Formation of a stable radical by oxidation of a tetraorganoborate

Braunschweig, Holger; Krummenacher, Ivo; Mailänder, Lisa; Pentecost, Leanne; Vargas, Alfredo

doi:10.1039/c6cc02916g

Cited by 6 publications

(3 citation statements)

References 32 publications

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“…Many recent examples of boron-containing radicals take advantage of π-delocalization to access persistent or stable species. Select examples (Figure 1) include Piers' reduced benzo[c]cinnoline adduct of 2,2′diborabiphenyl, 19 Jakle's 1,2-diborylated ferrocene dimer [CpFeC 5 H 3 BPh] 2 , 20 Gabbai ̈'s borylated acridine, 21 Nozaki's β-diiminate-based heterocyclic boron radical, 22 Bourissou's phosphine-coordinated boryl radical, 23 Braunschweig's spirocyclic zwitterionic radical, 24 and Marder's boryl-pyrene species. 14 One-electron reduction of B−B bonds was exploited by Gabbai 25 to generate the radical anion [C 10 H 6 (BMes 2 ) 2 ] •− .…”

Section: ■ Introductionmentioning

confidence: 99%

Reactions of Boron-Derived Radicals with Nucleophiles

et al. 2016

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Reactions of phenanthrenedione- and pyrenedione-derived borocyclic radicals, CHOB(CF) (n = 14 (1), 16 (3)), with a variety of nucleophiles have been studied. Reaction of 1 with P(t-Bu) affords the zwitterion 3-(t-Bu)PCHOB(CF) (5) in addition to the salt [HP(t-Bu)][CHOB(CF)] (6). In contrast, the reaction of 1 with PPh proceeds to give two regioisomeric zwitterions, 1-(PhP)CHOB(CF) (7a) and 3-(PhP)CHOB(CF) (7b), as well as the related boronic ester CHOB(CF) (2). In a similar fashion, 3 reacted with PPh to give 3-(PhP)CHOB(CF) (8a), 1-(PhP)CHOB(CF) (8b), and boronic ester CHOB(CF) (4). Reactions of secondary phosphines PhPH and tBuPH with 3 yield 3-(RPH)CHOB(CF) (R = Ph (9), t-Bu (10)). The reaction of 1 with N-heterocyclic carbene IMes afforded 3-(IMes)CHOB(CF) (11) and [IMesH][CHOB(CF)] (12), while the reactions with quinuclidine and DMAP afforded the species 3-(CHN)CHOB(CF) (13) and [H(NCH)][CHOB(CF)] (14), and the salt [9,10-(DMAP)CHOB(CF)][CHOB(CF)] (15), respectively. These products have been fully characterized, and the mechanism for the formation of these products is considered in the light of DFT calculations.

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Section: ■ Introductionmentioning

confidence: 99%

Reactions of Boron-Derived Radicals with Nucleophiles

et al. 2016

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“…Recently reported neutral spiro‐borate radical B [23] formally contains a tetrahedral borate center and s‐ cis ‐butadiene radical cation as the spin‐bearing site. In the crystal state, two π‐systems have different geometries, whereas the ESR data in solution was consistent with simultaneous delocalization of the unpaired spin over both π‐planes.…”

Section: Introductionmentioning

confidence: 99%

Stable Spiro‐Fused Diarylaminyl Radicals: A New Type of a Neutral Mixed‐Valence System

Sentyurin

Levitskiy

Bogdanov

et al. 2023

Chemistry A European J

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A new type of neutral mixed-valence system was synthesized using a facile one-pot procedure. The spiroconjugated framework is additionally "fastened" with a biphenyl bridge, which does not directly participate in spin delocalization but makes the molecule stable and influences the reorganization energy and the energy barrier of the intramolecular electron transfer. The in-depth experimental and quantum-chemical study allowed determining the radicals as the Class II Robin-Day-mixed-valence systems. The structure of the radicals was confirmed by the X-ray data, which are relatively rare for Class II MV molecules. Advanced properties of the radicals, such as an ambipolar redox behavior and panchromatic absorption in the visible and NIR regions, along with their stability, make them of interest for materials science. All radicals demonstrate the SOMO-HOMO inversion phenomenon, which was supported by the DFT and the experimental study.

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“…In conventional boron complexes, difluoride is very common because of its high stability and low synthetic difficulty. Meanwhile, some research groups tried replacing the two fluoride atoms with another unit [ 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 ]. The resulting spiro complexes have various unique features originating from cationic character and steric structures.…”

Section: Introductionmentioning

confidence: 99%

Modulation of Properties by Ion Changing Based on Luminescent Ionic Salts Consisting of Spirobi(boron ketoiminate)

et al. 2022

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We report development of luminescent ionic salts consisting of the boron ketoiminate structure, which is one of the robust skeletons for expressing aggregation-induced emission (AIE) properties. From the formation of the boron-centered spiro structure with the ketoiminate ligands, we obtained stable ionic salts with variable anions. Since the ionic salts show Tms below 100 °C, it was shown that these salts can be classified as an ionic liquid. By using PF6 anion, the single crystal—which is applicable for X-ray crystallography—was obtained. According to the optical measurements, it was proposed that electronic interaction should occur through the boron center. Moreover, intense emission was observed both in solution and solid. Finally, we demonstrated that the emission color of the PF6 salt was altered from crystal to amorphous by adding mechanical forces. Based on boron complexation and intrinsic solid-state luminescent characters, we achieved obtainment of emissive ionic materials with environmental responsivity.

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Formation of a stable radical by oxidation of a tetraorganoborate

Cited by 6 publications

References 32 publications

Reactions of Boron-Derived Radicals with Nucleophiles

Reactions of Boron-Derived Radicals with Nucleophiles

Stable Spiro‐Fused Diarylaminyl Radicals: A New Type of a Neutral Mixed‐Valence System

Modulation of Properties by Ion Changing Based on Luminescent Ionic Salts Consisting of Spirobi(boron ketoiminate)

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