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Synthesis, Structure, Reactivity and Electrochemistry of cis-Dioxoruthenium-(VI) and -(V) Complexes containing N,N,N',N',3,6-Hexamethyl-3,6-diazaoctane-1,8-diamine

DOI: 10.1039/DT9920002109

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2109 - 2116 (1992)

Update date:2022-08-11

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Authors:

Li, Chi-KeungLi, Chi-Keung

Che, Chi-MingChe, Chi-Ming

Tong, Wai-FongTong, Wai-Fong

Tang, Wai-TongTang, Wai-Tong

Wong, Kwok-YinWong, Kwok-Yin

Lai, Ting-FongLai, Ting-Fong

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Article abstract of DOI:10.1039/DT9920002109

The complexes cis-VILO2>2+, cis-VLO2>+ and cis-IIL(MeCN)2>2+ (L = N,N,N',N',3,6-hexamethyl-3,6-diazaoctane-1,8-diamine) have been prepared and their structures determined.The two Ru=O bonds in cis-VILO2>2+ are equivalent <1.795(9) Angstroem> and the O-Ru-O angle is 112.0(4) deg.In cis-VLO2>+ the two Ru=O distances are 1.751(3) and 1.756(4) Angstroem, and the O-Ru-O angle is 115.1(2) deg.The N(MeCN)-Ru-N(MeCN) angle in cis-IIL(MeCN)2>2+ is 86.1(2) deg.The cyclic voltammogram of cis-VILO2>2+ in acetonitrile exhibits a reversible one-electron RuVI-RuV couple at 0.53 V vs.Ag-AgNO3 (0.1 mol dm-3).In aqueous solutions, proton-coupled electron-transfer redox couples are observed.This complex is capable of oxidizing a wide variety of organic substrates including 2,3-dimethylbutane and adamantane.Oxidation of saturated alkanes occured preferentially at the tertiary C-H bond.

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