Antiaromatic 2-Azaboroles with π4σ2 Electronic Configuration.

Similar to pyridine, which is a structural analog of benzene, 2-azaborole can be viewed as a structural analog of borole, in which the CH group at the 2-position is replaced by an N atom. Due to its unique π4σ2 electronic configuration, it should exhibit Lewis acidity, antiaromaticity, as well as Lewis basicity simultaneously. However, this uniqueness also makes its synthesis and isolation particularly challenging. One anticipated issue is its readiness for self-dimerization. This work proposes 2-azaborole and targets the synthesis and characterization of its derivatives for the first time. By reacting benzoborirene C6H4{BN(SiMe3)2} with bulky nitriles, crystalline benzo-fused 2-azaboroles have been successfully achieved and fully characterized. The importance of steric hindrance has been experimentally verified, showing that insufficient kinetic protection results in the dimerization of benzo-fused 2-azaboroles to form BN-allenophanes, a class of 10-membered macrocyclic compounds featuring two BN-allene units. The unique electronic structure of 2-azaborole as well as the mechanism of dimerization has been corroborated by theoretical calculations. In addition, its ability to act both as a Lewis acid and a Lewis base is demonstrated through its reaction with 1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene (MeIiPr) and AlCl3, respectively, which also implies the potential of the 2-azaborole motif as a σ-donor ligand for main group and organometallic chemistry.

Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion.

Exploring the relationship between thermal expansion and structural complexity is a challenging topic in the study of modern materials where volume stability is required. This work reports a new family of negative thermal expansion (NTE) materials, AM(CN)4 with A = Li and Na and M = B, Al, Ga, and In. Here, the compounds of LiB(CN)4 and NaB(CN)4 were only synthesized; others were purely computationally studied. A critical role of nonrigid vibrational modes and spiral acoustical modes has been identified in NaB(CN)4. This understanding has been exploited to design the colossal NTE materials of NaM(CN)4 (M = Al, Ga, In). A joint study involving synchrotron X-ray diffraction, Raman spectroscopy, and first-principles calculations has been conducted to investigate the thermal expansion mechanism. It has been found that the A atoms can either increase the symmetry of the crystal structure, inducing stronger NTE, or lower the crystal symmetry, thus resulting in positive thermal expansion. Conversely, the M-site atoms do not affect the crystal structure. However, as the radius of the M atoms increases, the ionic nature of the C-M bonds strengthens and the CN vibrations become more flexible, thereby enhancing the NTE behavior. This study provides new insights to aid in the discovery and design of novel NTE materials and the control of thermal expansion.

Full Electron Delocalization across the Cluster in 1,12-bisBMes2-p-carborane Radical Anion.

Conjugation between three-dimensional (3D) carboranes and the attached substituents is commonly believed to be very weak. In this paper, we report that reducing 1,12-bis(BMes2)-p-carborane (B2pCab) with one electron gives a radical anion with a centrosymmetric semiquinoidal structure. This radical anion shows extensive electron delocalization between the two boron centers over the p-carborane bridge due to the overlap of carborane lowest unoccupied molecular orbital (LUMO) and the BMes2 LUMO. Unlike dianions of other C2B10H12 carboranes, which rearrange to a nido-form, two-electron reduction of B2pCab leads to a rearrangement into a basket-shaped intermediate.

Synthesis, Photophysical and Electronic Properties of a D-π-A Julolidine-Like Pyrenyl-o-Carborane.

We synthesized 2-(1-1,2-dicarbadodecaboranyl(12))-6,6,12,12-tetramethyl-7,8,11,12-tetrahydro-6H,10H-phenaleno[1,9-fg]pyrido[3,2,1-ij]quinoline (4), a julolidine-like pyrenyl-o-carborane, with pyrene substituted at the 2,7-positions on the HOMO/LUMO nodal plane. Using solid state molecular structures, photophysical data, cyclic voltammetry, DFT and LR-TDDFT calculations, we compare o-carborane and B(Mes)2 (Mes=2,4,6-Me3C6H2) as acceptor groups. Whereas the π-acceptor strength of B(Mes)2 is sufficient to drop the pyrene LUMO+1 below the LUMO, the carborane does not do this. We confirm the π-donor strength of the julolidine-like moiety, however, which raises the pyrene HOMO-1 above the HOMO. In contrast to the analogous pyrene-2-yl-o-carborane, 2-(1-1,2-dicarbadodecaboranyl(12))-pyrene VI, which exhibits dual fluorescence, because the rate of internal conversion between locally-excited (LE) and charge transfer (CT) (from the pyrene to the carborane) states is faster than the radiative decay rate, leading to a thermodynamic equilibrium between the 2 states, 4 shows only single fluorescence, as the CT state involving the carborane as the acceptor moiety in not kinetically accessible, so a more localized CT emission involving the julolidine-like pyrene moiety is observed.

A-Frame-Templated High-Coordinate Platinum(IV) cis-Bis(boryl) Complexes.

The addition of Et2O·BF3 or Me2S·BCl3 to the BNBN-cumulene-bridged Pt(II) A-frame complexes [(µ-1,1-BNBN(TMS)2)(µ-dmpm)2Pt2X2] (TMS = SiMe3, dmpm = CH2(PMe2)2, X = Br 1Br, I 1I) resulted in the oxidative addition of one B-F or B-Cl bond, respectively, to the internal BN bond of the bridging, iminoborane-like B-N≡B-N moiety, and coordination of one Pt(II) center to the resulting adjacent BF2 (complex 2Br-F) or BCl2 (complexes 2Br-Cl and 2I-Cl) moiety, respectively. X-ray crystallographic and multinuclear NMR-spectroscopic data show that the Pt→BF2 interaction in 2Br-F is very weak and merely electrostatic, while the Pt→BCl2 interaction in 2Br-Cl and 2I-Cl is a stronger donor-acceptor bond. In contrast, the reaction of Me2S·BBr3 with 1Br yielded a ca. 3:2 mixture of the analogous B-Br addition product to the iminoborane, 2Br-Br, and the product of a subsequent oxidative addition of one B-Br bond of the chelating BBr2 moiety to the adjacent platinum center, the mixed-valence boranediyl-bridged, Pt(II)-Pt(IV)-bromoboryl complex 3-Br5. The analogous reactions of Me2S·BI3 with 1Br and Me2S·BBr3 with 1I yielded complex product mixtures of Pt(II)-Pt(II)-borane (2Br-I and 2I-Br, respectively) and Pt(II)-Pt(IV)-boryl complexes (3-BrnI5-n, n = 1-3) analogous to 2X-Y and 3-Br5, respectively, the proportion of the latter increasing with the proportion of iodide in the precursor mixture. Both multinuclear NMR-spectroscopic and X-ray crystallographic data show evidence of complex and extensive inter- and intramolecular bromide-iodide exchanges between the soft, iodide-affine platinum centers and the harder, more bromide-affine boron centers. A clue to the mechanism of these halide exchanges is provided by the reactions of BBr2Ar (Ar = 2,4,6-Me3C6H2 (Mes), 2,3,5,6-Me4C6H (Dur)) with 1Br, which yielded the cationic Pt(II)-Pt(II)-borenium analogues of 2Br-Br, the complexes 4Br-Ar, generated by the sterics-induced displacement of the bromide substituent from the chelating Pt→BBrAr moiety, and displaying a rare metal→borenium donor-acceptor bond.

Nickel(II) Cyanoborates and Cyanoborate-Ligated Nickel(II) Complexes.

Nickel(II) cyanoborates Ni[BH2(CN)2]2·H2O (1b·H2O), Ni[BH(CN)3]2·0.5H2O (1c·0.5H2O), and Ni[B(CN)4]2·0.5H2O (1d·0.5H2O) were synthesized, and their reactivity with respect to dppeO2 (=1,2-bis-(diphenylphosphinoethane dioxide)), pyNO (=pyridine-N-oxide), dppe (=1,2-bis-(diphenylphosphinoethane), and DMSO (=dimethyl sulfoxide) was examined. Using these ligands, either cyanoborate (CB) complex salts of [Ni(dppe)2]2+ (2b-d) and [Ni(pyNO)6]2+ (3c-d) were isolated or complexes [Ni(DMSO)4{NC-B(CN)3}2] (1dDMSO) and [Ni(dppeO2)2{NC-B(CN)3}2] (1ddppeO2) were formed. Salt metathesis of [Ni(dppe)Cl2] with alkali metal cyanoborates resulted in mono- and disubstituted coordination compounds [Ni(dppe){NC-BH(CN)2}Cl] (5c) and [Ni(dppe){NC-BH2CN)2}] (4b), which decomposed to salts 2b-d. The synthetical pathways explored offer convenient routes to nickel(II) cyanoborates, nickel(II) complexes ligated with cyanoborates, and nickel(II) complex salts of cyanoborates. Further, our studies demonstrate the diverse character of cyanoborates in coordination chemistry as noncoordinating counteranions and also as medium coordinating anions forming novel transition-metal complexes and salts.

Fluoride Abstraction Induced by Tris(pentafluoroethyl)difluorophosphorane: A Convenient Way to Synthesize Cationic N-Heterocyclic Carbene- and Cyclic (Alkyl)(amino)carbene-Ligated Copper Alkyne and Arene Complexes.

We herein report the convenient synthesis of different N-heterocyclic carbene (NHC)- and cyclic (alkyl)(amino)carbene (cAAC)-ligated copper cations using the weakly coordinating tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C2F5)3PF3]-). The reaction of the fluorido complexes [(carbene)CuF] (carbene = NHC, cAACMe) 2a-2f and the tris(pentafluoroethyl)difluorophosphorane (C2F5)3PF2 in the presence of alkynes or arenes led to fluoride transfer from Cu to the phosphorane with formation of the cationic transition metal complexes [(carbene)Cu(L)]+ and the weakly coordinating counteranion [(C2F5)3PF3]- (FAP). Using this method, the complexes [(IDipp)Cu(L)]+FAP- (IDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolin-2-ylidene; L = PhC≡CPh, 4d; PhC≡CMe, 5d), [(cAACMe)Cu(L)]+FAP- (cAACMe = 1-(2,6-di-iso-propylphenyl)-3,3,5,5-tetramethyl-pyrrolidin-2-ylidene; L = PhC≡CPh, 4f; PhC≡CMe, 5f), [(SIDipp)Cu(C6Me6)]+FAP- (6e), (SIDipp = 1,3-bis(2,6-di-iso-propylphenyl)-imidazolidine-2-ylidene), and [(cAACMe)Cu(C6Me6)]+FAP- (6f) have been synthesized and characterized. The complexes [(IDipp)Cu(C6Me6)]+FAP- (6d) and [(cAACMe)Cu(C6Me6)]+FAP- (6f) have been used as catalysts for the copper(I)-catalyzed cycloaddition of benzyl azide to terminal alkynes.

Lewis Acid Decorated Hexacyanodiborane(6) Dianion.

First examples of diborane(6) dianions decorated with weakly coordination B(C6F5)3 (BCF) groups and SiEt3 + moieties have been synthesized demonstrating the synthetic potential of the [B2(CN)6]2- dianion. [B2{CNB(C6F5)3}6]2- (1) was isolated as potassium and tetrabutylammonium salt. 1 is a rare example for a weakly coordinating dianion and it was used for the stabilization of the carbocation [Ph3C]+ and the oxonium acid [H(OEt2)2]+. Reaction of [Ph3C]21 with HSiEt3 resulted in the silylated neutral diborane(6) [B2{CNB(C6F5)3}4(CNSiEt3)2] (2) in which two BCF groups have been selectively replaced by SiEt3 + substituents, underscoring the stability and chemical versatility of the [B2(CN)6]2- dianion. The chemical properties and physicochemical data of 1 and 2 provide insight into electronic, coordinating, and steric properties of theses novel diborane(6) compounds.

All-Inorganic sp-Chain Ligands: Isoelectronic B/N Analogues of E. O. Fischer's Alkynylcarbynes.

Borylation of a tungsten-bound N2 ligand and halide abstraction provides access to a cationic complex with an unprecedented linear NNBR ligand. This complex undergoes [3+2] cycloaddition with azides, and an unexpected chain-extension reaction with an iminoborane, leading to a complex with a five-atom B/N chain. These two [NNBR]-containing complexes, inorganic analogues of E. O. Fischer's alkynylcarbynes, are very rare examples of molecules containing all-inorganic chains of sp-hybridized atoms.

Synthesis and Reactivity of Tricoordinate Organoberyllium Azides.

A series of terminal mono- and disubstituted beryllium azides of the form [(CAAC)Be(N3)R] (R=CAACH, Dur; CAACH/CAAC=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-yl/idene, Dur=2,3,5,6-tetramethylphenyl) and [L2Be(N3)2] (L=CAACNH=1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-imine, IiPrMe=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene), respectively, were synthesized and characterized by NMR spectroscopy and X-ray crystallography. Thermolysis and photolysis products of these first examples of tricoordinate azidoberyllium complexes evidence extensive ligand scrambling and the formal insertion of nitrenes into the CAAC-Be bond, generating cyclic alkyl(amino)imine (CAAI) ligands. Furthermore, the reaction with a small N-heterocyclic carbene (NHC) leads to unexpected CAAC-NHC ligand exchange, while the reaction with pentaphenylborole yields the first γ-azide adduct of a borole, long postulated to be the first step in the synthesis of 1,2-azaborinines from boroles and azides.

Synthesis and Reactivity of a Dialane-Bridged Diradical.

Radicals of the lightest group 13 element, boron, are well established and observed in numerous forms. In contrast to boron, radical chemistry involving the heavier group 13 elements (aluminum, gallium, indium, and thallium) remains largely underexplored, primarily attributed to the formidable synthetic challenges associated with these elements. Herein, we report the synthesis and isolation of planar and twisted conformers of a doubly CAAC (cyclic alkyl(amino)carbene)-radical-substituted dialane. Extensive characterization through spectroscopic analyses and X-ray crystallography confirms their identity, while quantum chemical calculations support their open-shell nature and provide further insights into their electronic structures. The dialane-connected diradicals exhibit high susceptibility to oxidation, as evidenced by electrochemical measurements and reactions with o-chloranil and a variety of organic azides. This study opens a previously uncharted class of dialuminum systems to study, broadening the scope of diradical chemistry and its potential applications.

Giant Negative Thermal Expansion in Ultralight NaB(CN)4.

Negative thermal expansion (NTE) is crucial for controlling the thermomechanical properties of functional materials, albeit being relatively rare. This study reports a giant NTE (αV ∼-9.2 ⋅ 10-5  K-1 , 100-200 K; αV ∼-3.7 ⋅ 10-5  K-1 , 200-650 K) observed in NaB(CN)4 , showcasing interesting ultralight properties. A comprehensive investigation involving synchrotron X-ray diffraction, Raman spectroscopy, and first-principles calculations has been conducted to explore the thermal expansion mechanism. The findings indicate that the low-frequency phonon modes play a primary role in NTE, and non-rigid vibration modes with most negative Grüneisen parameters are the key contributing factor to the giant NTE observed in NaB(CN)4 . This work presents a new material with giant NTE and ultralight mass density, providing insights for the understanding and design of novel NTE materials.

Structure and Electronics of a Series of CAAC-Stabilized Diboron-Doped Acenes from 1,4-Diboranaphthalene to 6,13-Diborapentacene.

This combined experimental and theoretical study examines the influence of acene elongation, boron atom position, and acene substitution pattern on the structure and electronics of cyclic alkyl(amino)carbene (CAAC)-stabilized diboraacenes and presents the first syntheses of neutral diboranaphthalene (DBN) and diborapentacene (DBP). Whereas 2,3-diethyl-substituted 1,4-(CAAC)2-Et2DBN is isolated as a mixture of a planar (structurally characterized) NMR-active conformer and a presumably bent EPR-active conformer, 6,13-(CAAC)2-DBP resembles 9,10-(CAAC)2-DBA (DBA = diboraanthracene), with a highly puckered 6,13-DBP core and a typical biradical EPR signal. Both species are easily reduced to their puckered dianions. DFT calculations confirm that 6,13-(CAAC)2-DBP is only stable in its bent conformation, whereas 1,4-(CAAC)2-Et2DBN exists as both flat closed-shell and bent open-shell biradical conformers, which interchange by thermally activated ethyl and CAAC rotation/diboraacene bending processes. An in-depth computational study of the series of unsubstituted, CAAC-stabilized, symmetrically diboron-doped acenes from 1,4-(CAAC)2-DBN to 6,13-(CAAC)2-DBP was carried out. The results show interesting trends dependent on the position of the boron atoms within the acene framework as well as on the relative orientation of the CAAC ligands, which enable fine-tuning of the electronic and structural features.

Boron Insertion into the N≡N Bond of a Tungsten Dinitrogen Complex.

The 1,3-addition of 1,2-diaryl-1,2-dibromodiboranes (B2Br2Ar2) to trans-[W(N2)2(dppe)2] (dppe = κ2-(Ph2PCH2)2), which is accompanied by a Br-Ar substituent exchange between the two boron atoms, is followed by a spontaneous rearrangement of the resulting tungsten diboranyldiazenido complex to a 2-aza-1,3-diboraallenylimido complex displaying a linear, cumulenic B=N=B moiety. This rearrangement involves the splitting of both the B-B and N=N bonds of the N2B2 ligand, formal insertion of a BAr boranediyl moiety into the N=N bond, and coordination of the remaining BArBr boryl moiety to the terminal nitrogen atom. Density functional theory calculations show that the reaction proceeds via a cyclic NB2 intermediate, followed by dissociation into a tungsten nitrido complex and a linear boryliminoborane, which recombine by adduct formation between the nitrido ligand and the electron-deficient iminoborane boron atom. The linear B=N=B moiety also undergoes facile 1,2-addition of Brønsted acids (HY = HOPh, HSPh, and H2NPh) with concomitant Y-Br substituent exchange at the terminal boron atom, yielding cationic (borylamino)borylimido tungsten complexes.

Amber Light Control of Peptide Secondary Structure by a Perfluoroaromatic Azobenzene Photoswitch.

The incorporation of photoswitches into the molecular structure of peptides and proteins enables their dynamic photocontrol in complex biological systems. Here, a perfluorinated azobenzene derivative triggered by amber light was site-specifically conjugated to cysteines in a helical peptide by perfluoroarylation chemistry. In response to the photoisomerization (trans→cis) of the conjugated azobenzene with amber light, the secondary structure of the peptide was modulated from a disorganized into an amphiphilic helical structure.

Construction of a Diverse Range of Boron Heterocycles via Ring Expansion of a Carboranyl-Substituted 9-Borafluorene.

Direct insertion of unsaturated substrates into a five-membered borole ring is a useful method to obtain valuable heterocycles containing one or more three-coordinate boron atoms. A highly Lewis acidic 9-o-carboranyl-9-borafluorene, in which the o-carboranyl substituent is connected via one of the cluster carbon atoms to the boron atom of the 9-borafluorene unit, was found to react with a vast array of unsaturated molecules, such as alkynes, aldehydes and various organic azides, to form larger boraheterocyclic products. The ring expansion reactions of the central borole ring proceed rapidly at room temperature, cementing the role of the o-carboranyl substituent in enhancing the insertion reactivity of 9-borafluorenes.

Binding Properties of Small Electrophilic Anions [B6 X5 ]- and [B10 X9 ]- (X=Cl, Br, I): Activation of Small Molecules Based on π-Backbonding.

Superelectrophilic anions constitute a special class of molecular anions that show strong binding of weak nucleophiles despite their negative charge. In this study, the binding characteristics of smaller gaseous electrophilic anions of the types [B6 X5 ]- and [B10 X9 ]- (with X=Cl, Br, I) were computationally and experimentally investigated and compared to those of the larger analogues [B12 X11 ]- . The positive charge of vacant boron increases from [B6 X5 ]- via [B10 X9 ]- to [B12 X11 ]- , as evidenced by increasing attachment enthalpies towards typical σ-donor molecules (noble gases, H2 O). However, this behavior is reversed for σ-donor-π-acceptor molecules. [B6 Cl5 ]- binds most strongly to N2 and CO, even more strongly than to H2 O. Energy decomposition analysis confirms that the orbital interaction is responsible for this opposite trend. The extended transition state natural orbitals for chemical valence method shows that the π-backdonation order is [B6 X5 ]- >[B10 X9 ]- >[B12 X11 ]- . This predicted order explains the experimentally observed red shifts of the CO and N2 stretching fundamentals compared to those of the unbound molecules, as measured by infrared photodissociation spectroscopy. The strongest red shift is observed for [B6 Cl5 N2 ]- : 222 cm-1 . Therefore, strong activation of unreactive σ-donor-π-acceptor molecules (commonly observed for cationic transition metal complexes) is achieved with metal-free molecular anions.

Alkylcyanoborate Anions: Building Blocks for Fluorine-Free Low-Viscosity, Electrochemically and Thermally Stable Ionic Liquids.

A set of mixed-substituted potassium alkylcyano- and alkylcyanofluoroborates has been synthesized using easily accessible starting compounds and characterized by elemental analysis, NMR and vibrational spectroscopy, and mass spectrometry. In addition, single-crystal structures of salts of the cyanoborate anions have been derived from X-ray diffraction experiments. The 1-ethyl-3-methylimidazolium room temperature ionic liquids ([EMIm]+ -RTILs) with the new borate anions have been synthesized and their physicochemical properties, that is, high thermal and electrochemical stability, low viscosity, and high conductivity, have been compared to the properties of related [EMIm]+ -RTILs. The influence of the different alkyl substituents at boron has been assessed. The exemplary study on the properties with the [EMIm]+ -ILs with the mixed water stable alkylcyanoborate anions points towards the potential of these fluorine-free borate anions, in general.

Synthesis of Partially Fluorinated Alkyl Triflates by Electrochemical Fluorination (Simons Process).

A scalable straightforward synthesis of monofluoro- and difluoromethyl triflate CF3 SO2 OCH2 F (MH2F ) and CF3 SO2 OCHF2 (MHF2 ) through electrochemical fluorination (ECF, Simons process) of methyl triflate MH3 in anhydrous hydrogen fluoride at nickel anodes is presented. The ECF method is also feasible for the preparation of the deuterated analogues CF3 SO2 OCD2 F (MD2F ) and CF3 SO2 OCDF2 (MD2F ). Surprisingly, no H/D exchange occurs during ECF of CF3 SO2 OCD3 (MD3 ); this provides further evidence for a NiF3 /NiF4 -mediated ECF mechanism. The ECF of selected partially fluorinated ethyl triflates is described, and electrochemical fluorination of CF3 SO2 OCH2 CF3 (EH2F3 ) leads to the until now unknown chiral CF3 SO2 OCHFCF3 (EHFF3 ). The analogous fluoromethyl and fluoroethyl nonaflates are also accessible by ECF. This study contains detailed spectroscopic, structural, and thermal data on (fluoro)methyl and fluoro(ethyl) triflates.

Unlocking Heteroaromatic Ring Systems through Chalcogen Insertion into Boroles.

In this work, we report the reactivity of various annulated borole derivatives toward chalcogen (O, S, and Se) insertion. Among a series of 9-borafluorenes with different boron substituents (Ph, Br, or o-carboranyl) and a mixed thiophene-benzene-fused derivative, only the 9-o-carboranyl-substituted 9-borafluorene yielded the complete set of chalcogen-containing heteroarenes, including the first 1,2-selenaborinine derivative. To evaluate the aromaticity of this heterocyclic analogue of phenanthrene, nucleus-independent chemical shift (NICS) values were computed and compared to those of its lighter group 16 congeners.