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Isolation of Stable Borepin Radicals and Anions.

ABSTRACT: Borepin, a 7-membered boron-containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While electron-deficient borepins are well-established, reduced electron-rich species have remained elusive. Herein we report the first isolable, crystalline borepin radical (2 a, 2 b) and anion (3 a, 3 b) complexes, which have been synthesized by potassium graphite (KC₈ ) reduction of cyclic(alkyl)(amino) carbene-dibenzo[b,d]borepin precursors. Borepin radicals and anions have been characterized by EPR or NMR, elemental analysis, X-ray crystallography, and cyclic voltammetry. In addition, the bonding features have been investigated computationally using density functional theory.

SUBMITTER: Hollister KK

PROVIDER: S-EPMC9324096 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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Isolation of Stable Borepin Radicals and Anions.

Hollister Kimberly K KK Yang Wenlong W Mondol Ranajit R Wentz Kelsie E KE Molino Andrew A Kaur Aishvaryadeep A Dickie Diane A DA Frenking Gernot G Pan Sudip S Wilson David J D DJD Gilliard Robert J RJ

Angewandte Chemie (International ed. in English) 20220405 23

Borepin, a 7-membered boron-containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While electron-deficient borepins are well-established, reduced electron-rich species have remained elusive. Herein we report the first isolable, crystalline borepin radical (2 a, 2 b) and anion (3 a, 3 b) complexes, which have been synthesized by potassium graphite (KC<sub>8</sub> ) reduction of cyclic(alkyl)(amino) carbene-dibenzo[b,d]borepin p ...[more]

PMID: 35289046

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Project description:This study shows that methyl 2-aminobenzoate (also known as methyl anthranilate, hereafter MA) undergoes direct photolysis under UVC and UVB irradiation and that its photodegradation is further accelerated in the presence of H₂O₂. Hydrogen peroxide acts as a source of hydroxyl radicals (·OH) under photochemical conditions and yields MA hydroxyderivatives. The trend of MA photodegradation rate vs. H₂O₂ concentration reaches a plateau because of the combined effects of H₂O₂ absorption saturation and ·OH scavenging by H₂O₂. The addition of chloride ions causes scavenging of ·OH, yielding Cl₂·- as the most likely reactive species, and it increases the MA photodegradation rate at high H₂O₂ concentration values. The reaction between Cl₂·- and MA, which has second-order rate constant k C l 2 • - + M A = (4.0 ± 0.3) × 10⁸ M-1·s-1 (determined by laser flash photolysis), appears to be more selective than the ·OH process in the presence of H₂O₂, because Cl₂·- undergoes more limited scavenging by H₂O₂ compared to ·OH. While the addition of carbonate causes ·OH scavenging to produce CO₃·- ( k C O 3 • - + M A = (3.1 ± 0.2) × 10⁸ M-1·s-1), carbonate considerably inhibits the photodegradation of MA. A possible explanation is that the elevated pH values of the carbonate solutions make H₂O₂ to partially occur as HO₂-, which reacts very quickly with either ·OH or CO₃·- to produce O₂·-. The superoxide anion could reduce partially oxidised MA back to the initial substrate, with consequent inhibition of MA photodegradation. Fast MA photodegradation is also observed in the presence of persulphate/UV, which yields SO₄·- that reacts effectively with MA ( k S O 4 • - + M A = (5.6 ± 0.4) × 10⁸ M-1·s-1). Irradiated H₂O₂ is effective in photodegrading MA, but the resulting MA hydroxyderivatives are predicted to be about as toxic as the parent compound for aquatic organisms (most notably, fish and crustaceans).

Dataset Information

Isolation of Stable Borepin Radicals and Anions.

Publications

Isolation of Stable Borepin Radicals and Anions.

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