Notes. High-valent Ruthenium Oxo Complexes of NNN'N'-Tetramethyl-3,6-dimethyl-3,6-diazaoctane-1,8-diamine (L1). X-Ray Crystal Structure Determination of cis-III(L1)Cl2>ClO4
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Source and publish data:
Journal of the Chemical Society, Dalton Transactions p. 2885 - 2888 (1988)
Update date:2022-08-11
Topics:
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Authors:
Che, Chi-Ming
Tang, Wai-Tong
Lam, Michael Hon-Wah
Mak, Thomas C. W.
Article abstract of DOI:10.1039/DT9880002885
The reaction of K2 with NNN'N'-tetramethyl-3,6-dimethyl-3,6-diazaoctane-1,8-diamine (L1) in ethanol yielded cis-III(L1)Cl2>(1+), which was isolated as the ClO4(1-) salt.The optical spectrum of cis-III(L1)Cl2>ClO4 in acetonitrile displays one intense band at 375 nm attributed to a p?(Cl) <*> d?*(Ru) transition. cis-III(L1)Cl2>ClO4 has been characterized by X-ray crystallography: space group P21/c, a = 11.716(5), b = 13.089(4), c = 12.981(5) Angstroem, β=94.28(2) deg, Z = 4, and R = 0.076 for 1913 observed Mo-Kα data.The co-ordination geometry around the metal ion is distorted octahedral with cis arrangement of the two chloride ligands.The average Ru-N and Ru-Cl bond distances are 2.17(1) and 2.345(4) Anstroem, respectively.Treatment of cis-III(L1)Cl2>ClO4 with silver(I)p-toluenesulphonate in hot water and then H2O2 gave VI(L1)(O)2>(2+) isolated as the ClO4(1-) salt. VI(L1)(O)2>2 is diamagnetic (μeff = 0) and has an intense i.r. band at ca. 850 cm-1 attributed to νasym(Ru=O) stretching.The E1/2 value of the VI(L1)(O)2>(2+)/IV(L1)(O)(H2O)>(2+) couple in 0.1 mol dm-3 CF3CO2H is 0.79 V vs. a saturated calomel electrode.The reaction of VI(L1)(O)2>2 with styrene produced benzaldehyde.
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Full text of DOI:10.1039/DT9880002885