35895-70-6Relevant articles and documents
Calcium-Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Cores
Ertem, Mehmed Z.,Harland, Jill B.,Lehnert, Nicolai,Musselman, Bradley W.,Robinson, Jerome R.,Vargo, Natasha P.
, (2021)
Coupled dinuclear copper oxygen cores (Cu2O2) featured in type III copper proteins (hemocyanin, tyrosinase, catechol oxidase) are vital for O2 transport and substrate oxidation in many organisms. μ-1,2-cis peroxido dicoppe
Lewis Acidity Scale of Diaryliodonium Ions toward Oxygen, Nitrogen, and Halogen Lewis Bases
Legault, Claude Y.,Mayer, Robert J.,Mayr, Herbert,Ofial, Armin R.
supporting information, (2020/03/13)
Equilibrium constants for the associations of 17 diaryliodonium salts Ar2I+X- with 11 different Lewis bases (halide ions, carboxylates, p-nitrophenolate, amines, and tris(p-anisyl)phosphine) have been investigated by titrations followed by photometric or conductometric methods as well as by isothermal titration calorimetry (ITC) in acetonitrile at 20 °C. The resulting set of equilibrium constants KI covers 6 orders of magnitude and can be expressed by the linear free-energy relationship lg KI = sI LAI + LBI, which characterizes iodonium ions by the Lewis acidity parameter LAI, as well as the iodonium-specific affinities of Lewis bases by the Lewis basicity parameter LBI and the susceptibility sI. Least squares minimization with the definition LAI = 0 for Ph2I+ and sI = 1.00 for the benzoate ion provides Lewis acidities LAI for 17 iodonium ions and Lewis basicities LBI and sI for 10 Lewis bases. The lack of a general correlation between the Lewis basicities LBI (with respect to Ar2I+) and LB (with respect to Ar2CH+) indicates that different factors control the thermodynamics of Lewis adduct formation for iodonium ions and carbenium ions. Analysis of temperature-dependent equilibrium measurements as well as ITC experiments reveal a large entropic contribution to the observed Gibbs reaction energies for the Lewis adduct formations from iodonium ions and Lewis bases originating from solvation effects. The kinetics of the benzoate transfer from the bis(4-dimethylamino)-substituted benzhydryl benzoate Ar2CH-OBz to the phenyl(perfluorophenyl)iodonium ion was found to follow a first-order rate law. The first-order rate constant kobs was not affected by the concentration of Ph(C6F5)I+ indicating that the benzoate release from Ar2CH-OBz proceeds via an unassisted SN1-type mechanism followed by interception of the released benzoate ions by Ph(C6F5)I+ ions.
Atom transfer radical addition (ATRA) catalyzed by copper complexes with N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) ligand
Kaur, Aman,Gorse, Erin E.,Ribelli, Thomas G.,Jerman, Callista C.,Pintauer, Tomislav
, p. 246 - 252 (2015/03/04)
Synthesis, characterization, electrochemical studies and ATRA activity of copper complexes with N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) ligand in the presence of ascorbic acid as a reducing agent were reported. [CuII(TPEN′)Br][Br] (TPEN′ denotes tetracoordinated ligand) catalyst showed a very low activity in ATRA of CBr4 to 1-octene, methyl methacrylate, methyl acrylate and styrene in methanol, which is a typical solvent used for ATRA reactions employing ascorbic acid. On the contrary, the yields and stereoselectivity towards monoadduct formation were dramatically increased in slightly polar but aprotic acetone. Based on molecular structures of isolated [CuII(TPEN)][BPh4] and [CuII(TPEN′)Br][Br] complexes, as well as UV-Vis and cyclic voltammetry studies, an equilibrium was proposed involving inactive [CuII(TPEN)]2+ and ATRP active [CuII(TPEN′)Br]+ cations The halidophilicity of the bromide-based deactivating complex ([CuII(TPEN′)Br][Br]) decreased approximately 750 times upon changing the solvent from acetone (KBr = 3000 ± 230) to methanol (KBr = 4.1 ± 0.1), explaining poor catalytic activity in methanol. In acetone, [CuII(TPEN′)Br][Br] complex was nearly as active in ATRA reactions employing ascorbic acid as previously reported [CuII(TPMA)Br][Br].
