RESUMEN
Over the past decade, significant progress has been made in synthesizing atomically precise carbon nanostructures, particularly graphene nanoribbons (NRs), employing advanced synthetic methodologies. Despite these advancements, achieving control over the stereochemistry of twisted NRs has proven to be a formidable challenge. This manuscript presents a strategic approach to achieve absolute control over the single-handed helical conformation in a cove-edged NR. This strategy leverages enantiopure helicenes as a molecular wrench, intricately influencing the overall conformation of the NR. [7]helicenes stitched to the terminal K-regions of a conjugated pyrene NR through a stereospecific annulative π-extension reaction to produce a helically twisted NR with an end-to-end twist of 171°. Furthermore, a detailed investigation of the impact of twisting on the conformational population was studied by quantum chemical calculations.
RESUMEN
The chemistry of unsaturated boron heterocycles, including five-membered boroles, continues to attract substantial interest. Herein, we report the synthesis of 1,2,3-triphenyl-1-boraindene, a benzene-fused borole, and examine its Lewis acidic, electrophilic, and antiaromatic properties relative to non-fused and bis-benzannulated boroles (9-borafluorenes). Reactivity studies with organic azides reveal that the boraindene behaves similarly to other boroles, undergoing ring expansion to a BN-naphthalene through insertion of a nitrogen atom.
RESUMEN
While azides do not react with simple alkenes except under harsh conditions, a diboron alkene analogue, the doubly cyclic alkyl(amino)carbene (CAAC)-stabilized dicyanodiborene 1, reacts spontaneously with organic azides (7-10 equiv.) at room temperature to yield two equivalents of stable CAAC-stabilized imino(cyano)boranes (2-R). NMR-spectroscopic monitoring of the reaction mixtures shows the initial formation of a 1:1 mixture of 2-R and a relatively long-lived intermediate (Int), which in the presence of excess azide is converted into a second equivalent of 2-R. In the absence of excess azide, however, Int decomposes to 3, the product of an intramolecular CâH activation by a putative dicoordinate borylene intermediate "(CAAC)B(CN)". Mechanistic insights from trapping experiments, NMR-spectroscopic and high-resolution mass spectrometry data, as well as DFT computations reveal that Int is the terminal borylene end-on-dinitrogen adduct [(CAAC)B(CN)(η1-N2)]. The formation of the iminoboranes 2-R from diborene 1 and RN3 proceeds via an azide-diborene Huisgen-type [3+2] cycloaddition reaction, followed by a retro-[3+2] cycloaddition, yielding 2-R and [(CAAC)B(CN)(η1-N2)]. The latter then undergoes either N2 extrusion and intramolecular CâH activationto generate 3, or a Staudinger-type reaction with a second equivalent of azide to generate a second equivalent of the iminoborane 2-R.
RESUMEN
Borane coordination, B-H borane bond activation, and borane catenation via metal-mediated dehydrocoupling to form electron-precise B-B bonds are reported. The reaction of trans-[M(IMes)2Cl4] (M = W, Mo) (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) with borates Li[BH3R] (R = Mes, Dur; Mes = 2,4,6-Me3C6H2 and Dur = 2,3,5,6-Me4C6H) afforded the complexes [M(IMes)(η2-H2BR)2(η1-H2BR)] (M = W: R = Mes 1, R = Dur 3; M = Mo: R = Mes 2, R = Dur 4). Three borane ligands are coordinated in 1-4 to the group 6 metal atom via five (σ-B-H) bonds. Reaction of 1 with the phosphines PMe3 and PEt3, respectively, led to the elimination of one of the borane ligands and afforded the hydrido (σ-B-H)-boryl bis(σ-B-H)-borane complexes trans-[W(IMes)(PR3)(η1-HBMes)(η2-H2BMes)(H)] (R = Me 5, R = Et 6), in which the metal atom inserted into one of the remaining σ-B-H bonds of the borane ligands. Reaction of 1 with an additional equivalent borane BH2Mes resulted in borane dehydrocoupling and formation of complex [W(IMes)(η4-BH2Mes-BMes-BMes-BH2Mes)] 7, featuring a unique B4 chain as a ligand. Reaction of trans-[W(IMes)2Cl4] with NaBH4 also led to B-B coupling, and the metallaborane cluster [{W(IMes)(BH4)}2(B5H9)] 9 was formed, in which two tungsten atoms bridge a B5 chain.
RESUMEN
The photolytic or oxidative liberation of a cyclic (amino)(alkyl)carbene (CAAC)-stabilized arylborylene in the presence of organoazides yielded borylene-organoazide complexes (4a,b) has been achieved in a manner akin to the first step of the Staudinger reaction. Similarly, a CAAC-stabilized aminoborylene also afforded borylene-organoazide complexes (6a-c), which further undergo rearrangement to produce aminoborane triazene species (7a,b).
RESUMEN
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.
RESUMEN
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.
RESUMEN
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.â O. Fischer's alkynylcarbynes, are very rare examples of molecules containing all-inorganic chains of sp-hybridized atoms.
RESUMEN
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 PtâBF2 interaction in 2Br-F is very weak and merely electrostatic, while the PtâBCl2 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 PtâBBrAr moiety, and displaying a rare metalâborenium donor-acceptor bond.
RESUMEN
The addition of chlorotrimethylsilane to a boron-mediated, transition-metal-free N2 activation reaction leads to the isolation of multiple potassium boryl(silyl)hydrazido species, likely trapping products of a terminal dinitrogen complex of boron. One of these silylated N2 species can be protonated or methylated, providing access to mono- to tetrafunctionalized hydrazines in two steps from N2 and in the absence of transition metals.
RESUMEN
Diboradiazene compounds, derived in one step from the boron-mediated reduction of dinitrogen (N2), were treated separately with sulfur and acetic anhydride, providing heterocyclic compounds that are BN isosteres of thiophene and 1,3-oxazole, respectively. These simple reactions represent the final steps in two-step routes to complex heterocycles from N2 that both circumvent the need for transition metal reagents and completely bypass the traditional intermediate ammonia.
RESUMEN
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.
RESUMEN
Herein, we report the syntheses and electronic structures of crystalline dianionic as well as neutral diboron-centered classical diradicaloids as boron analogues of classical Thiele, Chichibabin, and Müller (this only for dianionic diradicaloids!) hydrocarbons. These are based on borane radical anion and NHC-stabilized boryl radical spin carriers, respectively. All these dianionic diboron-centered diradicaloids exhibit triplet population at room temperature regardless of the π-conjugated spacer: p-phenylene, p,p'-biphenylene, or p,pâ³-terphenylene. In the case of neutral diboron-centered diradicaloids, the employed π-conjugated spacer plays a crucial role for the triplet population at room temperature: EPR inactive for p-phenylene vs EPR active for p,p'-biphenylene. The findings emphasize the importance of the spin carriers for the resulting ground-state: borane radical anion vs NHC-stabilized boryl radical along with the pivotal role of the π-conjugated spacer as spin-coupler between two spins. Notably, 100 years (a century) after the first report by Krause of the triphenyl borane radical-anion, being isoelectronic to the triphenylmethyl radical, we convey borane radical anion-based diradicaloids. Furthermore, while donor-stabilized boryl radicals were introduced in the 1980s by Giles and Roberts, said concept is herewith being extended to NHC-stabilized boryl radical-based diradicaloids.
RESUMEN
Invited for the cover of this issue are the groups of Holger Braunschweig at the Julius-Maximilians-Universität Würzburg, Germany and Eufrânio N. da Silva Júnior at the Universidade Federal de Minas Gerais, UFMG, Brazil. The image depicts the electrochemical synthesis of selenium-containing BODIPY molecules with lightning symbolizing the electrifying synthetic process, while the surrounding elemental chaos hints at the red-shifted absorption and emission and the transformative photophysical properties of these new compounds. Read the full text of the article at 10.1002/chem.202303883.
RESUMEN
Hydrosilanes undergo mild, uncatalyzed single and double 1,2-addition across the B-B triple bonds of diborynes, leading to an unsymmetrical silyldiborene and compounds with novel non-cluster three-membered B2Si rings. The reactions are a new addition to the very few catalyst- and alkali-metal-free methods available for the construction of B-Si bonds.
RESUMEN
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.
RESUMEN
The reaction of a pyridyl-substituted, doubly Lewis base-stabilised diborene with different amounts of copper(I) precursors led to the formation of the first chelating π-diborene complexes, the first π-diborene complexes in which metals are bound to both faces of the BîB bond, and the first mixed-metal π-diborene species.
RESUMEN
The one-electron reduction of [(CAAC)Be(Dur)Br] (CAAC = cyclic alkyl(amino)carbene, Dur = 2,3,5,6-tetramethylphenyl = duryl) with lithium sand in diethyl ether yields the first neutral, tricoordinate, and moderately stable beryllium radical, [(CAAC)(Et2O)BeDur]⢠(2-Et2O), which undergoes a facile second one-electron reduction concomitant with the insertion of the beryllium center into the endocyclic C-NCAAC bond and a cyclopropane-forming C-H bond activation of an adjacent methyl group. In situ generation of 2-Et2O and addition of PMe3 yield the stable analogue, [(CAAC)(Me3P)BeDur]⢠(2-PMe3), which serves as a platform for PMe3-ligand exchange with stronger donors, generating the radicals [(CAAC)LBeDur]⢠(2-L, L = isocyanides, pyridines, and N-heterocyclic carbenes). X-ray structural analyses show trigonal-planar beryllium centers and strong π backbonding from the metal to the CAAC ligand. The EPR signals of all six isolated [(CAAC)LBeDur]⢠radicals display significant, albeit small, hyperfine coupling to the 9Be nucleus. DFT calculations show that the spin density is mostly delocalized over the CAAC π framework and, where present, the isocyanide CN moiety, with only a small proportion (3-6%) on the beryllium center. 2-PMe3 proved thermally unstable at 80 °C, first undergoing radical hydrogen abstraction with the solvent, followed by insertion of beryllium into the endocyclic C-NCAAC bond and PMe3 transfer to the former carbene carbon atom. The reactions with diphenyl disulfide and phenyl azide occur at the beryllium center and yield the corresponding Be(II) phenyl sulfide and amino complexes, respectively, the latter concomitant with radical transfer and hydrogen abstraction by the beryllium-bound nitrogen center.
RESUMEN
Peter Paetzold passed away on August 17, 2023 in Aachen, Germany. One of the great pioneers of low-valent boron and boron cluster chemistry, he will also be remembered for his outstanding teaching and the passion he brought to all of his many interests beyond research.
RESUMEN
Crystalline polymeric structures of trans-1,4-cyclohexylene bridged N-tethered bis-CAACs in the form of their LiOTf adducts were synthesized and isolated. These were further used as building blocks for the synthesis of crystalline (amino)(carboxy)-based diradicals. The triplet diradical character of these compounds was unambiguously confirmed by the presence of a half-field signal in their EPR spectra. Theoretical calculations show that the singlet state is marginally more stable than the triplet state.