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• 作者：Pei Zhao ; Hao Lei ; Chengbao Ni ; Jing-Dong Guo ; Saeed Kamali ; James C. Fettinger ; Fernande Grandjean ; Gary J. Long ; Shigeru Nagase ; Philip P. Power
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：September 21, 2015
• 年：2015
• 卷：54
• 期：18
• 页码：8914-8922
• 全文大小：467K
• ISSN：1520-510X

文摘

The bis(渭-oxo) dimeric complexes {Ar^iPr₈OM(渭-O)}₂ (Ar^iPr₈ = C₆H-2,6-(C₆H₂-2,4,6-ⁱPr₃)₂-3,5-ⁱPr₂; M = Fe (1), Co (2)) were prepared by oxidation of the M(I) half-sandwich complexes {Ar^iPr₈M(畏⁶-arene)} (arene = benzene or toluene). Iron species 1 was prepared by reacting {Ar^iPr₈Fe(畏⁶-benzene)} with N₂O or O₂, and cobalt species 2 was prepared by reacting {Ar^iPr₈Co(畏⁶-toluene)} with O₂. Both 1 and 2 were characterized by X-ray crystallography, UV鈥搗is spectroscopy, magnetic measurements, and, in the case of 1, M枚ssbauer spectroscopy. The solid-state structures of both compounds reveal unique M₂(渭-O)₂ (M = Fe (1), Co(2)) cores with formally three-coordinate metal ions. The Fe路路路Fe separation in 1 bears a resemblance to that in the Fe₂(渭-O)₂ diamond core proposed for the methane monooxygenase intermediate Q. The structural differences between 1 and 2 are reflected in rather differing magnetic behavior. Compound 2 is thermally unstable, and its decomposition at room temperature resulted in the oxidation of the Ar^iPr₈ ligand via oxygen insertion and addition to the central aryl ring of the terphenyl ligand to produce the 5,5鈥?peroxy-bis[4,6-ⁱPr₂-3,7-bis(2,4,6-ⁱPr₃-phenyl)oxepin-2(5H)-one] (3). The structure of the oxidized terphenyl species is closely related to that of a key intermediate proposed for the oxidation of benzene.