The First μ₆‐Peroxide Transition‐Metal Complex: [Ni₈(L)₁₂(O₂)]²⁺

Abstract

Caged peroxide: An octanuclear nickel complex, which exhibits peroxide in an unprecedented μ6‐(η1)3 coordination mode, was prepared (see structure: only the Ni8 unit with the central peroxo ligand and the bridging oxygen atoms is shown; green Ni, red O). This mode of binding finally completes the series of symmetrical μn‐(η1)n/2 peroxide binding modes in complexes.

Metal–dioxygen and metal–dinitrogen complexes: where are the electrons?

“…xxvi There are fewer examples of a single molecule of N 2 binding to more than two transition metals, but one especially notable one is a hydrazine-derived Au 6 complex. xxvii There are also examples of end-on binding of N 2 to transition metals concomitant with side-on binding to alkali metals.…”

“…23 There are also some examples of O 2 binding between more than two transition metals, including tetracopper 24 and tetrairon 25 complexes and a hexanickel complex. 26 There are fewer examples of a single molecule of N 2 binding to more than two transition metals, but one especially notable one is a hydrazine-derived Au 6 complex. 27 There are also examples of end-on binding of N 2 to transition metals concomitant with side-on binding to alkali metals.…”

Probing secondary coordination sphere influence on the oxygenation of zinc alkyls: formation of a unique zinc peroxide species

“…10 Interestingly, the unique central core of 3 resembles that observed for the octanuclear nickel cluster with entrapped peroxide species, [Ni 8 (L) 12 (O 2 )] 2+ (L = N-substituted 3-hydroxy-2-pyridinonate; the latter cluster was synthesized from an inorganic nickel salt and an aqueous solution of H 2 O 2 ). 11 Thus, the course of the metal-p-assisted oxygenation of zinc alkyls differs significantly from those of other organozinc systems systematically studied previously, in which formation of ZnOOR or ZnOR species was commonly observed. 12 The following question therefore arises: where have all the ethyl and/or ethoxy radicals gone?…”

Ein Side‐on‐Superoxonickel‐Komplex [LNi(O2)] mit quadratisch‐ planarem, vierfach koordinierten Nickel(II)‐Zentrum und seine Umwandlung in [LNi(μ‐OH)2NiL]

“…Da Ni II -Komplexe im Allgemeinen inert gegen O 2 sind, ist der am weitesten verbreitete Ansatz die Reaktion von H 2 O 2 mit Nickel(II)-Salzen zu Hydroperoxo-und Peroxokomplexen. [6] Eine vielversprechende Alternative für die Synthese von {NiO 2 }-Peroxokomplexen bietet die Zweielektronenreduktion von O 2 durch Nickel(0)-Komplexe. [7] [11] ergab, dass der Komplex einen beinahe planaren {C 3 N 2 Ni}-Sechsring enthält.…”