Beryllium compounds for the carbon-halogen bond activation of phenyl halides: the role of non-innocent ligands

Beryllium is a metallomimetic main-group element, i.e. , it behaves similarly to transition metals (TMs) in some bond activation processes. To investigate the ability of Be compounds to activate C-X bonds (X = F-I), we have computationally investigated, using DFT methods, the reaction of (CAAC) 2 Be...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2023-09, Vol.52 (37), p.1368-1378
Main Authors: Trujillo-González, Daniel E, González-García, Gerardo, Jiménez-Halla, J. Oscar C, Solà, Miquel
Format: Article
Language:English
Subjects:
Beryllium compounds
Chemical bonds
Electronegativity
Halides
Ligands
Reaction mechanisms
Transition metals
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Summary:Beryllium is a metallomimetic main-group element, i.e. , it behaves similarly to transition metals (TMs) in some bond activation processes. To investigate the ability of Be compounds to activate C-X bonds (X = F-I), we have computationally investigated, using DFT methods, the reaction of (CAAC) 2 Be (CAAC = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) and a series of five-membered heterocyclic beryllium bidentate ligands with phenyl halides. We have analysed all plausible reaction mechanisms and our results show that, after the initial C-X oxidative addition, migration of the phenyl group occurs towards the less electronegative heteroatom. Our theoretical study highlights the important role of bidentate non-innocent ligands in providing the required electrons for the initial Ph-X oxidative addition. In contrast, the monodentate ligand, CAAC, does not favour this oxidative addition. A detailed DFT mechanistic study is presented to describe the phenyl-halogen bond activation mediated by five-membered heterocyclic Be( ii ) bidentate ligands and (CAAC) 2 Be . Our study highlights the key role played by the ligands in this process.
ISSN:1477-9226
1477-9234
DOI:10.1039/d3dt02251j