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.

ConspectusBoron heterocycles represent an important subset of heteroatom-incorporated rings, attracting attention from organic, inorganic, and materials chemists. The empty pz 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 KC8 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 diborepin containing a dibora-quinone core.Our goal is to provide a guide explaining the current structure-function trends and isolation strategies for redox-active boron-incorporated polycyclic molecules to initiate the rational design and use of these types of compounds across a vast chemical space.

Synthesis and Ring-Opening Metathesis Polymerization of a Strained trans-Silacycloheptene and Single-Molecule Mechanics of Its Polymer.

The cis- and trans-isomers of a silacycloheptene were selectively synthesized by the alkylation of a silyl dianion, a novel approach to strained cycloalkenes. The trans-silacycloheptene (trans-SiCH) was significantly more strained than the cis isomer, as predicted by quantum chemical calculations and confirmed by crystallographic signatures of a twisted alkene. Each isomer exhibited distinct reactivity toward ring-opening metathesis polymerization (ROMP), where only trans-SiCH afforded high-molar-mass polymer under enthalpy-driven ROMP. Hypothesizing that the introduction of silicon might result in increased molecular compliance at large extensions, we compared poly(trans-SiCH) to organic polymers by single-molecule force spectroscopy (SMFS). Force-extension curves from SMFS showed that poly(trans-SiCH) is more easily overstretched than two carbon-based analogues, polycyclooctene and polybutadiene, with stretching constants that agree well with the results of computational simulations.

Approaching Dianionic Tetraoxadiborecine Macrocycles: 10-Membered Bora-Crown Ethers Incorporating Borafluorenate Units.

The addition of non-benzenoid quinones, acenapthenequinone or aceanthrenequinone, to the 9-carbene-9-borafluorene monoanion (1) affords the first examples of dianionic 10-membered bora-crown ethers (2-5), which are characterized by multi-nuclear NMR spectroscopy (1 H, 13 C, 11 B), X-ray crystallography, elemental analysis, and UV/Vis spectroscopy. These tetraoxadiborecines have distinct absorption profiles based on the positioning of the alkali metal cations. When compound 4, which has a vacant C4 B2 O4 cavity, is reacted with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, a color change from purple to orange serves as a visual indicator of metal binding to the central ring, whereby the Na+ ion coordinates to four oxygen atoms. A detailed theoretical analysis of the calculated reaction energetics is provided to gain insight into the reaction mechanism for the formation of 2-5. These data, and the electronic structures of proposed intermediates, indicate that the reaction proceeds via a boron enolate intermediate.

Activation of Carbon Dioxide by 9-Carbene-9-borafluorene Monoanion: Carbon Monoxide Releasing Transformation of Trioxaborinanone to Luminescent Dioxaborinanone.

The first structurally characterized example of a trioxaborinanone (2) is produced by the reaction of a 9-carbene-9-borafluorene monoanion and carbon dioxide. When compound 2 is heated or irradiated with UV light, carbon monoxide (CO) is released, and a luminescent dioxaborinanone (3) is formed. Notably, carbon monoxide releasing molecules (CORMs) are of interest for their ability to deliver a specific amount of CO. Due to the turn-on fluorescence observed as a result of the conversion to 3, CORM 2 serves as a means to optically observe CO loss "by eye" under thermal or photochemical conditions.

Air-Stable Thermoluminescent Carbodicarbene-Borafluorenium Ions.

Borenium ions, originally synthesized as fundamentally important laboratory curiosities, have attracted significant attention due to their applications in catalysis and frustrated Lewis pair chemistry. However, investigations of the materials properties of these types of compounds are exceptionally rare. Herein, we report the synthesis, molecular structures, and optical properties of a new class of air-stable borenium ions, stabilized by the strongly donating carbodicarbene (CDC) ligand (2, 3, 6). Notably, CDC-borafluorenium ions exhibit thermoluminescence in solution, a result of a twisted intramolecular charge transfer process. The temperature responsiveness, which is observable by the naked eye, is assessed over a 20 to -60 °C range. Significantly, compound 2 emits white light at lower temperatures. In the solid state, these borocations exhibit increased quantum yields due to aggregation-induced emission. CDC-borafluorenium ions with two different counteranions (Br-, BPh4-) were investigated to evaluate the effect of anion size on the solution and solid-state optical properties. In addition, CDCs containing both symmetrical and unsymmetrical N-heterocycles (bis(1-isopropyl-3-methylbenzimidazol-2-ylidene)methane and bis(1,3-dimethyl-1,3-dihydro-2H-benzo[d]imidazol-2-ylidene)methane) were tested to understand the implications of free rotation about the CDC ligand carbon-carbon bonds. The experimental work is complemented by a comprehensive theoretical analysis of the excited-state dynamics.

Systematic Electronic and Structural Studies of 9-Carbene-9-Borafluorene Monoanions and Transformations into Luminescent Boron Spirocycles.

The impact of the exact spatial arrangement of the alkali metal on the electronic properties of 9-carbene-9-borafluorene monoanions is assessed, and a series of [K][9-CAAC-9-borafluorene] complexes (1-4) have been isolated (CAAC = cyclic(alkyl)(amino) carbene, (2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl-pyrrolidin-5-ylidene). Compound 1, which contains [B]-K(THF)3 interactions, is compared to charge-separated 2-4, which were prepared by capturing the potassium cations with 18-crown-6, 2.2.2-cryptand, or 1,10-phenanthroline. Notably, the 11B NMR spectra of charge-separated borafluorene monoanions 2-4 show distinct low-field signatures compared to 1. Theoretical calculations indicate that charge separation may be exploited to influence the nucleophilic and electron transfer properties of 9-carbene-9-borafluorene monoanions. When [K(2.2.2-cryptand)][9-CAAC-9-borafluorene] (3) is reacted with 9,10-phenanthrenequinone and 1,10-phenanthroline-5,6-dione, the carbene ligand is displaced, and new air-stable R2BO2 spirocycles are formed (5 and 6, respectively). Remarkably, compounds 5 and 6 display fluorescence under UV light in both the solid and solution phases with quantum yields of up to 20%. In addition, a drastic red-shift in the emission color is observed in 6 because of the presence of the nitrogen atoms on the phenanthroline moiety. Mechanistic insights into the formation of these spirocycles are also described based on density functional theory calculations.

Isolation of Stable Borepin Radicals and Anions.

Borepin, a 7-membered boron-containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While electron-deficient borepins are well-established, reduced electron-rich species have remained elusive. Herein we report the first isolable, crystalline borepin radical (2 a, 2 b) and anion (3 a, 3 b) complexes, which have been synthesized by potassium graphite (KC8 ) reduction of cyclic(alkyl)(amino) carbene-dibenzo[b,d]borepin precursors. Borepin radicals and anions have been characterized by EPR or NMR, elemental analysis, X-ray crystallography, and cyclic voltammetry. In addition, the bonding features have been investigated computationally using density functional theory.

Reactions of 9-Carbene-9-Borafluorene Monoanion and Selenium: Synthesis of Boryl-Substituted Selenides and Diselenides.

Reactions of 9-carbene-9-borafluorene monoanion (1) with elemental selenium and selenium-containing reagents are reported. When compound 1 is reacted with grey selenium in THF, various boryl-substituted selenides and diselenides are produced (2-6), including molecules resulting from migration of the carbene ligand Dipp group (Dipp = 2,6-diisopropylphenyl). However, when a similar reaction between 1 and grey selenium is performed in toluene in the presence of 18-crown-6, boryl-substituted selenide 7 is obtained as the sole boron-containing product. As compound 7 is the monomeric variant of organoselenide 3, 18-crown-6 promotes both product selectivity and solubility in a nonpolar solvent. Diselenide 5, which features a trans-bent B-Se-Se-B core, was directly isolated via reaction of 1 with Se2Cl2 in THF. Computational modeling suggests that the formation of 5 proceeds via a radical mechanism. This was supported by an experiment demonstrating that the CAAC-borafluorene radical also reacts with SeCl2 to yield 5 [CAAC = (2,6-diisopropylphenyl)-4,4-diethyl-2,2-dimethyl-pyrrolidin-5-ylidene]. Energy decomposition analysis of 5 indicates a covalent borafluorene-diselenide bond (ΔEint, -168.9 kcal mol-1). All of the new compounds were fully characterized via single-crystal X-ray diffraction and multinuclear nuclear magnetic resonance (1H, 13C, 11B, and 77Se).

Stabilization of the Elusive 9-Carbene-9-Borafluorene Monoanion.

Two-electron reduction of carbene-supported 9-bromo-9-borafluorenes with excess KC8 , Na, or Li-naphthalenide affords six N-heterocyclic carbene (NHC)- or cyclic(alkyl)(amino) carbene (CAAC)-stabilized borafluorene anions (3-8)-the first isolated and structurally authenticated examples of the elusive 9-carbene-9-borafluorene monoanion. The electronic structure, bonding, and aromaticity of the boracyclic anions were comprehensively investigated via computational studies. Compounds 5 and 8 react with metal halides via salt elimination to give new B-E (E=Au, Se, Ge)-containing materials (9-12). Upon reaction with diketones, the carbene ligand cleanly dissociates from 5 or 8 to yield new B-O containing spirocycles (13-14) that cannot be easily obtained using "normal" valent borafluorene compounds. Collectively, these results support the notion that carbene-stabilized monoanionic borafluorenes may serve as a new platform for the one-step construction of higher-value boracyclic materials.