Electrophilic insertion and ring growth in 1,2,5-azadiborolidines: theoretical evidence for boron-driven expansion
This study computationally investigates the reactivity of 1,2,5-azadiborolidine derivatives toward carbon monoxide (CO), extending ring-expansion mechanisms from borole chemistry. Establishing structural and electronic analogies through isosterism, we propose that endocyclic CO insertion operates in...
| Autores: | , , , , |
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| Tipo de documento: | artigo |
| Estado: | Versão publicada |
| Data de publicação: | 2025 |
| País: | España |
| Recursos: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositório: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/27439 |
| Acesso em linha: | http://hdl.handle.net/10256/27439 |
| Access Level: | Acceso aberto |
| Palavra-chave: | Reactivitat (Química) Reactivity (Chemistry) Bor Boron |
| Resumo: | This study computationally investigates the reactivity of 1,2,5-azadiborolidine derivatives toward carbon monoxide (CO), extending ring-expansion mechanisms from borole chemistry. Establishing structural and electronic analogies through isosterism, we propose that endocyclic CO insertion operates in this new class of boron heterocycles. 1,2,5-Tri-tert-butyl-1,2,5-azadiborolidine emerged as the optimal candidate, exhibiting a favourable three-step pathway: CO insertion, dimerization of the ring-expanded intermediate, and subsequent double [1,2]-migration. Thermochemical analysis confirms viability under mild conditions, with solvents (DCM, n-pentane, THF) providing similar barriers and reaction Gibbs energies. Key reactivity indicators include B–C(O) and C–O bond lengths, while correlations between kinetic barriers and σ → π*(CO) backdonation energies provide predictive insight. This work broadens boron-based reactivity by proposing a fourth class of CO-inserting boracycles and highlights 1,2,5-azadiborolidines as versatile, metal-free frameworks for small-molecule activation |
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