Nucleophilic reactivity of a mononuclear cobalt(iii)–bis(tert-butylperoxo) complex

Abstract

<p>A mononuclear cobalt(III)–bis(tert-butylperoxo) adduct (CoIII–(OOtBu)2) bearing a tetraazamacrocyclic ligand was synthesized and characterized by various physicochemical methods, such as X-ray, UV-vis, ESI-MS, EPR, and NMR analyses. The crystal structure of...</p>

Electrocatalytic Atom Transfer Radical Addition with Turbocharged Organocopper(II) Complexes

“…Here, it is worth noting that the geometric constraints of the small 12-membered macrocyclic ring in L1 make an “ideal” trigonal bipyramidal geometry (β = 180° and α = 120°) impossible for any metal complex. The largest coordinate angle for all known L1 complexes is the trans N2–M–N4 angle (Figure numbering) of ∼165° in its Co III complex . All other metal ions exhibiting longer coordinate bonds (including Cu II ) enforce smaller coordinate angles for [Cu II (L1)­(NCMe)] 2+ (161.1°), [Cu II (L1)­Cl] + (153.8°), and [Cu II (L1)­Br] + (154.0°, both cations).…”

“…The largest coordinate angle for all known L1 complexes is the trans N2− M−N4 angle (Figure 1 numbering) of ∼165°in its Co III complex. 25 All other metal ions exhibiting longer coordinate bonds (including Cu II ) enforce smaller coordinate angles for [Cu II (L1)(NCMe)] 2+ (161.1°), [Cu II (L1)Cl] + (153.8°), and [Cu II (L1)Br] + (154.0°, both cations). This dictates τ 5 values much less than unity, as τ 5 is directly proportional to β.…”

Formation of cobalt–oxygen intermediates by dioxygen activation at a mononuclear nonheme cobalt(ii) center

“…It is worth noting that other metal-(hydro)alkylperoxide complexes have shown reactivities in both electrophilic and nucleophilic reactions. 58,[61][62][63][64][65][66][67][68][69][70]…”

A comprehensive insight into aldehyde deformylation: mechanistic implications from biology and chemistry

“…Please do not adjust margins Please do not adjust margins [Co III (OOtBu)2] bearing a tetraazamacrocyclic ligand. 184 The complex is capable of undergoing nucleophilic reaction efficiently.…”