Meso- and macrocyclic polydentate amine ligands have been widely explored in oxidation catalysis and for the stabilization of unstable metal-superoxide, -peroxide, and -oxo intermediates. Herein we report on the design and synthesis of a novel mesocyclic, tripodal, triamine ligand that we believe will be an excellent addition to this field. We explored a number of synthetic procedures towards t...

The synthesis, X-ray structures and photophysics of ten complexes of CuX (X = I or Br) with bridging N-substituted and N,N'-disubstituted piperazines (Pip) are presented. Depending on the steric demand of the Pip substituents, the complexes fall into four categories: (CuX)(4)(Pip)(2), which are networks of linked Cu(4)X(4) cubane units, (CuX)(2)(Pip), which are chains of linked Cu(2)X(2) rhombs...

Understanding the properties of synthetic copper-oxygen intermediates is important for evaluating mechanisms of oxidations by enzymes and other catalysts.1,2 A growing class of reactive copper-oxygen complexes have been isolated or identified spectroscopically to date, including well-studied examples with [Cu2(O2)], [Cu2(μ-O)2], or [CuO2] cores.3 Mononuclear copperoxo species ([CuII-O-• T CuIII...

Two copper(I)–NHC complexes bearing an azide group were reacted with alkyne-decorated magnetic Fe3O4 nanoparticles without the use of external copper source. In case least sterically congested complex, resulting displayed a catalytic activity in copper-catalyzed alkyne cycloaddition and some reusability highlighting covalent grafting molecular catalyst by this mild simple strategy.

Three new neutral di-ferrocenyl-ethynylpyridinyl copper complexes, [L2(CuCl)2(PPh3)2] (), [L2(CuBr)2(PPh3)2] (), and [L2(CuI)2(PPh3)2] () were synthesized from the ferrocenyl-ethynylpyridine ligand (L) (), the appropriate copper halide CuX (with X = Cl(-), Br(-), I(-)) and triphenylphosphine. These neutral complexes were fully characterized by spectroscopic methods and by single crystal X-ray c...

A facile large-scale synthesis of the “push–pull”-substituted ligand bis(diethylamino)(pentafluorophenyl)phosphane is reported. A selenophosphorane as well as complexes with CuI and PdCl2, can be formed almost quantitatively from suitable starting materials. The PdII complex shows a square-planar coordination with significant distortions of the Cl–Pd–Cl moiety in the solid state. In contrast, t...

The reaction mechanism of Cu-catalyzed C-H hydroxylation/C-S coupling was studied using electrospray ionization high resolution mass spectrometry (ESI-HR MS) and density functional theory calculations (DFT). Notably, a series of CuI and CuIII complexes were observed as key intermediates and identified using ESI-HR MS. Furthermore, a catalyst cycle involving proton abstraction/oxidative addition...