Heterolytic versus Homolytic: Theoretical Insight into the Ni⁰‑Catalyzed Ph–F Bond Activation

The Ni0-catalyzed borylation of fluorobenzene (PhF) was theoretically investigated. Density functional theory (DFT) calculations disclosed that the Ph–F bond activation occurred heterolytically via an unprecedented nucleophilic aromatic substitution reaction (SNAr) assisted by an sp2–sp3 diboron complex [B2nep2·(OPh)]‑Na+, which forms a Ni0-ate complex as an active species. The diboron-ate complex stabilizes the transition state of the Ph–F bond activation through three interactions, a Ni···O coordination, a Na+···F cationic dipole interaction, and a charge transfer arising from NaOPh. On the other hand, the Ph–F bond activation catalyzed by Ni0(dcpe) and Ni0(PCy3)2 complexes has also been studied to allow a comparison between the monophosphine and bisphosphine ligands. Results suggest that Ni0(PCy3)2 is less effective than Ni0(dcpe) for the concerted oxidative addition of the Ph–F bond because the Ni dπ orbital of Ni0(PCy3)2 is at a lower energy level than that of Ni0(dcpe) in the equilibrium geometry. The characteristic molecular orbital features of Ni0-catalyzed Ph–F bond activation via both the nucleophilic aromatic substitution reaction (heterolytic) and the concerted oxidative addition (homolytic) were theoretically disclosed

Theoretical Insight into the Multiple Roles of LiHMDS in Pd-Catalyzed Borylation of Fluorobenzene

Pd-catalyzed borylation of fluorobenzene was theoretically studied. DFT calculations revealed that the reaction occurs through an unprecedented 3 + 6-membered ring transition state, in which one LiHMDS (HMDS = hexamethyldisilazane) acts as a ligand and another LiHMDS is essential to provide Li···N and Li···F interactions, overcoming the large destabilization of the strong phenyl–F bond distortion. The characteristic feature of LiHMDS was elucidated by comparing it with HMDS and NaHMDS analogues

Heterolytic versus Homolytic: Theoretical Insight into the Ni⁰‑Catalyzed Ph–F Bond Activation

The Ni0-catalyzed borylation of fluorobenzene (PhF) was theoretically investigated. Density functional theory (DFT) calculations disclosed that the Ph–F bond activation occurred heterolytically via an unprecedented nucleophilic aromatic substitution reaction (SNAr) assisted by an sp2–sp3 diboron complex [B2nep2·(OPh)]‑Na+, which forms a Ni0-ate complex as an active species. The diboron-ate complex stabilizes the transition state of the Ph–F bond activation through three interactions, a Ni···O coordination, a Na+···F cationic dipole interaction, and a charge transfer arising from NaOPh. On the other hand, the Ph–F bond activation catalyzed by Ni0(dcpe) and Ni0(PCy3)2 complexes has also been studied to allow a comparison between the monophosphine and bisphosphine ligands. Results suggest that Ni0(PCy3)2 is less effective than Ni0(dcpe) for the concerted oxidative addition of the Ph–F bond because the Ni dπ orbital of Ni0(PCy3)2 is at a lower energy level than that of Ni0(dcpe) in the equilibrium geometry. The characteristic molecular orbital features of Ni0-catalyzed Ph–F bond activation via both the nucleophilic aromatic substitution reaction (heterolytic) and the concerted oxidative addition (homolytic) were theoretically disclosed

Electronic Structures and Unusual Chemical Bonding in Actinyl Peroxide Dimers [An₂O₆]²⁺ and [(An₂O₆)(12-crown‑4 ether)₂]²⁺ (An = U, Np, and Pu)

As known, actinyl peroxides play important roles in environmental transport of actinides, and they have strategic importance in the application of nuclear industry. Compared to the most studied uranyl peroxides, the studies of transuranic counterparts are still few, and more information about these species is needed. In this work, experimentally inspired actinyl peroxide dimers ([An2O6]2+, An = U, Np, and Pu) have been studied and analyzed by using density functional theory and multireference wave function methods. This study determines that the three [An2O6]2+ have unique electronic structures and oxidation states, as [(UVIO2)2(O2)2–]2+, [(NpVIIO2)2(O2–)2]2+, and mixed-valent [(PuVI/VO2)2(O2)1–]2+. This study demonstrates the significance of two bridging oxo ligands with at most four electron holes availability in ionically directing actinyl and resulting in the unusual multiradical bonding in [(PuVI/VO2)2(O2)1–]2+. In addition, thermodynamically stable 12-crown-4 ether (12C4) chelated [(An2O6)(12C4)2]2+ complexes have been predicted, that could maintain these unique electronic structures of [An2O6]2+, where the An ← O12C4 dative bonding shows a trend in binding capacity of 12C4 from κ4 (U) to κ3 (Np) and κ4 (Pu). This study reveals the interesting electronic character and bonding feature of a series of early actinide elements in peroxide complexes, which can provide insights into the intrinsic stability of An-containing species