10.1021/acs.cgd.5b00282
The research aims to understand how the crystal structure of [HgBr2(L3,4?diCl)] is influenced by its single-component precursors [HgBr2(L3?Cl)] and [HgBr2(L4?Cl)], where L represents a N-(chlorinatedphenyl)-2-pyrazinecarboxamide ligand. The researchers found that the crystal packing of [HgBr2(L3,4?diCl)] retains the Cl···N and Cl···Br halogen bonding synthons reminiscent of the single components, demonstrating structural modularity based on halogen bonding interactions. This is the first report on structural modularity in coordination compounds and could be instrumental in inorganic crystal engineering, particularly in polymorphism and crystal structure prediction. The chemicals used in the process include 3-chloroaniline, 4-chloroaniline, 3,4-dichloroaniline, pyrazinecarboxylic acid, and HgBr2.
10.1021/jo902669j
The research explores the application of the photo-SN1 reaction on 4-chloroanilines under solar irradiation to develop a metal-free arylation method. The study aims to improve the environmental sustainability of arylations by using sunlight, more environmentally friendly solvents, and reducing the excess of trapping agents. The researchers optimized the reaction conditions using a solar simulator and then tested the reactions under direct sunlight. They found that the process could be scaled up to a gram scale with satisfactory yields, even with higher starting concentrations of halides and lower proportions of trapping agents. The study concludes that solar-induced photo-ArSN1 arylations are a viable and environmentally friendly alternative to traditional metal-catalyzed arylations, with the added benefit of being powered by renewable solar energy. 4-Chloro-N,N-dimethylaniline (1a) serves as the starting material for generating the 4-N,N-dimethylaminophenyl cation upon irradiation. Mesitylene (2a) acts as a p-trap in the reaction. R-Methylstyrene (2b) is another nucleophile used in the study. Allyltrimethylsilane (2c) serves as a nucleophile in the reaction.
10.1021/jo1024656
The research focuses on the synthesis and characterization of a hypervalent pentacoordinate boron compound featuring an N-B-N three-center four-electron bond. The experiments involved the preparation of a tridentate ligand precursor with two dimethylpyrimidine rings and the incorporation of a boron moiety. Key reactants included 4-chloroaniline, iodine, copper(II) bromide, t-butyl nitrite, and tin derivatives, among others. The synthesis process involved multiple steps, such as bromination, Stille coupling reactions, and lithiation, to ultimately obtain the boron compound with the tridentate ligand. Analyses used to characterize the compounds included X-ray crystallographic analyses, density functional theory (DFT) calculations, 1H NMR, 11B NMR, 13C NMR, and 119Sn NMR spectroscopy. These techniques were employed to determine the structural parameters, bond lengths, bond angles, and dihedral angles, as well as to estimate the bond energy of the N-B-N interaction and the energy contributions to the stability of the pentacoordinate versus tetracoordinate states. The study revealed that the conjugation energy difference was a crucial factor for shifting stability towards the pentacoordinate structure.
T，
N，
F
T:Toxic;
