Activation of dioxygen molecules on dinuclear metal centers

Proceedings / Indian Academy of Sciences - Tập 111 - Trang 413-424 - 1999
Yoshihiko Moro-Oka1
1Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Yokohama, Japan

Tóm tắt

Activation of dioxygen molecules on transition metal centers, especially dinuclear metal centers was systematically investigated using hydrotris(3,5-dialkylpyrazolyl)borate ligands from both organometallic and bioinorganic viewpoints. Physicochemical data and X-ray crystallography of synthesized dicopper-O2 complexes revealed aμ-η 2:η 2 coordination mode which was proposed as the most probable model ofoxyhemocyanin. Dioxygen species bound to dinuclear cobalt and nickel centers are quite active and react rapidly with C-H groups in ligands giving oxygenated products even at room temperature. The stability of (μ-η 2:η 2-O2)M2 complexes depends on the electron-donating ability of the central metal atoms and the difference arises mainly from the extent of back donation to the antibonding O-O orbital.

Tài liệu tham khảo

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