1015228-11-1Relevant articles and documents
Reductive bromination of N, N-bis(4-tert-butylphenyl)hydroxylamine
Golubev,Kim, Yu. D.
, p. 1293 - 1297 (2019)
Unlike most arenes, N, N-bis(4-tert-butylphenyl)hydroxylamine reacts with Br2via the reductive bromination mechanism. Here, two hydrogens in ortho positions of benzene rings are substituted by Br2 and provide two-electron reduction o
Oxidation and reductive bromination of Bis(4-tert-butylphenyl)aminoxyl
Golubev,Sen'
, p. 1143 - 1149 (2013/10/01)
One-electron oxidation of bis(4-tert-butylphenyl)aminoxyl with antimony pentachloride and bromine leads to the formation of oxoammonium salts with anions SbCl 6 - and Br 3 - respectively. The salt with the Br 3 - anion converted at heating into a mixture of bromodiphenylamines which formed also from the aminoxyl as a result of previously unknown reaction of three-electron reductive bromination. The mechanisms of these reactions were assumed.
Design, testing and kinetic analysis of bulky monodentate phosphorus ligands in the mizoroki-heck reaction
Dodds, Deborah L.,Boele, Maarten D.K.,Van Strijdonck, Gino P.F.,De Vries, Johannes G.,Van Leeuwen, Piet W.N.M.,Kamer, Paul C. J.
experimental part, p. 1660 - 1671 (2012/05/19)
A series of new monodentate phosphane ligands 2 have been evaluated in the Mizoroki-Heck arylation reaction of iodobenzene and styrene and compared with our previously reported ligands, 1, 3 and 4. The concept of rational ligand design is discussed, and we describe how the performance of this new ligand family could be predicted. Employing our best ligand, 3,3'-di-tert-butyl-5,5'- dimethoxybiphenyl-2,2'-diyl diisopropylphosphoramidite (3b), we explored the scope of the reaction with regards to solvent and the substrate. We also investigated the electronic dependence of the reaction by analysing the relationship between the rate and Hammett constant. Sufficient steric bulk is required to enforce the catalytic reaction to proceed through the mono-coordinated palladium species, thereby increasing its reactivity. The electronic properties determine the concentration of the active species from the monomer dimer equilibrium and their intrinsic reactivity. The cyclic phosphoramidite 3b provides an optimum in both properties within the systems studied, resulting in a rate limiting migratory insertion step. Copyright
Probing the electronic structures of [CU2(μ-XR 2)]n+ diamond cores as a function of the bridging X atom (X = N or P) and charge (n = 0, 1, 2)
Harkins, Seth B.,Mankad, Neal P.,Miller, Alexander J. M.,Szilagyi, Robert K.,Peters, Jonas C.
, p. 3478 - 3485 (2008/09/20)
A series of dicopper diamond core complexes that can be isolated in three different oxidation states ([Cu2(μ-XR2)]n+, where n = 0, 1, 2 and X = N or P) is described. Of particular interest is the relative degree of oxidation of the respective copper centers and the bridging XR2 units, upon successive oxidations. These dicopper complexes feature terminal phosphine and either bridging amido or phosphido donors, and as such their metal-ligand bonds are highly covalent. Cu K-edge, Cu L-edge, and P K-edge spectroscopies, in combination with solid-state X-ray structures and DFT calculations, provides a complementary electronic structure picture for the entire set of complexes that tracks the involvement of a majority of ligand-based redox chemistry. The electronic structure picture that emerges for these inorganic dicopper diamond cores shares similarities with the Cu 2(μ-SR)2 CuA sites of cytochrome c oxidases and nitrous oxide reductases.
