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Geometric and electronic structure and reactivity of a mononuclear "side-on" nickel(III)-peroxo complex.

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)(O(2))](+) (1) (12-TMC = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane). Different from the end-on Ni(II)-superoxo complex, the Ni(III)-peroxo complex is not reactive in electrophilic reactions, but is capable of conducting nucleophilic reactions. The Ni(III)-peroxo complex transfers the bound dioxygen to manganese(II) complexes, thus affording the corresponding nickel(II) and manganese(III)-peroxo complexes. The present results demonstrate the significance of supporting ligands in tuning the geometric and electronic structures and reactivities of metal-O(2) intermediates that have been shown to have biological as well as synthetic usefulness in biomimetic reactions.

SUBMITTER: Cho J

PROVIDER: S-EPMC2920495 | biostudies-literature | 2009 Oct

REPOSITORIES: biostudies-literature

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Geometric and electronic structure and reactivity of a mononuclear "side-on" nickel(III)-peroxo complex.

Cho Jaeheung J Sarangi Ritimukta R Annaraj Jamespandi J Kim Sung Yeon SY Kubo Minoru M Ogura Takashi T Solomon Edward I EI Nam Wonwoo W

Nature chemistry 20091001 7

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 ...[more]

PMID: 20711413

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Project description:Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating reactivities of oxygen-containing metal complexes in a variety of biological and biomimetic reactions, including dioxygen activation/formation and functionalization of organic substrates. Mononuclear nonheme iron(III)-peroxo species are invoked as active oxygen intermediates in the catalytic cycles of dioxygen activation by nonheme iron enzymes and their biomimetic compounds. Here, we report mononuclear nonheme iron(III)-peroxo complexes binding redox-inactive metal ions, [(TMC)FeIII(O2)]+-M3+ (M3+ = Sc3+ and Y3+; TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), which are characterized spectroscopically as a 'side-on' iron(III)-peroxo complex binding a redox-inactive metal ion, (TMC)FeIII-(?,?2:?2-O2)-M3+ (2-M). While an iron(III)-peroxo complex, [(TMC)FeIII(O2)]+, does not react with electron donors (e.g., ferrocene), one-electron reduction of the iron(III)-peroxo complexes binding redox-inactive metal ions occurs readily upon addition of electron donors, resulting in the generation of an iron(IV)-oxo complex, [(TMC)FeIV(O)]2+ (4), via heterolytic O-O bond cleavage of the peroxide ligand. The rates of the conversion of 2-M to 4 are found to depend on the Lewis acidity of the redox-inactive metal ions and the oxidation potential of the electron donors. We have also determined the fundamental electron-transfer properties of 2-M, such as the reduction potential and the reorganization energy in electron-transfer reaction. Based on the results presented herein, we have proposed a mechanism for the reactions of 2-M and electron donors; the reduction of 2-M to the reduced species, (TMC)FeII-(O2)-M3+ (2'-M), is the rate-determining step, followed by heterolytic O-O bond cleavage of the reduced species to form 4. The present results provide a biomimetic example demonstrating that redox-inactive metal ions bound to an iron(III)-peroxo intermediate play a significant role in activating the peroxide O-O bond to form a high-valent iron(IV)-oxo species.

Project description:The study is aimed at a deeper understanding of the electronic structure of the T-shaped nickel(i) complex [LigiPr(iso)Ni] (1b), bearing the iso-PyrrMeBox (bis(oxazolinylmethylidene)pyrrolidinido) pincer ligand, and its CO adduct [LigiPr(iso)Ni(CO)] (2b) as well as to provide insight into the mechanism of autoxidation of the different nickel peroxo species of this ligand type. CO was found to react reversibly with complex 1b resulting in the corresponding CO adduct 2b. The EPR data as well as the results of DFT modeling revealed significant differences in the electronic structure of 1b and 2b. Reaction of [LigPh(iso)Ni] and [LigiPr(iso)Ni] (1a and b) with dioxygen yielded the 1,2-μ-peroxo complexes [Lig(iso)NiO]23a and b which reacted with hydrogen peroxide to give the hydroperoxo complexes [Lig(iso)NiOOH] 5a and b. Thermal aerobic decomposition of the peroxo species 3a and 5a in the presence of O2 led to a C-H activation of the ligand at the benzylic position of the oxazoline ring forming diastereomeric cyclic peroxo complexes 6 and 6'. For the 1,2-μ-peroxo complex 3b the autoxidation of the pincer in the absence of O2 occurred at the tertiary C-H bond of the iPr-group and led to a selective formation of the terminal hydroxo complex [LigiPr(iso)NiOH] 7b and the cyclic alkoxy complex 8 in equimolar quantities, while the corresponding cyclic peroxo species 9 was formed along with 7b in the presence of oxygen. Whether or not O-O bond cleavage occurred in the generation of 9 was established upon performing labeling experiments which indicate that the transformation does not involve an initial O-O bond cleaving step. Based on these observations and a series of stoichiometric transformations a tentative proposal for the processes involved in the anaerobic and aerobic decomposition of 3b has been put forward. Finally, the nickel(ii) methyl complex [LigPh(iso)NiMe] 14 reacted with O2 to give the methylperoxo complex [LigPh(iso)NiOOMe] 15 which slowly converted to a mixture of near equal amounts of the formato and the hydroxo complexes, [LigPh(iso)NiOOCH] 16 and [LigPh(iso)NiOH] 7a, along with half an equivalent of methanol. The formato complex 16 itself decomposed at elevated temperatures to CO2, dihydrogen as well as the nickel(i) species 1a.

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Geometric and electronic structure and reactivity of a mononuclear "side-on" nickel(III)-peroxo complex.

Publications

Geometric and electronic structure and reactivity of a mononuclear "side-on" nickel(III)-peroxo complex.

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