Redox- and Charge-State Dependent Trends in 5, 6, and 7-Membered Boron Heterocycles: A Neutral Ligand Coordination Chemistry Approach to Boracyclic Cations, Anions, and Radicals

Abstract

Metrics & MoreArticle Recommendations CONSPECTUS: Boron heterocycles represent an important subset of heteroatom-incorporated rings, attracting attention from organic, inorganic, and materials chemists. The empty p z orbital at the boron center makes them stand out as quintessential Lewis acidic molecules, also serving as a means to modulate electronic structure and photophysical properties in a facile manner. As boracycles are ripe for extensive functionalization, they are used in catalysis, chemical biology, materials science, and continue to be explored as chemical synthons for conjugated materials and reagents.Neutral boron(III)-incorporated polycyclic molecules are some of the most studied types of boracycles, and understanding their redox transformations is important for applications relying on electron transfer and charge transport. While relevant redox species can often be electrochemically observed, it remains challenging to isolate and characterize boracycles where the boron center and/or polycyclic skeleton have been chemically reduced. We describe our recent work isolating 5-, 6-, and 7-membered boracyclic radicals, anions, and cations, focusing on stabilization strategies, ligand-mediated bonding situations, and reactivity. We present a versatile neutral ligand coordination chemistry approach that permits the transformation of boracycles from potent electrophiles to powerful nucleophilic heterocycles that facilitate diverse electron transfer and bond activation chemistry. Although there are a wide range of suitable stabilizing ligands, we have employed both diamino-N-heterocyclic carbenes (NHCs) and cyclic(alkyl)(amino) carbenes (CAACs), which led to boracycles with tunable electronic structures and aromaticity trends. We highlight successful isolation of borafluorene radicals and demonstrate their reversible redox behavior, undergoing oxidation to the cation or reduction to the anion. The borafluorene anion is a chemical synthon that has been used to prepare boryl main-group and transition-metal bonds, luminescent oxabora-spirocycles, borafluorenate-crown ethers, and CO-releasing molecules via carbon dioxide activation. We expanded to 6-membered boracycles and characterized neutral bis(NHC-supported 9-boraphenanthrene)s and the corresponding bis(CAAC-stabilized 9-boraphenanthrene) biradical. We detail the interconvertible multiredox states of boraphenalene, where the boraphenalenyl radical, anion, and cation mimic the charge-states of the all-hydrocarbon analogue. Reactivity studies of the boraphenalenyl anion displayed unusual nucleophilic reactivity at multiple sites on the periphery of the boraphenalenyl tricyclic scaffold. Reduced borepins, 7-membered boron containing heterocycles, have also been isolated. We used a stepwise one-pot synthesis combining the halo-borepin precursor, CAAC, and KC 8 to afford the monomeric borepin radicals and anions. The π-system was extended to contain two borepin rings fused in a pentacyclic scaffold, which permitted isolation of diborepin biradicals and a diborep...

Mono- and Bis-Phosphine Promoted Incorporation of Boron, Nitrogen, and Phosphorus into Heterocycles via Staudinger Reactions of Borafluorene Azides

“…9-Borafluorenes are a popular class of boron-centered polycyclic molecules which feature a central 5-membered boron-containing heterocycle with a phenyl ring fused to each side. − In recent years, there have been a substantial number of key advances toward their fundamental reaction chemistry, − optical properties, − and use as chemical synthons for more complex molecules. ,− While investigations of tricoordinate borafluorenes are well-established, less is known regarding the reactivity of tetracoordinate borafluorene compounds despite the fact that a significant number of suitable precursors exist . Our laboratory has used carbene-coordinated borafluorene halides to access rare examples of cationic , and anionic borafluorenes, − as well as stable radicals with spin density delocalized throughout the polycyclic aromatic hydrocarbon (PAH) framework . More recently, we synthesized a series of mono­(phosphine)-coordinated borafluorene azides which, under thermal or photochemical conditions, afforded an array of compounds containing 4-membered B 2 N 2 rings with an exocyclic phosphinimine moiety (Figure A) .…”