Pseudodiborenes: hydride-bridged diboranes(5) as two-electron reductants of chalcogens

Prieschl, Dominic; Dietz, Maximilian; Muessig, Jonas H.; Wagner, Katharina; Krummenacher, Ivo; Braunschweig, Holger

doi:10.1039/c9cc04692e

Cited by 9 publications

(8 citation statements)

References 56 publications

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“…Compounds 1 represent, to our knowledge, the first incursion into the field of diborane(4)-azide chemistry and are rare examples of structurally characterized boryl-substituted triazenes beyond 1,2,3-triazolate derivatives. ,,,− Only two examples of five-membered rings with the BBNNN sequence are currently known, and these are derived from nonclassical boron clusters. , The closest example of a nontriazole boryl–triazene adduct with a borane group is the borole ring-expansion intermediate reported by Martin et al Closely related examples are those of triazenes borylated at the terminal position, ,, including examples of ring-expansion reactivity of azides with boroles, and compounds in which an azide group bridges two boryl moieties . Compounds 1 are also new sp 2 –sp 3 diboranes, a class of diboranes that are unusual examples of nucleophilic boron species. , …”

Section: Resultsmentioning

confidence: 99%

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Synthesis of Complex Boron–Nitrogen Heterocycles Comprising Borylated Triazenes and Tetrazenes Under Mild Conditions

et al. 2019

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The reactions of organic azides with diaryl(dihalo)diboranes(4) were explored, resulting in the observation of a number of surprising reactivity patterns. The reaction of phenyl azide with 1,2-diaryl-1,2-dihalodiboranes(4) resulted in the formation of five-membered rings comprising diboryl-triazenes with retention of the boron–boron bond, while the reaction of the peculiar 1,1-di(9-anthryl)-2,2-difluorodiborane(4) with phenyl azide yielded a six-membered ring bearing a diboryl-triazene, whereby the B–B bond was ruptured by the insertion of an arylnitrene-like reactive intermediate. Both types of heterocycles feature unprecedented connectivity patterns and are very rare examples of boryl triazenes beyond the more common 1,2,3-triazolatoboranes. They are also the product of a unique type of aryl migration from a boron center to the phenyl azide γ-nitrogen center. Lastly, the substitution of 1,2-diaryl-1,2-dihalodiboranes(4) with azide groups, using trimethylsilyl azide as the transfer reagent, yielded boryl-tetrazaboroles and diboryldiazadiboretidines (as side-products), invoking the intermediacy of the first N-boryl-substituted iminoboranes, which are BN isosteres of monoborylated alkynes. The synthetic results are complemented with mechanistic proposals derived from quantum-chemical calculations.

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Section: Resultsmentioning

confidence: 99%

“…42 Compounds 1 are also new sp 2 −sp 3 diboranes, a class of diboranes that are unusual examples of nucleophilic boron species. 43,44 Reaction of an Unsymmetrical Diborane(4) with Phenyl Azide. 1,1-Di(9-anthryl)-2,2-difluorodiborane(4) (An 2 BBF 2 ), [26][27][28][29]45 an unsymmetrical diborane(4) that Scheme 3.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of Complex Boron–Nitrogen Heterocycles Comprising Borylated Triazenes and Tetrazenes Under Mild Conditions

et al. 2019

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“…The decomposition of 6 Me may be linked to the propensity of certain NHC-stabilised hydroboranes to undergo NHC ring-opening and -expansion reactions. 22,[54][55][56][57] The solid-state structure of 6 H (Fig. 4) shows two different conformers, (A) and (B), present in the asymmetric unit in a ca.…”

Section: Hydrogenation Of 1 Rmentioning

confidence: 99%

1,2-Dialkynyldiboranes(4): B–B versus CC bond reactivity

et al. 2022

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“…LIFDI-Orbitrap applications became quite numerous but while the results presented in these publications are heavily relying on accurate mass data by LIFDI-Orbitrap, they generally do not show these spectra. [172][173][174][175][176][177][178][179] It is a general phenomenon that in the field of LIFDI-MS there are quite a number of custom solutions available that deliver good analytical results in routine use, while the exact setup of some of them has unfortunately never been published.…”

Section: Mass Analyzers For Fi Fd and Lifdimentioning

confidence: 99%

“…The best option to realize high-resolution accurate mass measurements in FI, FD or LIFDI mode is to combine them with mass analyzers that do not require internal calibration, which is the case with FT-ICR [59][60][61][62]141,142,[164][165][166][167][168] and Orbitrap systems. [172][173][174][175][176][177][178][179] Gas chromatography-field ionization-mass spectrometry Gas chromatography-field ionization (GC-FI) is the easiest to set up hyphenation within the FI/FD/ LIFDI family, because for the most part, it just means doing FI with sample introduction from a gas chromatograph, and therefore has been accomplished soon after the introduction of FI-MS. [221][222][223] In GC-FI, all parameters of the gas chromatographic separation that may have been established in EI mode can be used without any modification. Differences to EI are caused by much lower ion currents, and consequently, the strong need to optimize the ion yield.…”

Section: Accurate Mass Measurementsmentioning

confidence: 99%

From the discovery of field ionization to field desorption and liquid injection field desorption/ionization-mass spectrometry—A journey from principles and applications to a glimpse into the future

Gross

2020

Eur J Mass Spectrom (Chichester)

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The discovery of the ionizing effect of strong electric fields in the order of volts per Ångstrom in the early 1950s eventually led to the development of field ionization-mass spectrometry (FI-MS). Due to the very low ion currents, and thus, limited by the instrumentation of the 1960s, it took some time for the, by then, new technique to become adopted for analytical applications. In FI-MS, volatile or at least vaporizable samples mainly deliver molecular ions, and consequently, mass spectra showing no or at least minor numbers of fragment ion signals. The next major breakthrough was achieved by overcoming the need to evaporate the analyte prior to ionization. This was accomplished in the early 1970s by simply depositing the samples onto the field emitter and led to field desorption-mass spectrometry (FD-MS). With FD-MS, a desorption ionization method had become available that paved the road to the mass spectral analysis of larger molecules of low to high polarity and even of organic salts. In FD-MS, all of these analytes deliver spectra with no or at least few fragment ion peaks. The last milestone was the development of liquid injection field desorption/ionization (LIFDI) in the early 2000s that allows for sample deposition under the exclusion of atmospheric oxygen and water. In addition to sampling under inert conditions, LIFDI also enables more robust and quicker operation than classical FI-MS and FD-MS procedures. The development and applications of FI, FD, and LIFDI had mutual interference with the mass analyzers that were used in combination with these methods. Vice versa, the demand for using these techniques on other than magnetic sector instruments has effectuated their adaptation to different types of modern mass analyzers. The journey started with magnetic sector instruments, almost skipped quadrupole analyzers, encompassed Fourier transform ion cyclotron resonance (FT-ICR) and orthogonal acceleration time-of-flight (oaTOF) analyzers, and finally arrived at Orbitraps. Even interfaces for continuous-flow LIFDI have been realized. Even though being niche techniques to some degree, one may be confident that FI, FD, and LIFDI have a promising future ahead of them. This Account takes you on the journey from principles and applications of the title methods to a glimpse into the future.

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Pseudodiborenes: hydride-bridged diboranes(5) as two-electron reductants of chalcogens

Abstract: Two neutral, hydride-bridged diboranes(5) were found to serve as two-electron reductants of chalcogens and thereby mimics of B–B multiply bound species.

Cited by 9 publications

References 56 publications

Synthesis of Complex Boron–Nitrogen Heterocycles Comprising Borylated Triazenes and Tetrazenes Under Mild Conditions

Synthesis of Complex Boron–Nitrogen Heterocycles Comprising Borylated Triazenes and Tetrazenes Under Mild Conditions

1,2-Dialkynyldiboranes(4): B–B versus CC bond reactivity

From the discovery of field ionization to field desorption and liquid injection field desorption/ionization-mass spectrometry—A journey from principles and applications to a glimpse into the future

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