Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 26, 2019
Previous Article Next Article

Structure and reactivity of the first-row d-block metal-superoxo complexes

Author affiliations

Abstract

In the first-row of d-block metals, ten elements are included, such as scandium (Sc, 3d1), titanium (Ti, 3d2), vanadium (V, 3d3), chromium (Cr, 3d54s1), manganese (Mn, 3d5), iron (Fe, 3d6), cobalt (Co, 3d7), nickel (Ni, 3d8), copper (Cu, 3d104s1) and zinc (Zn, 3d10). The synthesis, characterization, and reactivity of first-row d-block metal-superoxo complexes are discussed together with the structures of the end-on (η1) and side-on (η2) metal-superoxo complexes in this review article. Electron transfer from electron donors to O2 is enhanced by binding of Sc3+ to produce an end-on type Sc(III)-superoxo complex. Metal-superoxo complexes such as Ti(IV)-superoxo, oxovanadium(V)-superoxo, Cr(III)-superoxo, Fe(III)-superoxo, Co(III)-superoxo, Ni(III)-superoxo and Cu(II)-superoxo species generally undergo hydrogen atom transfer reactions. A Cr(III)-superoxo complex undergoes not only hydrogen atom transfer but also oxygen atom transfer reactions. In the presence of protons (e.g., trifluoromethanesulfonic acid, HOTf), much enhanced acid catalysis was observed in oxygen atom transfer reactions from a nonheme Cr(III)-superoxo complex, [(Cl)(TMC)CrIII(O2)]+, to thioanisole. The enhanced reactivity of [(Cl)(TMC)CrIII(O2)]+ by HOTf results from proton-coupled electron transfer (PCET) from electron donors, including thioanisole, to [(Cl)(TMC)CrIII(O2)]+. A manganese(IV)-superoxo complex plays a very important role in thermal and photoinduced dioxygen activation by a Mn(III) corrolazine complex. A metal-superoxide complex using the last element in the first-row of transition metals, that is a Zn(II)-superoxide complex, is produced to accelerate the reduction of O2˙ in a SOD (superoxide dismutase) model.

Graphical abstract: Structure and reactivity of the first-row d-block metal-superoxo complexes

Back to tab navigation

Article information


Submitted
02 Apr 2019
Accepted
01 May 2019
First published
01 May 2019

Dalton Trans., 2019,48, 9469-9489
Article type
Perspective

Structure and reactivity of the first-row d-block metal-superoxo complexes

S. Fukuzumi, Y. Lee and W. Nam, Dalton Trans., 2019, 48, 9469
DOI: 10.1039/C9DT01402K

Social activity

Search articles by author

Spotlight

Advertisements