Bi-Catalyzed Trifluoromethylation of C(sp²)–H Bonds under Light

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(47), С. 25538 - 25544

Опубликована: Ноя. 14, 2023

We disclose a Bi-catalyzed C–H trifluoromethylation of (hetero)arenes using CF3SO2Cl under light irradiation. The catalytic method permits the direct functionalization various heterocycles bearing distinct functional groups. structural and computational studies suggest that process occurs through an open-shell redox manifold at bismuth, comprising three unusual elementary steps for main group element. cycle starts with rapid oxidative addition to low-valent Bi(I) catalyst, followed by light-induced homolysis Bi(III)–O bond generate trifluoromethyl radical upon extrusion SO2, is closed hydrogen-atom transfer Bi(II) intermediate.

Язык: Английский

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Bismuth in Radical Chemistry and Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(8)

Опубликована: Ноя. 22, 2023

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

Язык: Английский

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NCN-pincer organopnictogen(iii) bis(aryloxides)

New Journal of Chemistry, Год журнала: 2024, Номер 48(12), С. 5523 - 5529

Опубликована: Янв. 1, 2024

New hypercoordinated organopnictogen( iii ) bis(aryloxides), ArPn(SC 6 H 3 R 2 -2,6) (Pn = Sb, Bi; Ar NCN-pincer ligand; i Pr, OMe), have been prepared and their solution solid state structures investigated.

Язык: Английский

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Comparative Study of the Structures and Reactivities of Cationic Nickel and Palladium Complexes with a Bismuth-Bisphosphine (PBiP) Ligand

Organometallics, Год журнала: 2025, Номер unknown

Опубликована: Март 21, 2025

Язык: Английский

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Molecular Design of Al(II) Intermediates for Small Molecule Activation

JACS Au, Год журнала: 2025, Номер 5(5), С. 2076 - 2088

Опубликована: Май 8, 2025

Promoting societally important small molecule activation processes with earth-abundant metals is foundational for a sustainable chemistry future. In this context, mapping new reaction pathways that would enable abundant main-group elements to mimic the behaviors of d- and f-block facilitated by exploring unusual oxidation states. The most metal on earth, aluminum, has been well studied in Lewis acidic +III basic +I states but rarely potentially biphilic +II state until recently, when renaissance Al-(II) emerged from range research groups. Perspective, we review mononuclear Al radicals, including both Al-centered radicals (i.e., compounds) redox non-innocent systems formally species are physically Al-(III) ligand-centered radicals), an emphasis reactivity. We also provide meta-analysis literature summarize how different design strategies (e.g., non-innocence, strained coordination geometries) have shown impart character tune their behavior, thus allowing certain ions such as Ti-(III) Sm-(II). expect these molecular concepts inform future studies continues grow.

Язык: Английский

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Bismuth in Radical Chemistry and Catalysis

Angewandte Chemie, Год журнала: 2023, Номер 136(8)

Опубликована: Ноя. 22, 2023

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

Язык: Английский

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Pnictogen Chemistry: From Light to Heavy Compounds

ChemPlusChem, Год журнала: 2024, Номер 89(12)

Опубликована: Авг. 23, 2024

Pnictogen compounds offer a broad and highly tunable set of characteristics, including pronounced Lewis acidity basicity, privileged ligand behavior, the reversible switching between different oxidation states, accessibility low-valent species, intriguing photophysical properties. In recent renaissance p-block chemistry, researchers are focusing their efforts to investigate exploit these properties, reveal unprecedented reactivity patterns design fascinating applications based on modern innovative pnictogen chemistry. This special issue presents current trends in field

Язык: Английский

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Arylative difunctionalization of olefins using easily accessed organobismuth (V) reagents

Chem, Год журнала: 2024, Номер 10(10), С. 2945 - 2947

Опубликована: Окт. 1, 2024

Язык: Английский

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