2 research outputs found
“Criss-Crossed” Dinucleating Behavior of an N4 Schiff Base Ligand: Formation of a μ‑OH,μ‑O<sub>2</sub> Dicobalt(III) Core via O<sub>2</sub> Activation
No full textWe
report the synthesis and structural characterization of a dicobalt(III)
complex with a μ-OH,μ-O<sub>2</sub> core, namely μ-OH,μ-O<sub>2</sub>-[Co(enN4)]<sub>2</sub>(X)<sub>3</sub> [<b>1(ClO</b><sub><b>4</b></sub><b>)</b><sub><b>3</b></sub> and <b>1(BF</b><sub><b>4</b></sub><b>)</b><sub><b>3</b></sub>]. The dinuclear core is cross-linked by two N4 Schiff base
ligands that span each cobalt center. The formally Co<sup>III</sup>–Co<sup>III</sup> dimer is formed spontaneously upon exposure
of the mononuclear Co(II) complex to air and exhibits a ν(O–O)
value at 882 cm<sup>–1</sup> that shifts to 833 cm<sup>–1</sup> upon substitution with <sup>18</sup>O<sub>2</sub>. The CV of <b>1(BF</b><sub><b>4</b></sub><b>)</b><sub><b>3</b></sub> exhibits a reversible {Co<sup>III</sup>–Co<sup>III</sup>}↔{Co<sup>III</sup>–Co<sup>IV</sup>} redox process,
and we have investigated the oxidized {Co<sup>III</sup>–Co<sup>IV</sup>} species by EPR spectroscopy (<i>g</i> = 2.02,
2.06; <i>S</i> = 1/2 signal) and DFT calculations
“Criss-Crossed” Dinucleating Behavior of an N4 Schiff Base Ligand: Formation of a μ‑OH,μ‑O<sub>2</sub> Dicobalt(III) Core via O<sub>2</sub> Activation
No full textWe
report the synthesis and structural characterization of a dicobalt(III)
complex with a μ-OH,μ-O<sub>2</sub> core, namely μ-OH,μ-O<sub>2</sub>-[Co(enN4)]<sub>2</sub>(X)<sub>3</sub> [<b>1(ClO</b><sub><b>4</b></sub><b>)</b><sub><b>3</b></sub> and <b>1(BF</b><sub><b>4</b></sub><b>)</b><sub><b>3</b></sub>]. The dinuclear core is cross-linked by two N4 Schiff base
ligands that span each cobalt center. The formally Co<sup>III</sup>–Co<sup>III</sup> dimer is formed spontaneously upon exposure
of the mononuclear Co(II) complex to air and exhibits a ν(O–O)
value at 882 cm<sup>–1</sup> that shifts to 833 cm<sup>–1</sup> upon substitution with <sup>18</sup>O<sub>2</sub>. The CV of <b>1(BF</b><sub><b>4</b></sub><b>)</b><sub><b>3</b></sub> exhibits a reversible {Co<sup>III</sup>–Co<sup>III</sup>}↔{Co<sup>III</sup>–Co<sup>IV</sup>} redox process,
and we have investigated the oxidized {Co<sup>III</sup>–Co<sup>IV</sup>} species by EPR spectroscopy (<i>g</i> = 2.02,
2.06; <i>S</i> = 1/2 signal) and DFT calculations
