Xn:Harmful;95-94-3Relevant articles and documents
Facile Synthesis of a Fully Fused, Three-Dimensional ?-Conjugated Archimedean Cage with Magnetically Shielded Cavity
Han, Yi,Jiao, Tianyu,Li, Zhengtao,Ni, Yong,Wu, Jishan,Wu, Shaofei,Zhang, Qiuyu,Zhu, Jun
supporting information, p. 14314 - 14321 (2021/09/13)
The synthesis of molecular cages consisting of fully fused, ?-conjugated rings is rare due to synthetic challenges including preorganization, large strain, and poor solubility. Herein, we report such an example in which a tris-2-aminobenzophenone precursor undergoes acid-mediated self-condensation to form a truncated tetrahedron, one of the 13 Archimedean solids. Formation of eight-membered [1,5]diazocine rings provides preorganization and releases the strain while still maintains weak ?-conjugation of the backbone. Thorough characterizations were performed by X-ray, NMR, and UV-vis analysis, assisted by theoretical calculations. The cage exhibits a rigid backbone structure with a well-defined cavity that confines a magnetically shielded environment. The solvent molecule, o-dichlorobenzene, is precisely encapsulated in the cavity at a 1:1 ratio with multiple ?···?, C-H···?, and halogen···πinteractions with the cage skeleton, implying its template effect for the cage closing reaction. Our synthetic strategy opens the opportunity to access more complex, fully fused, three-dimensional ?-conjugated cages.
Selective C-F/C-H bond activation of fluoroarenes by cobalt complex supported with phosphine ligands
Li, Junye,Zheng, Tingting,Sun, Hongjian,Xu, Wengang,Li, Xiaoyan
, p. 5740 - 5748 (2013/07/11)
The reactions of pentafluoropyridine C5NF5, hexafluorobenzene C6F6, and perfluoronaphthalene C 10F8 with cobalt(0) complex, Co(PMe3) 4, were investigated. The Co(i) complexes (4-C5NF 4)Co(PMe3)3 (1), (C6F 5)Co(PMe3)3 (2), (C10F 7)Co(PMe3)3 (3), (4-C5NF 4)Co(PMe3)4 (4) and (C10F 7)Co(PMe3)4 (6) were obtained by selective activation of the C-F bonds. The reactions of 1 and 2 with CO afforded dicarbonyl cobalt(i) complexes (4-C5NF4)Co(CO) 2(PMe3)2 (7), (C6F 5)Co(CO)2(PMe3)2 (8). Under similar reaction conditions, 2 as a C-H bond activation product was obtained from the reaction of pentafluorobenzene, C6F5H, with Co(PMe 3)4. The byproducts, hydrodefluorination product 1,2,4,5-C6F4H2 and F2PMe3 from the reaction of C6F5H and Co(PMe3) 4 were also observed. The reaction mechanism of C6F 5H with Co(PMe3)4 is proposed and partly-experimentally verified. The reaction of C6F5H with Co(PMe3)4 under 1 bar of CO at room temperature afforded hydrido dicarbonyl cobalt(ii) complex (C6F5)Co(H)(CO) 2(PMe3)2 (11). Treatment of the mixtures of C6F5H/Co(PMe3)4 with hexachlorobenzene, C6Cl6, resulted in (C6F 5)CoCl(PMe3)3 (12) via C-H bond cleavage with the hydrodechlorination product pentachlorobenzene, C6Cl 5H, and 1,2,4,5-tetrachlorobenzene, C6Cl4H 2. The structures of complexes 1, 2, 6, 7, 8, 11 and 12 were determined by X-ray diffraction.
New look into the synthesis of polyhalogenoarylphosphanes
Nycz, Jacek E.
experimental part, p. 2605 - 2612 (2010/08/06)
The present study shows new aspects of the synthesis of polyhalogenoarylphosphanes. The sterically hindered anions Ph(R)P-Y- (1a-c, Y = O, lone pair; R = Ph, But) have been used to show the complexity of the reaction between phosphorus nucleophiles and hexahalogenobenzenes or 9-bromofluorene (E3). The Ph(But)P-O-(1a) anion reacts with hexachlorobenzene (E1), hexafluorobenzene (E2), or E3 to give Ph(R)P(O)X (4a-c, X = F, Cl, Br) with the release of the corresponding carbanion as a nucleofuge, followed by side reactions. In contrast, the lithium phosphides Ph(R)PLi (1b,c) react with hexahalogenobenzenes to give the corresponding diphosphanes 5a,b as the main product and traces of P-arylated products, i.e., Ph(R)P-C6X 5 (10a,b, X = Cl, F). Unexpectedly, Ph(But)PLi (1b) reacts with an excess of 9-bromofluorene to give only halogenophosphane Ph(Bu t)P-X. Taylor & Francis Group, LLC.
