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

Chi Keung Li, Chi Ming Che, Wai Fong Tong, Wai Tong Tang, Kwok Yin Wong, Ting Fong Lai

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Abstract

The complexes cis-[RuVILO2]2+, cis-[RuVLO2]+ and cis-[RuIIL(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-[RuVILO2]2+ are equivalent [1.795(9) Å] and the O-Ru-O angle is 112.0(4)°. In cis-[RuVLO2]+ the two Ru=O distances are 1.751(3) and 1.756(4) Å, and the O-Ru-O angle is 115.1(2)°. The N(MeCN)-Ru-N(MeCN) angle in cis-[RuIIL(MeCN)2]2+ is 86.1(2)°. The cyclic voltammogram of cis-[RuVILO2]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 oxidising a wide variety of organic substrates including 2,3-dimethylbutane and adamantane. Oxidation of saturated alkanes occurred preferentially at the tertiary C-H bond.
Original languageEnglish
Pages (from-to)2109-2116
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number13
DOIs
Publication statusPublished - 1 Dec 1992
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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