1,2-Acylphosphinylation of Styrenes to Access β-Aryl-γ-ketophosphine Oxides by Irradiation-Induced Radical Relay

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

An acylphosphinylation reaction has been devised for the synthesis of β-aryl-γ-ketophosphine oxides, employing styrenes and acyl azolium salts through an irradiation-induced radical relay mechanism. This method effectively constructs C–C C–P bonds while demonstrating excellent functional group tolerance. Mechanistic studies revealed that a radical-addition–coupling–elimination cascade process was involved in this reaction.

Language: Английский

Amphoteric Zinc(II) Hydride Cations [ZnH]⁺: Effect of a Bipyridyl Ligand

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 23, 2025

Terminal zinc hydride cations [(Me2bpy)ZnH(L)][BArF4] (Me2bpy = 6,6'-dimethyl-2,2'-dipyridyl; ArF 3,5-(CF3)2C6H3; L THF, 1a; 4-(dimethylamino)pyridine, DMAP, 1b; pyridine, 1c; 4-(trifluoromethyl)pyridine, 1d) show Zn-H distances in the expected range, as exemplified by single-crystal X-ray diffraction for THF adduct 1a and pyridine 1c. With exception of labile 1a, ν(ZnH) stretching frequencies correlate with electron donating character ligand. The bond shows amphoteric behavior. Reaction ZnEt2 gives cationic ethyl complex [(Me2bpy)ZnEt(thf)][BArF4] (2a), while it undergoes CO2 insertion to form formato [(Me2bpy)Zn(OCHO)(thf)][BArF4] (3a). Thermolysis 3a at 80 °C dinuclear metalation product 4a, which is also formed photolysis 1a. acts a proton donor when treated N-heterocyclic carbene ItBu (ItBu 1,3-di-tert-butylimidazol-2-ylidene), giving imidazolium salt [ItBuH][BArF4], metal, Me2bpy. deprotonation occurs ZnCp*2 (Cp* pentamethylcyclopentadienyl) give dizinc(I) cation [(Me2bpy)Zn-ZnCp*(thf)][BArF4] (6a) Cp*H. Cp2MoH2 (Cp η5-cyclopentadienyl) leads heterobimetallic [(Me2bpy)Zn(μ-H)MoCp2]+[BArF4]- (7) under H2 elimination.

Language: Английский

Hypervalent Zinc(I) Complexes with an N,N,N,N-Macrocycle: C-H Bond Activation Across the Zinc(I)-Zinc(I) Bond

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(80), P. 11359 - 11362

Published: Jan. 1, 2024

Hetero- and homoleptic dinuclear zinc(I) complexes containing the macrocycle Me

Language: Английский