Synthesis, structural, and spectroscopic characterization and reactivities of mononuclear cobalt(III)-peroxo complexes.
Metal-dioxygen adducts are key intermediates detected in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. In this study, mononuclear cobalt(III)-peroxo complexes bearing tetraazamacrocyclic ligands, [Co(12-TMC)(O(2))](+) and [Co(13-TMC)(O(2))](+), were synthesized by reacting [Co(12-TMC)(CH(3)CN)](2+) and [Co(13-TMC)(CH(3)CN)](2+), respectively, with H(2)O(2) in the presence of triethylamine. The mononuclear cobalt(III)-peroxo intermediates were isolated and characterized by various spectroscopic techniques and X-ray crystallography, and the structural and spectroscopic characterization demonstrated unambiguously that the peroxo ligand is bound in a side-on η(2) fashion. The O-O bond stretching frequency of [Co(12-TMC)(O(2))](+) and [Co(13-TMC)(O(2))](+) was determined to be 902 cm(-1) by resonance Raman spectroscopy. The structural properties of the CoO(2) core in both complexes are nearly identical; the O-O bond distances of [Co(12-TMC)(O(2))](+) and [Co(13-TMC)(O(2))](+) were 1.4389(17) Å and 1.438(6) Å, respectively. The cobalt(III)-peroxo complexes showed reactivities in the oxidation of aldehydes and O(2)-transfer reactions. In the aldehyde oxidation reactions, the nucleophilic reactivity of the cobalt-peroxo complexes was significantly dependent on the ring size of the macrocyclic ligands, with the reactivity of [Co(13-TMC)(O(2))](+) > [Co(12-TMC)(O(2))](+). In the O(2)-transfer reactions, the cobalt(III)-peroxo complexes transferred the bound peroxo group to a manganese(II) complex, affording the corresponding cobalt(II) and manganese(III)-peroxo complexes. The reactivity of the cobalt-peroxo complexes in O(2)-transfer was also significantly dependent on the ring size of tetraazamacrocycles, and the reactivity order in the O(2)-transfer reactions was the same as that observed in the aldehyde oxidation reactions.
Department of Bioinspired Science, Center for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea.
Jaeheung
J
Cho
Ritimukta
R
Sarangi
Hye Yeon
HY
Kang
Jung Yoon
JY
Lee
Minoru
M
Kubo
Takashi
T
Ogura
Edward I
EI
Solomon
Wonwoo
W
Nam
D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D047028:Macrocyclic Compounds / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D011789:Quantum Theory; D013057:Spectrum Analysis
D008024:Ligands; D047028:Macrocyclic Compounds; D009942:Organometallic Compounds; D003035:Cobalt; D010100:Oxygen