Cleavage of BN triple bonds by main group reagents

Winner, Lena; Hermann, Alexander; Bélanger‐Chabot, Guillaume; González-Belman, Oscar F.; Jiménez‐Halla, J. Óscar C.; Kelch, Hauke; Braunschweig, Holger

doi:10.1039/c8cc02317d

Cited by 17 publications

(9 citation statements)

References 39 publications

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“…In 2018, the Braunschweig group described the insertion of two main group reagents into the B�N triple bond. [45] Isolable silylene 112 reacted with di-tertbutyliminoborane 24 smoothly to form the bicyclic silaimineborane 113 via total cleavage of the BN triple bond (Scheme 18a). Compound 113 features two typical BÀ N single bonds…”

Section: Cleavage Of Bn Triple Bondsmentioning

confidence: 99%

Recent Advances in the Chemistry of Iminoborane Derivatives

2022

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Iminoboranes are important unsaturated organoboron compounds with the formula RB≡NR’. They are isoelectronic with alkynes, yet normally exhibit higher reactivity due to their polarity, thus enabling versatile applications in coordination, synthetic and materials chemistry. This review briefly describes the most recent progress in iminoborane derivatives with the focus on new persistent species and their diverse reactivity, which greatly enrich the iminoborane chemistry. In addition, the promising research directions are also provided.

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Section: Cleavage Of Bn Triple Bondsmentioning

confidence: 99%

Recent Advances in the Chemistry of Iminoborane Derivatives

2022

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“…Aside from oxoboranes, iminoboranes (RBNR′) represent another type of multiple-bonded organoboron compounds and have been extensively investigated since the seminal works by Paetzold and Noth . With respect to the isoelectronic alkynes, iminoboranes display an increased reactivity toward self-oligomerization and intramolecular C–H activation because of the intrinsic polarity and relative weakness of the BN triple bond. , Therefore, such species are typically generated by vacuum gas-phase pyrolysis of (trimethylsilylamino)boron halides using specialized apparatuses . However, with the help of sterically bulky organyls on either side of the BN triple bond, a variety of monomeric iminoboranes IV have been isolated and structurally characterized (Chart c) .…”

Section: Introductionmentioning

confidence: 99%

Acid/Base-Free Acyclic Anionic Oxoborane and Iminoborane Bearing Diboryl Groups

et al. 2022

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Anionic oxoboranes and neutral iminoboranes, which are isoelectronic to ketones and alkynes, respectively, have attracted much attention because of their unique structures and various reactivity. However, acid/base-free oxoboranes and iminoboranes are still limited, and readily accessible examples with diverse electronic and steric characteristics are highly desirable. Herein, we report the first syntheses of the acyclic anionic oxoborane 2 and iminoborane 4 bearing two boryl ligands, both of which are acid/base-free. Spectroscopic analysis, X-ray crystallography, and theoretical calculations reveal that 2 and 4 possess a polarized terminal B�O double bond and central B�N triple bond, respectively.

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“…Subsequently, Bertrand et al demonstrated the cyclic (alkyl)(amino)carbene (CAAC)-induced elimination of a trimethylsilyl halide of (Me 3 Si) 2 NBX 2 to give the haloiminoborane–carbene adduct II . The Braunschweig group isolated two carbene-coordinated iminoboranes III and IV through complexation between t BuBN t Bu and CAAC and N-heterocyclic carbene (NHC), respectively . Nevertheless, both III and IV are thermally unstable and decompose above −45 °C gradually.…”

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confidence: 99%

New Approaches to N-Heterocyclic-Carbene-Coordinated Iminoborane and Borenium Species

et al. 2020

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The synthesis, characterization, and reactivity of an iminoborane–N-heterocyclic carbene (NHC) adduct were described. The reaction of DmpNHB(OEt)Br [1; Dmp = 2,6-bis(2,4,6-trimethylphenyl)phenyl] with 2 equiv of 1,3-diimethyl-4,5-dimethylimidazol-2-ylidene (IMe4) resulted in the formation of an iminoborane–NHC complex 2. Both X-ray analysis and density functional theory calculations revealed the double-bond character of the BN bond in 2. Interestingly, compared with the corresponding Lewis-base-free iminoborane, 2 features a nitrogen atom with increased electron density, which could be attributed to coordination of the NHC. Similar to the isoelectronic species imine, this nitrogen center in 2 can be easily attacked by electrophiles. Indeed, the reaction of 2 with trimethylsilyl triflate (Me3SiOTf) afforded an NHC-stabilized borenium cation 3, representing a facile strategy to prepare cationic tricoordinate boron species.

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Cleavage of BN triple bonds by main group reagents

Cited by 17 publications

References 39 publications

Recent Advances in the Chemistry of Iminoborane Derivatives

Recent Advances in the Chemistry of Iminoborane Derivatives

Acid/Base-Free Acyclic Anionic Oxoborane and Iminoborane Bearing Diboryl Groups

New Approaches to N-Heterocyclic-Carbene-Coordinated Iminoborane and Borenium Species

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