6156-37-2Relevant articles and documents
Molecular and electronic structure of MM quadruply bonded complexes containing O2CC6H4N(Ph)2 supporting ligands
Chisholm, Malcolm H.,Durr, Christopher B.,Lewis, Sharlene A.
, p. 339 - 345 (2013)
The complexes trans-M2(TiPB)2(O 2CC6H4-4-NPh2)2 where M = Mo (I), and M = W (II) were prepared from the reaction between M 2(TiPB)4 and the carboxylic acid Ph 2N-4-C6H4CO2H (～2 equiv.) in toluene (TiPB = 2,4,6-triisopropylbenzoate). The compounds were isolated as microcrystalline powders that are yellow, I or purple II, and are air-sensitive. Compound I was characterized by single-crystal X-ray crystallography and shown to have a centrosymmetric structure and a planar central C6H4-CO2M2O 2C-C6H4 unit. Calculations indicate that the HOMO is principally M2δ with mixing of the filled π-orbitals of the N,N-diphenyl-4-aminobenzoate. Oxidation of I and II yield cationic species that have been characterized by EPR and UV-Vis-NIR spectroscopy. The radical cations show EPR spectra characteristic of M25+ centers having the MM configuration σ2π4δ 1 and compound I+ shows a low energy NIR transition assignable to a ligand to metal charge transfer transition. The homoleptic compound Mo2(O2CC6H4-4-N-Ph 2)4, III, was prepared from the reaction between Mo(CO)6 and Ph2N-4-C6H4CO 2H in refluxing ortho-dichlorobenzene and is shown to exhibit similar spectroscopic features to those of I.
Assembly and optical properties of 1D helical bundles induced by triphenylamine, side chains and solvents in crystals
Li, Baolin,Pang, Zhi,Qi, Ting
supporting information, p. 5555 - 5562 (2021/07/02)
Two novel helical aromatic foldamer derivativesTPA-Q6(n-He)andTPA-Q6(i-Bu)were synthesized and characterized by introducingn-hexyloxy and isobutoxy side chains, respectively, and modifying quinoline amide foldamers with the triphenyl
Ni-Catalyzed Carboxylation of C(sp2)-S Bonds with CO2: Evidence for the Multifaceted Role of Zn
Yanagi, Tomoyuki,Somerville, Rosie J.,Nogi, Keisuke,Martin, Ruben,Yorimitsu, Hideki
, p. 2117 - 2123 (2020/02/28)
Nickel-catalyzed reductive carboxylation reactions of aryl electrophiles typically require the use of metallic reducing agents. At present, the prevailing perception is that these serve as both a source of electrons and as a source of Lewis acids that may aid CO2 insertion into the Ni-C bond. Herein, we provide evidence for the in situ formation of organometallic species from the metallic reductant, a step that has either been ruled out or has been unexplored in catalytic carboxylation reactions with metal powder reductants. Specifically, we demonstrate that Zn(0) acts as a reductant and that Zn(II) generates arylzinc species that might play a role in the C(sp2)-S carboxylation of arylsulfonium salts. Overall, the reductive Ni-catalyzed C(sp2)-S carboxylation reaction proceeds under mild conditions in a non-amide solvent, displays a wide substrate scope, and can be applied to the formal para C-H carboxylation of arenes.
