RESUMEN

We experimentally demonstrate a new type of the intramolecular reaction between non-activated alkyne units and the dialkylboryl group (9-BBN), which was previously only hypothesized and studied on a calculational level. The reaction described here can formally be classified as a 1,2-hydroboration reaction, but, in contrast to the classical mechanism via a cyclic four-membered transition state, the reaction proceeds by a pericyclic mechanism involving a six-membered transition state. In practice, the reaction allows the synthesis of a new class of the borolenes fused with silole or dihydrosilole units. Thus, the heating (125°C) of 2,3-dihydrosiloles or 2,3-dihydrosilolo[2,3-b]silole bearing 9-BBN and propargyl or dimethylpropargyl groups in positions 4 and 5, respectively, affords, in high to moderate yields, di- and tricyclic compounds containing a borolo[3,2-b]silole unit. In all cases, the reactions are accompanied by an unprecedented dehydroboration of the 9-BBN fragment, leading, in the final products, to a cyclooct-4-enyl group on the boron atom. The effects of the substituents on the rate and the selectivity of the reaction are discussed. The structures of all the new compounds have been determined from HRMS together with multinuclear 1D and 2D NMR spectroscopy, the results of which are in excellent agreement with DFT calculated chemical shifts.

RESUMEN

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.

RESUMEN

Structurally authenticated free B-alkyl boroles are presented and electronic implications of alkyl substitution were assessed. Deprotonation of a boron-bound exocyclic methyl group in a B-methyl borole yields the first 5-boratafulvene anion-an isomer to boratabenzene. Boratafulvene was structurally characterized and its electronic structure probed by DFT calculations. The pKa value of the exocyclic B-CH3 in a set of boroles was computationally approximated and confirmed a pronounced acidic character caused by the boron atom embedded in an anti-aromatic moiety. The non-aromatic boratafulvene reacts as a C-centered nucleophile with the mild electrophile Me3 SnCl to give a stannylmethyl borole, regenerating the anti-aromaticity. As nucleophilic synthons for boroles, boratafulvenes thus open an entirely new avenue for synthetic strategies toward this highly reactive class of heterocycles. Boratafulvene reacts as a methylene transfer reagent in a bora-Wittig-type reaction generating a borole oxide.

RESUMEN

Using 4-phenylpyridine or 2-phenylpyridine in place of biphenyl, two electron-poor phenylpyridyl-fused boroles, [TipPBB1]4 and TipPBB2 were prepared. [TipPBB1]4 adopts a unique coordination mode and forms a tetramer with a cavity in both the solid state and solution. The boron center of TipPBB2 is 4-coordinate in the solid state but the system dissociates in solution, leading to 3-coordinate borole species. Compared to its borafluorene analogues, the electron-accepting ability of TipPBB2 is largely enhanced by the pyridyl group. TipPBB2 exhibits dual fluorescence in solution due to an equilibrium between free TipPBB2 and a weak intermolecular coordination adduct with a second molecule. This equilibrium was further investigated by low-temperature NMR spectroscopy and photophysical studies. Theoretical studies indicate that the highest occupied molecular orbital (HOMO) of TipPBB2 localizes at the Tip group, in contrast to its borafluorene derivatives, wherein the HOMOs are localized on the borafluorene cores.

RESUMEN

This work describes the synthesis and characterization of a highly reactive cationic borole. Halide abstraction with Li{Al[OC(CF3 )3 ]4 } from the NHC-chloroborole adduct yields the first stable NHC-supported 1-(Me NHC)-2,5-(SiMe3 )2 -3,4-(Ph*)2 -borole cation. Electronically, it features both a five-membered cyclic conjugated 4 π-electron system and a cationic charge and thus resembles the yet elusive cyclopentadienyl cation. The borole cation was characterized crystallographically, spectroscopically (NMR, UV/Vis), by cyclovoltammetry, microanalysis and mass-spectrometry and its electronic structure was probed computationally. The cation reacts with tolane and reversibly binds carbon monoxide. Direct comparison with the structurally related, yet neutral, 1-mesityl borole reveals strong Lewis acidity, reduced HOMO-LUMO gaps, and increased anti-aromatic character.

RESUMEN

The pentaaryl borole (Ph*C)4 BXylF [Ph*=3,5-tBu2 (C6 H3 ); XylF =3,5-(CF3 )2 (C6 H3 )] reacts with low-valent Group 13 precursors AlCp* and GaCp* by two divergent routes. In the case of [AlCp*]4 , the borole reacts as an oxidising agent and accepts two electrons. Structural, spectroscopic, and computational analysis of the resulting unprecedented neutral η5 -Cp*,η5 -[(Ph*C)4 BXylF ] complex of AlIII revealed a strong, ionic bonding interaction. The formation of the heteroleptic borole-cyclopentadienyl "aluminocene" leads to significant changes in the 13 C NMR chemical shifts within the borole unit. In the case of the less-reductive GaCp*, borole (Ph*C)4 BXylF reacts as a Lewis acid to form a dynamic adduct with a dative 2-center-2-electron Ga-B bond. The Lewis adduct was also studied structurally, spectroscopically, and computationally.

RESUMEN

Establishing access to a bulky tetraaryl dilithiobutadiene (Ph*C)4 Li2 (Ph*=3,5-tBu2 (C6 H3 )) allowed for the synthesis of five-membered heterocycles with incorporated main-group elements. Along with an amino borole, a set of substituted pentaaryl boroles (Ph*C)4 BAr has been synthesized. The examination of their absorption spectra and computational studies by means of DFT granted insight into the influence of peripheral substituents on the electronic features of the parent pentaphenyl borole (PhC)4 BPh. Introduction of the more electron-rich Ph* residue at the carbon atoms increases the HOMO energy, redshifting the visible π/π*-absorption bands compared with the parent pentaphenyl borole. The influence on the frontier orbitals of three different boron-bound aryls with electronically modulating substituents in the remote 3,5-positions Ar=3,5-R2 -C6 H3 (R=Me, H, CF3 ) was studied. The substituents were found to increase (+I effect, Me) or decrease (-I effect, CF3 ) the LUMO energy, thus directly affecting the visible absorption spectra. This represents the first study on HOMO-LUMO-gap adjustments by a combined push-pull approach of a substituted pentaphenylborole.

RESUMEN

The reactions of a monomeric borole and a dimeric borole with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene were investigated. The monomeric borole reacted at ambient temperature whereas heat was required to crack the dimer to form the monomer and induce reactivity. 2,3-Dimethyl-1,3-butadiene reacts to give diverse products resulting from a cycloaddition process with the B-C moiety of the boroles acting as a dienophile, followed by rearrangements to furnish bicyclic species. For 1,3-cyclohexadiene, a [4+2] process is observed in which 1,3-cyclohexadiene serves as the dienophile and the boroles as the diene partner. The experimental results are corroborated with mechanistic theoretical calculations that indicate boroles can serve as either a diene or dienophile in cycloaddition reactions with dienes.

RESUMEN

The synthesis of two η5 -aminoborole complexes of germanium(II) from the reaction of a germole dianion with aminoboron dichlorides is reported. This reaction constitutes a remarkable example of a germole-to-borole transformation. The two aminoborole complexes of germanium(II) were fully characterized by multinuclear NMR spectroscopy, IR spectroscopy, HRMS, and, in one case, by X-ray crystallography. The results of quantum-mechanical calculations favor the electronic structure of a half-sandwich complex of GeII over an ionic representation with a germanium dication stabilized by an aromatic aminoborole dianion.

RESUMEN

Boroles undergo dimerization reactions to give Diels-Alder (DA) dimers, bridged-bicyclic (BB) dimers or spiro dimers (SD) depending on the substituents on the borole. We performed DFT calculations to investigate how different substituents at the carbon atoms of the butadiene backbone as well as at the boron atom influence the dimerization reaction pathways. The DFT results show that, in general, both the DA and BB dimers are easily accessible kinetically, and the DA dimers are thermodynamically more stable than the BB dimers. When the substituent-substituent repulsive steric interactions are alleviated to a certain extent, the BB dimers are more stable than the DA dimer, and become accessible. The SD dimers are generally kinetically difficult to obtain. However, we found that aryl substituents promote the formation of the SD dimers.

RESUMEN

Photolysis of the cyclic phosphine oligomer [PPh]5 in the presence of pentaarylboroles leads to the formation of 1,2-phosphaborines by the formal insertion of a phenylphosphinidene fragment into the endocyclic CB bond. The solid-state structure features a virtually planar central ring with bond lengths indicating significant delocalization. Appreciable ring current in the 1,2-phosphaborine core, detected in nuclear independent chemical shift (NICS) calculations, are consistent with aromatic character. These products are the first reported 1,2-BPC4 conjugated heterocycles and open a new avenue for BP as a valence isoelectronic substitute for CC in arene systems.

RESUMEN

We have exploited the reactivity of antiaromatic boroles, gaining access to aryl-substituted monocyclic 1,2-azaborinines. The observed ring-expansion reaction of inherently electron-deficient boroles with organometallic and organic azides is demonstrated for representative examples. This substance class is expected to provide a new avenue into 1,2-azaborinine chemistry, especially in the area of functional organoboron materials. Our results are based on NMR and UV/Vis spectroscopy as well as single-crystal X-ray crystallography and provide a virtually quantitative approach that also offers numerous points of variation.

RESUMEN

Despite the synthesis of a boryl anion by Yamashita et al. in 2006, compounds that show boron-centered nucleophilicity are still rare and sought-after synthetic goals. A number of such boryl anions have since been prepared, two of which were reported to react with methyl iodide in apparent nucleophilic substitution reactions. One of these, a borolyl anion based on the borole framework, has now been found to display single-electron-transfer (SET) reactivity in its reaction with triorganotetrel halides, which was confirmed by the isolation of the first neutral borole-based radical. The radical was characterized by elemental analysis, single-crystal X-ray crystallography, and EPR spectroscopy, and has implications for the understanding of boron-based nucleophilic behavior and the emergent role of boron radicals in synthesis. This radical reactivity was also exploited in the synthesis of compounds with rare B-Sn and B-Pb bonds, the latter of which was the first isolated and structurally characterized compound with a "noncluster" B-Pb bond.

RESUMEN

The 2,5-bis(borolyl)thiophene 2, a conjugated acceptor-π-acceptor system, can be reduced to the monoradical anion [2](.-) , the dianion [2](2-) , and the tetraanion [2](4-) . The dianion [2](2-) was also prepared by a comproportionation reaction and features an absorption maximum in the near-IR region (λmax =800 nm), which is characteristic of a bipolaron with a quinoidal structure.

Asunto(s)

Compuestos de Boro/química , Tiofenos/química , Aniones/química , Cristalografía por Rayos X , Oxidación-Reducción

RESUMEN

Chemical single-electron reduction of 1-mesityl-2,3,4,5-tetraphenylborole (3) gave a stable radical anion [CoCp*2 ][3] as shown in earlier investigations. Herein, we present the reaction of [CoCp*2 ][3] with the 2,2,6,6-tetramethylpiperidine-N-oxyl radical (TEMPO), a common radical trap. Instead of radical recombination, the reaction proceeds through a redox pathway involving oxidation of the borole radical anion combined with reduction of TEMPO. This electron-transfer process is accompanied by a deprotonation reaction of the cobaltocenium counterion by the base TEMPO(-) to give TEMPO-H and a neutral cobalt(I) fulvene complex (7). The latter was not observed directly during the reaction, because it instantaneously reacts as a nucleophile attacking at the boron center of the in situ generated borole 3 to give the borate 6. However, 7 was synthesized independently by deprotonation of [CoCp*2 ][PF6 ]. In addition, the obtained zwitterionic cobaltocenium borate 6 undergoes a photolytic rearrangement to form the borata-alkene derivative 9 that thermally transforms to the chiral cobaltocenium borate 12. Our investigations are based on spectroscopic evidence, X-ray crystallography, elemental analysis, as well as DFT calculations.