Boryl Anions Research Articles

Evaluation of the σ-Donating and π-Accepting Properties of N-Heterocyclic Boryl Anions.

The relative σ-donating and π-accepting capacities of a range of synthetically relevant boryl anions have been evaluated by examining the geometric, thermochemical, and electronic properties of their adducts to the Li+ cation and Se atom, as compared to the properties of the analogous neutral N-heterocyclic carbenes (NHCs), by theoretical methods. The results indicate that boryl anions have a weaker π-accepting capability compared to NHCs, but it is still a non-negligible factor in the bonding contributions between boryl and the Se atom. The tunability of the π-accepting capacity of boryl anions is similar to that of NHCs, indicating a potential for the modification of the electronic properties of metal complexes incorporating either boryl or NHC ligands. In all cases, the boryl ligands were found to be superior σ-donors to NHCs.

NNB-Type Tridentate Boryl Ligands Enabling a Highly Active Iridium Catalyst for C⁻H Borylation.

Boryl ligands play a very important role in catalysis because of their very high electron-donating property. In this paper, NNB-type boryl anions were designed as tridentate ligands to promote aryl C–H borylation. In combination with [IrCl(COD)]2, they generate a highly active catalyst for a broad range of (hetero)arene substrates, including highly electron-rich and/or sterically hindered ones. This work provides a new NNB-type tridentate boryl ligand to support homogeneous organometallic catalysis.

A New Perspective on Borane Chemistry: The Nucleophilicity of the B-H Bonding Pair Electrons.

A number of recently discovered nucleophilic boron compounds, such as boryl anions and borylenes, are breaking the rules regarding boron and boron-containing compounds and their reputation as Lewis acids/electrophiles. In a similar fashion, the B-H bonding pair electrons in boranes also show nucleophilicity which is ascribed to the lower electronegativity of boron relative to that of hydrogen. However, this nucleophilicity of the B-H bond has received far less attention. Explorations of the nucleophilicity of the B-H bonding pair electrons have led to the formation of B-H-B bonded units and B-H⋅⋅⋅H-Y dihydrogen bonds, based on which new chemistry has been uncovered, including the elucidation of the mechanism of formation of aminodiborane (ADB), the diammoniate of diborane (DADB), and lithium or sodium salts of octahydrotriborates (B3 H8 - ), as well as the development of more convenient and straightforward synthetic routes to these reagents. Moreover, the recognition of the nucleophilic properties of the B-H bonding pair electrons will also help to more deeply understand the different mechanisms operating in hydroboration reactions.

Diborane heterolysis: breaking and making B-B bonds at magnesium.

Reaction of the dimeric β-diketiminato magnesium hydride [(BDI)MgH]2 (BDI = HC{(Me)CN-2,6-i-Pr2C6H3}2) with bis-pinacolatodiborane (B2pin2) resulted in B-O bond activation and formation of a magnesium complex of an unusual borylborohydride anion. In contrast, similar treatment of the mononuclear organomagnesium [{BDI}Mg(n-Bu)] with 4,4,4',4',6,6'-hexamethyl-2,2'-bi(1,3,2-dioxaborinane) (B2hex2) provided a B(sp2)-B(sp3) diborane anion, [(hex)BB(n-Bu)(hex)]-, with a constitution which is analogous to that formed in the previously reported reaction with bis(pinacolato)diboron (B2pin2). Subsequent addition of 4-dimethylaminopyridine to a solution of this compound induced alkylborane displacement and provided a magnesium boryl derivative containing a terminal Mg-B(hex) interaction (Mg-B 2.319(3) Å), a result which reinforces the generality of this approach for the synthesis of boryl anions by B-B bond heterolysis. Further studies of the reactivity of the initially formed B(sp2)-B(sp3) anions with diborane small molecules also resulted in alkylborane displacement and the production of triboron anions, which are propagated by contiguous and electron precise (2c-2e) B-B-B interactions.

Easy access to nucleophilic boron through diborane to magnesium boryl metathesis

Organoboranes are some of the most synthetically valuable and widely used intermediates in organic and pharmaceutical chemistry. Their synthesis, however, is limited by the behaviour of common boron starting materials as archetypal Lewis acids such that common routes to organoboranes rely on the reactivity of boron as an electrophile. While the realization of convenient sources of nucleophilic boryl anions would open up a wealth of opportunity for the development of new routes to organoboranes, the synthesis of current candidates is generally limited by a need for highly reducing reaction conditions. Here, we report a simple synthesis of a magnesium boryl through the heterolytic activation of the B–B bond of bis(pinacolato)diboron, which is achieved by treatment of an easily generated magnesium diboranate complex with 4-dimethylaminopyridine. The magnesium boryl is shown to act as an unambiguous nucleophile through its reactions with iodomethane, benzophenone and N,N′-di-isopropyl carbodiimide and by density functional theory.

Completing the series of boron-nucleophilic cyanoborates: boryl anions of type NHC-B(CN)2.

Since the first seminal report of boron-centred nucleophiles, the area of boryl anions has developed only sporadically and requires further systematisation. The boryl anions of type NHC-B(CN)2- (NHC = N-heterocyclic carbene) described herein complete a consistent series with the known anions cAAC-B(CN)2- [cAAC = cyclic(alkyl)(amino)carbene] and B(CN)32-. A novel approach towards NHC-stabilised cyanoboranes based on alkylthio-cyano exchange at boron is presented, and in contrast to other methods affords the products in better purity and yield. Reduction of suitable NHC-dicyanoboranes gave two unprecedented examples of NHC-B(CN)2- boryl anions. The latter were shown to react as boron-centred nucleophiles with facile formation of B-E bonds, where E = C, Si, Sn, P, Au. Bonding analysis by DFT calculations suggests a systematic variation of the energy of the boron-centred HOMO depending on the carbene, which in turn can control the nucleophilic character.

Phosphine-Stabilized Borylenes and Boryl Anions as Ligands? Redox Reactivity in Boron-Based Pincer Complexes.

Stabilized borylenes (L2 BH:) with weakly π-accepting substituents L, such as phosphines, were previously believed to be unstable. In the current manuscript, we describe a series of complexes formally containing a phosphine-stabilized borylene or boryl anion. In contrast to common trivalent boron compounds, the boron-based ligands in this study act as electron-donating ligands. The reported iron hydride complexes exhibit a unique reactivity pattern, undergoing a reversible B-H reductive elimination concomitant with oxidation of the boron(I) center.

Hoveyda-Grubbs complexes with boryl anions are predicted to be fast metathesis catalysts

A series of potential metathesis catalyst based on Hoveyda-Grubbs ruthenium system with the N-heterocyclic carbene replaced by N-heterocyclic carbene boryl anion were investigated using the M06 density functional approach. We show that these hypothetical metathesis precatalysts have two stable conformations depending on the position of the benzylidene moiety with respect to the NHC part of the complex. Estimates of the free Gibbs energy of initiation for these systems predict that they can be one of the fastest initiating metathesis catalysts, on the level of 3rd generation Grubbs complexes.

A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene.

A potassium diboryllithate (B2 LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2 LiK, revealed ionic interactions between the two bridging boryl anions and Li(+) and K(+) . Upon standing in benzene, B2 LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K(+) .

A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene

AbstractA potassium diboryllithate (B2LiK) was synthesized and structurally characterized. DFT calculations, including NPA and AIM analyses of B2LiK, revealed ionic interactions between the two bridging boryl anions and Li+ and K+. Upon standing in benzene, B2LiK deprotonated the solvent to form a hydroborane and a phenylborane. On the basis of DFT calculations, a detailed reaction mechanism, involving deprotonation and hydride/phenyl exchange processes, is proposed. An NBO analysis of the transition state for the deprotonation of benzene suggests that the deprotonation should be induced by the coordination of benzene to the K+.

Double N,B-Type Bidentate Boryl Ligands Enabling a Highly Active Iridium Catalyst for C-H Borylation.

Boryl ligands hold promise in catalysis due to their very high electron-donating property. In this communication double N,B-type boryl anions were designed as bidentate ligands to promote an sp(2) C-H borylation reaction. A symmetric pyridine-containing tetraaminodiborane(4) compound (1) was readily prepared as the ligand precursor that could be used, in combination with [Ir(OMe)(COD)]2, to in situ generate a highly active catalyst for a broad range of (hetero)arene substrates including highly electron-rich and/or sterically hindered ones. This work provides the first example of a bidentate boryl ligand in supporting homogeneous organometallic catalysis.

Assessing the Brønsted basicity of diaminoboryl anions: reactivity toward methylated benzenes and dihydrogen.

Treatment of toluene or p-xylene with diaminoboryllithium results in consecutive reactions, involving boryl-anion-mediated deprotonation at the benzylic position followed by nucleophilic substitution at the boron center, producing benzylborane species and LiH. Diaminoboryllithium also cleaves H2 heterolytically affording diaminohydroborane and LiH, while the reaction of lithium diaminoboryl(bromo)cuprate with H2 takes place accompanied by reduction of Cu(I) to give diaminohydroborane, LiH, and Cu(0).

Evidence for Extensive Single‐Electron‐Transfer Chemistry in Boryl Anions: Isolation and Reactivity of a Neutral Borole Radical

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.

ChemInform Abstract: Synthesis and Reactions of N‐Heterocyclic Carbene Boranes

AbstractReview: ca. 170 refs.

ChemInform Abstract: Creation of Nucleophilic Boryl Anions and Their Properties

AbstractReview: 146 refs.

Creation of Nucleophilic Boryl Anions and Their Properties

Abstract A series of anionic boron compounds, possessing a polarized boron–metal bond, were synthesized and structurally characterized. Detailed analyses of these boryl anions using NMR spectroscopy, X-ray crystallography, reactivity with electrophiles, and DFT calculations revealed that these compounds have anionic and nucleophilic character on the boron center in contrast to conventional boron-containing molecules with a Lewis acidic character. Some applications of boryl anions toward organic synthesis, organometallic chemistry, and main group chemistry are also described.

Synthesis and Reactions of N‐Heterocyclic Carbene Boranes

Boranes are widely used Lewis acids and N-heterocyclic carbenes (NHCs) are popular Lewis bases, so it is remarkable how little was known about their derived complexes until recently. NHC-boranes are typically readily accessible and many are so stable that they can be treated like organic compounds rather than complexes. They do not exhibit "borane chemistry", but instead are proving to have a rich chemistry of their own as reactants, as reagents, as initiators, and as catalysts. They have significant potential for use in organic synthesis and in polymer chemistry. They can be used to easily make unusual complexes with a broad spectrum of functional groups not usually seen in organoboron chemistry. Many of their reactions occur through new classes of reactive intermediates including borenium cations, boryl radicals, and even boryl anions. This Review provides comprehensive coverage of the synthesis, characterization, and reactions of NHC-boranes.

ChemInform Abstract: Boryl Anion: Syntheses and Properties of Novel Borylmetals

AbstractReview: ca. 100 refs.

Synthesis and Structure of a Carbene‐Stabilized π‐Boryl Anion

Attack with π electrons: Reduction of a chloroborole coordinated by an N-heterocyclic carbene results in the formation of a carbene-stabilized borole monoanion (see scheme; Mes=mesityl), the molecular structure of which has been determined by X-ray analysis. Computational and reactivity studies of this boracycle confirm the presence of a π-nucleophilic boron atom, which represents a rare example in the chemistry of boryl anions.

ボリルアニオン：新しいボリル金属種の合成と性質

This account reviews our recent research on chemistry of “boryl anion”. Boryl anions can be classified with their metallic counterpart, such as Li, Mg, Cu, and Zn in a similar manner to the classification of carbanion. Syntheses and characterizations of boryllithium compounds have been achieved by using bulky substituents to prevent a dimerization of a boryl radical intermediate and nitrogen–containing heterocycle to gain an electronic stabilization. Transmetallation of boryllithium afforded a series of borylmetals having Mg, Zn, Cu, Ag, Au, Ti, or Hf. Some of these borylmetals can be regarded as a boryl anion species possessing a nucleophilic character towards organic electrophiles. Detailed analyses of group 11 borylmetal species showed a strong trans influence of boryl ligand. Borylhafnium complex could be utilized as a catalyst precursor for olefin polymerization.