Synthesis of Symmetrically and Unsymmetrically Substituted Cationic Diborane(4) Compounds with Distinct Structural Motifs and Properties

Filbeck, Eric; Kistner, Lucas; Vogler, Daniel; Gasser, David Bučak; Martins, Lilliana Florido; Schöner, Maximilian; Kaifer, Elisabeth; Himmel, Hans‐Jörg

doi:10.1002/ejoc.202201105

Cited by 4 publications

(5 citation statements)

References 56 publications

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“…With 1.7097(1) Å, the BÀ B bond length is in a typical range for related BÀ B single bonds. [24] In this case, no electron-transfer is involved. The conversion was followed by 1 H NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Halide‐Coupled Double Electron Transfer with Electron‐Rich Diboranes

Filbeck,

Cremer,

Jansen

et al. 2023

Chemistry A European J

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The ditriflato‐diborane B2(μ‐hpp)2(OTf)2 (hpp = 1,3,4,6,7,8‐hexahydro‐2H‐pyrimido[1,2‐a]pyrimidinate) acts as a stable surrogate of the elusive dication [B2(hpp)2]2+, being both electrophilic (vacant boron p orbitals) and nucleophilic (filled B‐B bond orbital). This combination of seemingly contrasting behaviors could be used to develop a metallomimetic diborane chemistry, with Lewis σ‐basic and π‐acidic substrates being bound and reduced at the diborane. Here, we report on a novel reaction type within this general theme, in which double electron transfer from the diboron unit to the boron‐bound organic substrate is coupled with halide transfer in the other direction. Novel diborylated dienamines are synthesized in this way. The scope of this unprecedented reaction motif and the reaction pathways are elucidated.

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Section: Resultsmentioning

confidence: 99%

Halide‐Coupled Double Electron Transfer with Electron‐Rich Diboranes

Filbeck,

Cremer,

Jansen

et al. 2023

Chemistry A European J

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“…The cyclic rings of 5 and 6 exhibit a larger cavity than the previously reported polycationic cyclophanes with two or three diborane units that result from reaction of the ditriflato-diborane B 2 (hpp) 2 (OTf) 2 with di-or tri-pyridines. [24][25][26]…”

Section: Resultsmentioning

confidence: 99%

On the Coordination Chemistry of Triazolyl‐substituted Diborane Ligands, Prepared by 1,3‐dipolar Cycloaddition Reactions between Diazido‐diboranes and Alkynes

Vogler,

Schenker,

et al. 2023

Eur J Inorg Chem

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Metal‐free cycloaddition reactions between a diazido‐diborane and alkynes are used to synthesize new ditriazolyl‐diborane molecules, a bis(ferrocenyl‐1,2,3‐triazolyl)‐diborane and a bis(2‐pyridyl‐1,2,3‐triazolyl)‐diborane. Then, the bis(2‐pyridyl‐1,2,3‐triazolyl)‐diborane was used as polydentate ligand for the synthesis of larger architectures. Reaction with ditriflato‐diborane yielded a tetracationic hexaboron compound, and reaction with metal salts yielded dicationic ring compounds with two hexacoordinate metal atoms and two integrated diborane units.

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“…DFT computations suggested that the boron‐boron dehydrocouping with iodine is thermodynamically favored. Additionally, they successfully synthesized a series of guanidinate group‐stabilized cationic diboron species and other derivatives [61–64] …”

Section: Neutral B−b Bonded Diboron Compoundsmentioning

confidence: 99%

“…Additionally, they successfully synthesized a series of guanidinate group-stabilized cationic diboron species and other derivatives. [61][62][63][64] Including BÀ B bond in the small ring system is an excellent way to increase its reactivity. Xie and co-workers reported a carborane-fused four-membered boracycle 67 through the reaction of 1,2-Li 2 -o-carborane with B 2 Br 4 (SMe 2 ) 2 (Scheme 19).…”

Section: R E V I E W T H E C H E M I C a L R E C O R Dmentioning

confidence: 99%

Neutral and Anionic Diboron Compounds Bearing Electron‐Precise B−B Bond

Li,

Xu,

et al. 2023

The Chemical Record

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Electron‐precise B−B bonded compounds are valuable reagents in organic syntheses, which can be used as key starting material for the synthesis of functionalized organoboranes. Bis(pinacolato)diborane(4) B2pin2 and its derivatives are among the most studied diboron species. However, their B−B bonds usually need to be activated by transition metal catalysts or bases for further transformations. Recently, many well‐designed/reactive electron‐precise B−B bonded compounds have been developed, which could facilitate direct reactions with small molecules, unsaturated substrates, and electrophiles. This review highlights the synthesis, structure, and reactivity of neutral and anionic B−B bonded compounds.

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Synthesis of Symmetrically and Unsymmetrically Substituted Cationic Diborane(4) Compounds with Distinct Structural Motifs and Properties

Cited by 4 publications

References 56 publications

Halide‐Coupled Double Electron Transfer with Electron‐Rich Diboranes

Halide‐Coupled Double Electron Transfer with Electron‐Rich Diboranes

On the Coordination Chemistry of Triazolyl‐substituted Diborane Ligands, Prepared by 1,3‐dipolar Cycloaddition Reactions between Diazido‐diboranes and Alkynes

Neutral and Anionic Diboron Compounds Bearing Electron‐Precise B−B Bond

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