies

This review summarizes the mechanistic models of Ni-catalyzed amide C–N bond cleavage and discusses their applications in related transformations.

scholarly journals Dehydrocoupling of phosphine–boranes using the [RhCp*Me(PMe3)(CH2Cl2)][BArF4] precatalyst: stoichiometric and catalytic studies

2016 ◽  
Vol 7 (3) ◽  
pp. 2414-2426 ◽  
Author(s):  
Thomas N. Hooper ◽  
Andrew S. Weller ◽  
Nicholas A. Beattie ◽  
Stuart A. Macgregor
Keyword(s):  
Bond Activation ◽  
Computational Studies ◽  
Secondary Phosphine

Detailed experimental and computational studies are reported on the fundamental B–H and P–H bond activation steps involved in the dehydrocoupling/dehydropolymerization of primary and secondary phosphine–boranes, H3B·PPhR′H (R = Ph, H), using the [RhCp*(PMe3)Me(ClCH2Cl)][BArF4] catalyst.

scholarly journals Smooth C(alkyl)–H bond activation in rhodium complexes comprising abnormal carbene ligands

2011 ◽  
Vol 40 (38) ◽  
pp. 9911 ◽  
Author(s):  
Anneke Krüger ◽  
L. Jonas L. Häller ◽  
Helge Müller-Bunz ◽  
Olha Serada ◽  
Antonia Neels ◽  
...  
Keyword(s):  
Bond Activation ◽  
Rhodium Complexes ◽  
Carbene Ligands

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 Abnormal N-heterocyclic Carbenes: More than Just Exceptionally Strong Donor Ligands

2011 ◽  
Vol 64 (8) ◽  
pp. 1113 ◽  
Author(s):  
Anneke Krüger ◽  
Martin Albrecht
Keyword(s):  
Water Oxidation ◽  
Bond Activation ◽  
Heterocyclic Carbenes ◽  
Oxidation Catalysis ◽  
Donor Ligands ◽  
Free Alcohol ◽  
Carbene Ligands ◽  
Transfer Processes ◽  
Oxidative Transformations ◽  
Electron Transfer Processes

Complexes comprising a so-called abnormal carbene ligand, which displays pronounced mesoionic character, have recently been shown to be competent catalyst precursors for bond activation processes and oxidative transformations, including base-free alcohol oxidation and water oxidation. In this highlight we propose that these abnormal carbene ligands are not just useful spectator ligands but also actively participate in the bond activation step. This mode of action is partially based on the exceptionally strong donor properties of the ligand and, specifically, on the mesoionic character of these abnormal carbenes. The mesoionic properties provide a reservoir for charges and holes and thus induce efficient ligand-metal cooperativity, which is beneficial in particular for oxidation catalysis that involves concerted proton and electron transfer processes.

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