We found a match
Your institution may have rights to this item. Sign in to continue.
- Title
Geometric and electronic structure and reactivity of a mononuclear ‘side-on’ nickel(iii)–peroxo complex.
- Authors
Jaeheung Cho; Sarangi, Ritimukta; Annaraj, Jamespandi; Sung Yeon Kim; Kubo, Minoru; Ogura, Takashi; Solomon, Edward I.; Wonwoo Nam
- Abstract
Metal-dioxygen adducts, such as metal-superoxo and -peroxo species, are key intermediates often detected in the catalytic cycles of dioxygen activation by metalloenzymes and biomimetic compounds. The synthesis and spectroscopic characterization of an end-on nickel(II)-superoxo complex with a 14-membered macrocyclic ligand was reported previously. Here we report the isolation, spectroscopic characterization, and high-resolution crystal structure of a mononuclear side-on nickel(III)-peroxo complex with a 12-membered macrocyclic ligand, [Ni(12-TMC)(O2)]+ (1) (12-TMC = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). In contrast to the end-on nickel(II)-superoxo complex, the nickel(III)-peroxo complex is not reactive in electrophilic reactions, but is capable of conducting nucleophilic reactions. The nickel(III)-peroxo complex transfers the bound dioxygen to manganese(II) complexes, thus affording the corresponding nickel(II) and manganese(III)-peroxo complexes. Our results demonstrate the significance of supporting ligands in tuning the geometric and electronic structures and reactivities of metal–O2 intermediates that have been shown to have biological as well as synthetic usefulness in biomimetic reactions.
- Subjects
ELECTRONIC structure; REACTIVITY (Chemistry); SPECTROSCOPIC imaging; BIOMIMETIC chemicals; NICKEL; LIGANDS (Chemistry); NUCLEOPHILIC reactions; MANGANESE; OXYGEN
- Publication
Nature Chemistry, 2009, Vol 1, Issue 7, p568
- ISSN
1755-4330
- Publication type
Article
- DOI
10.1038/nchem.366