TY - JOUR
T1 - 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
AU - Li, Chi Keung
AU - Che, Chi Ming
AU - Tong, Wai Fong
AU - Tang, Wai Tong
AU - Wong, Kwok Yin
AU - Lai, Ting Fong
PY - 1992/12/1
Y1 - 1992/12/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=37049067216&partnerID=8YFLogxK
U2 - 10.1039/DT9920002109
DO - 10.1039/DT9920002109
M3 - Journal article
SN - 1472-7773
SP - 2109
EP - 2116
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 13
ER -