ChemInform Abstract: Thermal Decomposition of Trimethyl‐ and Triethylarsine in the Gas Phase.

Yablokov, V. A.; Zelyaev, I. A.; Makarov, E.I.; Gatilov, Yu. F.; Gonina, V.A.; Зорин, А. Д.

doi:10.1002/chin.198639131

Cited by 2 publications

(4 citation statements)

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“…[49] The thermal decomposition of triethylbismuth at 200 °C leads to the formation of ethylene, butane and butenes as major gaseous products, suggesting the formation of ethyl radicals via homolysis of the BiÀ C(sp 3 ) carbon bonds (Scheme 4, top). [50] Besides thermal homolysis, early work in the 1960s showed that the BiÀ C(sp 2 ) bond in BiPh 3 can also be homolyzed under UV light irradiation, releasing phenyl radicals. These ensuing radicals were subsequently trapped by (hetero)aromatic toluene and pyridine, giving products of phenylation, benzene and metallic bismuth (Scheme 4, bottom).…”

Section: Historical Perspectivementioning

confidence: 99%

“…As described in the first two sections, Bi−E bonds have been established for a long time to be relatively weak [38,50–52,72] . This weakness arises from the minimal overlap of the large and diffuse orbitals of bismuth, and hence, results on facile homolytic cleavages that can happen under both thermal or photochemical conditions.…”

Section: Generation Characterization and Properties Of Bismuth Radicalsmentioning

confidence: 99%

“…This process can be slowed down by increasing the steric encumbrance around the bismuth‐alkyl bond; for example, bis(2,4,6‐tri‐isopropylphenyl)methyl Bi(III) can even be purified by flash column chromatography under air [49] . The thermal decomposition of triethylbismuth at 200 °C leads to the formation of ethylene, butane and butenes as major gaseous products, suggesting the formation of ethyl radicals via homolysis of the Bi−C(sp 3 ) carbon bonds (Scheme 4, top) [50] . Besides thermal homolysis, early work in the 1960s showed that the Bi−C(sp 2 ) bond in BiPh 3 can also be homolyzed under UV light irradiation, releasing phenyl radicals.…”

Section: Historical Perspectivementioning

confidence: 99%

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Bismuth in Radical Chemistry and Catalysis

Mato,

Cornella

2023

Angew Chem Int Ed

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Whereas indications of radical reactivity in bismuth compounds can be traced back to the 19th century, the preparation and characterization of both transient and persistent bismuth‐radical species has only been established in recent decades. These advancements led to the emergence of the field of bismuth radical chemistry, mirroring the progress seen for other main‐group elements. The seminal and fundamental studies in this area have ultimately paved the way for the development of catalytic methodologies involving bismuth‐radical intermediates, a promising approach that remains largely untapped in the broad landscape of synthetic organic chemistry. In this review, we delve into the milestones that eventually led to the present state‐of‐the‐art in the field of radical bismuth chemistry. Our focus aims at outlining the intrinsic discoveries in fundamental inorganic/organometallic chemistry and contextualizing their practical applications in organic synthesis and catalysis.

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Section: Historical Perspectivementioning

confidence: 99%

Section: Generation Characterization and Properties Of Bismuth Radicalsmentioning

confidence: 99%

Section: Historical Perspectivementioning

confidence: 99%

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Bismuth in Radical Chemistry and Catalysis

Mato,

Cornella

2023

Angew Chem Int Ed

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“…As described in the first two sections, BiÀ E bonds have been established for a long time to be relatively weak. [38,[50][51][52]72] This weakness arises from the minimal overlap of the large and diffuse orbitals of bismuth, and hence, results on facile homolytic cleavages that can happen under both thermal or photochemical conditions. Indeed, many Bi(III) compounds have been identified as photosensitive or unstable at room temperature, such as BiCp 3 , [73] and Bi(NMe 2 ) 3 , [74] among others.…”

Section: Generation Of Bismuth Radicals Via Homolysis Of Bi(iii)à E B...mentioning

confidence: 99%