The pentadentate ligands 2PyN2Q and N4Py, and their Cu(II) and Zn(II) complexes: A synthetic, spectroscopic and crystallographic structural study

Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)‐Oxo Complexes

“…As the Mn IV b 1 (d x 2 -y 2 ) acceptor MO is Mn-N4py σ-antibonding, the 4 E energy, and hence HAT and OAT reactivity, should be sensitive to perturbations in the equatorial ligand field. In this study, we test this model using new Mn IV -oxo complexes supported by electron-rich DMM N4py [10] and sterically encumbered 2pyN2Q [11] (Figure 2). These derivatives modulate the equatorial ligand field of the Mn IV center, influencing the 4 E energy, and leading to large rate variations.…”

Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)‐Oxo Complexes

“…As the Mn IV b1(dx 2 -y 2 ) acceptor MO is Mn-N4py -antibonding, the 4 E energy, and hence HAT and OAT reactivity, should be sensitive to perturbations in the equatorial ligand field. In this study, we test this model using new Mn IV -oxo complexes supported by electron-rich DMM N4py [10] and sterically encumbered 2pyN2Q [11] (Figure 2). These derivatives modulate the equatorial ligand field of the Mn IV center, influencing the 4 E energy, and leading to large rate variations.…”

Non-innocent ground state electronic structure of a polynuclear copper complex with picolinate bridges

“…[18]. This is compounded by the presence of an inner sphere coordinated anionic ligand in the latter.…”

“…Cu II/I couple was found to be chemically reversible at the potential of E 0 = +0.060 V. This value is very similar to that of 1, which may be explained by the dissociation of 2 in the presence of excess of (Bu 4 N)ClO 4 salt. In order to gain insights into the formation of 2, the oxidation and insertion of 2-pyridinecarboxaldehyde was followed by dioxygen uptake measurements using gas volumetry and 18 O labelling and concomitant ESI-MS and FTIR analysis. Figure 9).…”

“…Both complexes were characterized by single crystal X-ray crystallography (SCXRD), electrospray ionization mass spectrometry (ESI-MS), cyclic voltammetry (CV), ultraviolet-visible (UV-vis), and infrared spectroscopy (IR). Furthermore, 18 O labelled dioxygen uptake experiments were carried out to confirm O 2 insertion into complex 2.…”