A Pd(II) → Pd(0) → Pd(II) Catalytic Cycle Enables the Generation of Bis(o-carborane)s: Confirmed by Reproduced Yields and Ratios, Regioselectivities, Additive and Substituent Effects DOI
Wei‐Hua Mu, Lin Zhu,

Jiawei Yu

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: June 3, 2025

The palladium-catalyzed generation of bis(o-carborane)s via regioselective B-B coupling was explored by using density functional theory (DFT). It is found that the reaction proceeds through sequential B4-H activation, B4'-H/B5'-H and reductive elimination, yielding ultimately. palladium catalyst tends to experience a Pd(II) → Pd(0) rather than Pd(IV) catalytic cycle, in which second B-H (B4'-H/B5'-H) activation serves as rate-determining step (RDS). Computed RDS step's barriers (27.0/29.0 kcal·mol-1, TS2a_I/TS2a'_I) consist well with experimental yields selectivities (P1a:P2a = 57%:23%). regioselectivity primarily controlled process, electronic effect playing key role steric hindrance influencing somewhat, confirmed natural bond orbital (NBO) noncovalent interaction (NCI) analyses. free-energy (27.0/29.6/31.1 kcal·mol-1) for AgOAc/AgF/NiCl2-co-assisted (Path a_I), AgOAc/AgF-co-assisted a_II), AgOAc-assisted a_III) cases agree perfectly corresponding trends (obtained 57%/43%/12% P1a, respectively). Theoretical predictions substituent effects also demonstrate consistency observations. This perfect agreement between experiments computations validates providing crucial insights into o-carboranes thus aiding controllable synthesis carborane materials.

Language: Английский

A Pd(II) → Pd(0) → Pd(II) Catalytic Cycle Enables the Generation of Bis(o-carborane)s: Confirmed by Reproduced Yields and Ratios, Regioselectivities, Additive and Substituent Effects DOI
Wei‐Hua Mu, Lin Zhu,

Jiawei Yu

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: June 3, 2025

The palladium-catalyzed generation of bis(o-carborane)s via regioselective B-B coupling was explored by using density functional theory (DFT). It is found that the reaction proceeds through sequential B4-H activation, B4'-H/B5'-H and reductive elimination, yielding ultimately. palladium catalyst tends to experience a Pd(II) → Pd(0) rather than Pd(IV) catalytic cycle, in which second B-H (B4'-H/B5'-H) activation serves as rate-determining step (RDS). Computed RDS step's barriers (27.0/29.0 kcal·mol-1, TS2a_I/TS2a'_I) consist well with experimental yields selectivities (P1a:P2a = 57%:23%). regioselectivity primarily controlled process, electronic effect playing key role steric hindrance influencing somewhat, confirmed natural bond orbital (NBO) noncovalent interaction (NCI) analyses. free-energy (27.0/29.6/31.1 kcal·mol-1) for AgOAc/AgF/NiCl2-co-assisted (Path a_I), AgOAc/AgF-co-assisted a_II), AgOAc-assisted a_III) cases agree perfectly corresponding trends (obtained 57%/43%/12% P1a, respectively). Theoretical predictions substituent effects also demonstrate consistency observations. This perfect agreement between experiments computations validates providing crucial insights into o-carboranes thus aiding controllable synthesis carborane materials.

Language: Английский

Citations

0