Boron-Doped Pentacenes: Isolation of Crystalline 5,12- and 5,7-Diboratapentacene Dianions.

The syntheses, molecular structures, reactivities, and computational assessment of dipotassium diboratapentacene isomers are described (1 and 2). These compounds represent the first examples of aromatized diboraacenes where the boron atoms are spatially separated in different rings of the acene framework. Both 1 and 2 react with carbon dioxide (CO2) via diastereoselective carboxylation of the pentacene backbone that likely proceeds by a frustrated Lewis pair-like mechanism. The placement of the boron atoms and the reactivity studies provide a platform for later stage functionalization of diboraacenes beyond the central ring of the polycyclic aromatic hydrocarbon core.

Bis(9-Boraphenanthrene) and Its Stable Biradical.

Selective and site-specific boron-doping of polycyclic aromatic hydrocarbon frameworks often give rise to redox and/or photophysical properties that are not easily accessible with the analogous all-carbon systems. Herein, we report ligand-mediated control of boraphenanthrene closed- and open-shell electronic states, which has led to the first structurally characterized examples of neutral bis(9-boraphenanthrene) (2-3) and its corresponding biradical (4). Notably, compounds 2 and 3 show intramolecular charge transfer absorption from the 9-boraphenanthrene units to p-quinodimethane, exhibiting dual (red-shifted) emission in solution due to excited state conjugation enhancement (ESCE). Moreover, while boron-centered monoradicals are ubiquitous, biradical 4 represents a rare type of open-shell singlet compound with 95% biradical character, among the highest of any reported boron-based polycyclic species with two radical sites.

A Multidimensional Approach to Carbodiphosphorane-Bismuth Coordination Chemistry: Cationization, Redox-Flexibility, and Stabilization of a Crystalline Bismuth Hydridoborate.

Bismuth complexes stabilized by carbon-based donor ligands are underserved by their instability, often due to facile ligand dissociation and deleterious protonolysis. Herein, we show that the ortho-bismuthination of hexaphenylcarbodiphosphorane enables a robust framework with geometrically constrained carbone-bismuth bonding interactions, which are highly tunable by cationization. The carbodiphosphorane bismuth halides (1 and 2) are remarkably air-stable and feature unprecedented trans carboneC-Bi-X ligation, resulting in highly elongated Bi-X bonds. In contrast to known carbone-bismuth complexes, hydrolytic activation of the carbone yields well-defined organobismuth complexes, and subsequent dehydrohalogenation is feasible using potassium bis(trimethylsilyl)amide or N-heterocyclic carbenes. The redox-flexibility of this framework was evaluated in the high catalytic activity of 1 and 2 for silylation of 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) under mild conditions (50 °C, 24-96 h) and low catalyst loadings (5-10 mol %), which suggests the accessibility of short-lived hydridic and radical bismuth species. The reaction of 1, PhSiH3, and tris(pentafluorophenyl)borane (BCF) yields the first crystallographically characterized bismuth hydridoborate complex as an ionic species (9), presumably by BCF-mediated hydride abstraction from an unobserved [Bi]-H intermediate. All isolated compounds have been characterized by heteronuclear NMR spectroscopy and X-ray crystallography, and the bonding situation in representative complexes (1, 2, 5, and 9) were further evaluated using density functional theory.

N-Heterocyclic Carbene-Assisted Reversible Migratory Coupling of Aminoborane at Magnesium.

A combined synthetic and theoretical investigation of N-heterocyclic carbene (NHC) adducts of magnesium amidoboranes is presented, which involves a rare example of reversible migratory insertion within a normal valent s-block element. The reaction of (NHC)Mg(N(SiMe3 )2 )2 (1) and dimethylamine borane yields the tris(amide) adduct (NHC-BN)Mg(NMe2 BH3 )(N(SiMe3 )2 ) (2; NHC-BN = NHC-BH2 NMe2 ). In addition to Me2 N=BH2 capture at the NHC C-Mg bond, mechanistic investigations suggest the likelihood of aminoborane migratory insertion from an RMg(NMe2 BH2 NMe2 BH3 ) intermediate. To elucidate these processes, the carbene complexes (NHC)Mg(NMe2 BH3 )2 (8) and (NHC)Mg(NMe2 BH2 NMe2 BH3 )2 (9) were synthesized, and a dynamic migration of Me2 N=BH2 between Mg-N and NHC C-Mg bonds was observed in 9. This unusual reversible migratory insertion is presumably induced by dissimilar charge localization in the - {NMe2 BH2 NMe2 BH3 } anion, as well as the capacity of NHCs to reversibly capture Me2 N=BH2 in the presence of Lewis acidic magnesium species.

Surfactant Removal for Colloidal Nanocrystal Catalysts Mediated by N-Heterocyclic Carbenes.

We report the facile removal of surfactants from colloidally synthesized nanocrystals via ligand exchange with N-heterocyclic carbenes (NHCs). Subsequent protonation of the NHC ligands in acid efficiently cleans the nanocrystals' surface while preserving their uniform morphology and structure for catalysis. The broad efficacy of this strategy is validated using monodisperse Pt, Pd, and Au nanocrystals, each prepared with strongly bound phosphine stabilizers. The surface-activated nanocrystals exhibit significantly improved catalytic activities, superior to those obtained with other surface cleaning methods, as demonstrated in two centrally important electrochemical reactions (glycerol oxidation and CO2 reduction). This work highlights a new surface activation strategy for catalysis and other applications that enables the efficient use of well-defined nanocrystal libraries prepared by colloidal chemistry.

A Thermally Stable Magnesium Phosphaethynolate Grignard Complex.

The 2-phosphaethynolate (OCP) anion has found versatile applications across the periodic table but remains underexplored in group 2 chemistry due to challenges in isolating thermally stable complexes. By rationally modifying their coordination environments using 1,3-dialkyl-substituted N-heterocyclic carbenes (NHCs), we have now isolated and characterized thermally stable, structurally diverse, and hydrocarbon soluble magnesium phosphaethynolate complexes (2, 4Me, and 8-10), including the novel phosphaethynolate Grignard reagent (2iPr). The methylmagnesium phosphaethynolate and magnesium diphosphaethynolate complexes readily activate dioxane with subsequent H-atom abstraction to form [(NHC)MgX(µ-OEt)]2 [X = Me (3) or OCP (8 and 9)] complexes. Their reactivities increased with the Lewis acidity of the Mg2+ cation and may be attenuated by Lewis base saturation or a slight increase in carbene sterics. Solvent effects were also investigated and led to the surreptitious isolation of an ether-free sodium phosphaethynolate (NHC)3Na(OCP) (6), which is soluble in aromatic hydrocarbons and can be independently prepared by the reaction of NHC and [Na(dioxane)2][OCP] in toluene. Under forcing conditions (105 °C, 3 days), the magnesium diphosphaethynolate complex (NHC)3Mg(OCP)2 (10) decomposes to a mixture of organophosphorus complexes, among which a thermal decarbonylation product [(NHC)2PI][OCP] (11) was isolated.

Stepwise Reduction at Magnesium and Beryllium: Cooperative Effects of Carbenes with Redox Non-Innocent α-Diimines.

In the past two decades, the organometallic chemistry of the alkaline earth elements has experienced a renaissance due in part to developments in ligand stabilization strategies. In order to expand the scope of redox chemistry known for magnesium and beryllium, we have synthesized a set of reduced magnesium and beryllium complexes and compared their resulting structural and electronic properties. The carbene-coordinated alkaline earth-halides, (Et2CAAC)MgBr2 (1), (SIPr)MgBr2 (2), (Et2CAAC)BeCl2 (3), and (SIPr)BeCl2 (4) [Et2CAAC = diethyl cyclic(alkyl)(amino) carbene; SIPr = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazole-2-ylidene] were combined with an α-diimine [2,2-bipyridine (bpy) or bis(2,6-diisopropylphenyl)-1,4-diazabutadiene (DippDAB)] and the appropriate stoichiometric amount of potassium graphite to form singly- and doubly-reduced compounds (Et2CAAC)MgBr(DippDAB) (5), (Et2CAAC)MgBr(bpy) (6), (Et2CAAC)Mg(DippDAB) (7), (Et2CAAC)Be(bpy) (8), and (SIPr)Be(bpy) (9). The doubly-reduced compounds 7-9 exhibit substantial π-bonding interactions across the diimine core, metal center, and π-acidic carbene. Each complex was fully characterized by UV-vis, FT-IR, X-ray crystallography, 1H, 13C, and 9Be NMR, or EPR where applicable. We use these compounds to highlight the differences in the organometallic chemistry of the lightest alkaline earth metals, magnesium and beryllium, in an otherwise identical chemical environment.

Cyclic(alkyl)(amino) Carbene-Promoted Ring Expansion of a Carbodicarbene Beryllacycle.

Recent synthetic efforts have uncovered several bond activation pathways mediated by beryllium. Having the highest charge density and electronegativity, the chemistry of beryllium often diverges from that of its heavier alkaline earth metal congeners. Herein, we report the synthesis of a new carbodicarbene beryllacycle (2). Compound 2 converts to 3 via an unprecedented cyclic(alkyl)(amino) carbene (CAAC)-promoted ring expansion reaction (RER). While CAAC activates a carbon-beryllium bond, N-heterocyclic carbene (NHC) coordinates to beryllium to give the tetracoordinate complex 4, which contains the longest carbeneC-Be bond to date at 1.856(4) Å. All of the compounds were fully characterized by X-ray crystallography, Fourier transform infrared spectroscopy, and 1H, 13C, and 9Be NMR spectroscopy. The ring expansion mechanism was modeled with both NHC and CAAC using density functional theory calculations. While the activation energy for the observed beryllium ring expansion with CAAC was found to be 14 kJ mol-1, the energy barrier for the hypothetical NHC RER is significantly higher (199.1 kJ mol-1).

Geminal bimetallic coordination of a carbone to main-group and transition metals.

The non-bonding carbone lone pair in geometrically-constrained antimony and bismuth carbodiphosphorane complexes readily complexed AuCl to afford rare examples of geminal bimetallic carbone coordination featuring a main-group metal.

Air- and photo-stable luminescent carbodicarbene-azaboraacenium ions.

Substitution of a C=C bond by an isoelectronic B-N bond is a well-established strategy to alter the electronic structure and stability of acenes. BN-substituted acenes that possess narrow energy gaps have attractive optoelectronic properties. However, they are susceptible to air and/or light. Here we present the design, synthesis and molecular structures of fully π-conjugated cationic BN-doped acenes stabilized by carbodicarbene ligands. They are luminescent in the solution and solid states and show high air and moisture stability. Compared with their neutral BN-substituted counterparts as well as the parent all-carbon acenes, these species display improved quantum yields and small optical gaps. The electronic structures of the azabora-anthracene and azabora-tetracene cations resemble higher-order acenes while possessing high photo-oxidative resistance. Investigations using density functional theory suggest that the stability and photo-physics of these conjugated systems may be ascribed to their cationic nature and the electronic properties of the carbodicarbene.

Soluble, crystalline, and thermally stable alkali CO2 - and carbonite (CO2 2-) clusters supported by cyclic(alkyl)(amino) carbenes.

The mono- and dianions of CO2 (i.e., CO2 - and CO2 2-) have been studied for decades as both fundamentally important oxycarbanions (anions containing only C and O atoms) and as critical species in CO2 reduction and fixation chemistry. However, CO2 anions are highly unstable and difficult to study. As such, examples of stable compounds containing these ions are extremely limited; the unadulterated alkali salts of CO2 (i.e., MCO2, M2CO2, M = alkali metal) decompose rapidly above 15 K, for example. Herein we report the chemical reduction of a cyclic (alkyl)(amino) carbene (CAAC) adduct of CO2 at room temperature by alkali metals, which results in the formation of CAAC-stabilized alkali CO2 - and CO2 2- clusters. One-electron reduction of CAAC-CO2 adduct (1) with lithium, sodium or potassium metal yields stable monoanionic radicals [M(CAAC-CO2)] n (M = Li, Na, K, 2-4) analogous to the alkali CO2 - radical, and two-electron alkali metal reduction affords dianionic clusters of the general formula [M2(CAAC-CO2)] n (5-8) with reduced CO2 units which are structurally analogous to the carbonite anion CO2 2-. It is notable that crystalline clusters of these alkali-CO2 salts may also be isolated via the "one-pot" reaction of free CO2 with free CAAC followed by the addition of alkali metals - a process which does not occur in the absence of carbene. Each of the products 2-8 was investigated using a combination of experimental and theoretical methods.