Activation of σ‐Bonds by Group 13/Ylide‐Based Ambiphiles: Understanding and Design DOI Creative Commons
Daniel González‐Pinardo, Felix Krämer, Frank Breher

et al.

ChemistryEurope, Journal Year: 2024, Volume and Issue: 2(3-4)

Published: May 1, 2024

Abstract The factors controlling the activation of σ‐bonds promoted by hidden Frustrated Lewis Pairs have been computationally explored using quantum chemical tools. To this end, influence both nature group 13 element acting as acid well cooperative action antagonists on bond was quantitatively analyzed means strain model reactivity in combination with energy decomposition analysis method. It is found that while polar E X −H bonds (E 15 =group element; 16 element) feasible, analogous processes involving non‐polar 14 (CH 4 , SiH or H 2 ) proceed much higher barriers. Nevertheless, these processes, and particular dihydrogen activation, can be realizable (i. e. proceeding a feasible barrier) through rational design.

Language: Английский

Aromaticity transfer in an annulated 1,4,2-diazaborole: Facile access to Cs symmetric 1,4,2,5-diazadiborinines DOI

Vignesh Pattathil,

Conor Pranckevicius

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(60), P. 7705 - 7708

Published: Jan. 1, 2024

A tricyclic annulated 1,4,2-diazaborole is readily accessed

Language: Английский

Citations

1
Mono(Lewis Base)‐Stabilized Gallium Iodide: An Unexplored Class of Promising Ligands DOI

Sahtaz Ahmed,

Himashri Das,

Daniel González‐Pinardo

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(13)

Published: Dec. 18, 2023

Abstract Quantum‐chemical (DFT) calculations on hitherto unknown base(carbene)‐stabilized gallium monoiodides (LB→GaI) suggest that these systems feature one lone pair of electrons and a formally vacant p‐orbital – both centered at the central atom exhibit metallomimetic behavior. The calculated reaction free energies as well bond dissociation LB→GaI are capable forming stable donor‐acceptor complexes with group 13 trichlorides. Examination ligand exchange reactions iron nickel indicates their potential use ligands in transition metal chemistry. In addition, it is found title compounds also able to activate various enthalpically robust bonds. Further, detailed mechanistic investigation small molecule activation processes reveals non‐innocent behavior carbene (base) moiety attached GaI fragment, thereby indicating cooperative nature processes. energy decomposition analysis (EDA) strain model (ASM) reactivity were employed quantitatively understand rationalize different

Language: Английский

Citations

1
Activation of σ‐Bonds by Group 13/Ylide‐Based Ambiphiles: Understanding and Design DOI Creative Commons
Daniel González‐Pinardo, Felix Krämer, Frank Breher

et al.

ChemistryEurope, Journal Year: 2024, Volume and Issue: 2(3-4)

Published: May 1, 2024

Abstract The factors controlling the activation of σ‐bonds promoted by hidden Frustrated Lewis Pairs have been computationally explored using quantum chemical tools. To this end, influence both nature group 13 element acting as acid well cooperative action antagonists on bond was quantitatively analyzed means strain model reactivity in combination with energy decomposition analysis method. It is found that while polar E X −H bonds (E 15 =group element; 16 element) feasible, analogous processes involving non‐polar 14 (CH 4 , SiH or H 2 ) proceed much higher barriers. Nevertheless, these processes, and particular dihydrogen activation, can be realizable (i. e. proceeding a feasible barrier) through rational design.

Language: Английский

Citations

0