Ruthenium oxo complexes of macrocyclic tertiary amines. Synthesis, electrochemistry, and reactivities of ruthenium oxo complexes of meso-2,3,7,11,12-pentamethyl-3,7,11,17-tetra-azabicyclo[11.3.1]heptadeca-1(17), 13,15-triene (L1), and X-ray crystal structure of trans-[RuIVL1(O)(NCO)]ClO4

Chi Ming Che, Wai Tong Tang, Wai On Lee, Wing Tak Wong, Ting Fong Lai

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Abstract

The new complexes trans-[RuIIIL1Cl2]Cl, trans-[RuIVL1(O)(NCO)]ClO4, and trans-[RuVI-L1(O)2][ClO4]2{L1= meso-2,3,7,11,12-pentamethyl-3,7,11,17-tetra-azabicyclo[1 1.3.1] heptadeca-1 (17),13,15-triene} have been prepared. Their redox chemistry was studied in comparison with the related Ru-L2-oxo system (L2= 1,4,8,11-tetramethyl-1,4,8,11 -tetra-azacyclotetradecane). At pH 1.1, the E°, of the trans-[RuVIL1(O)2]2+/trans-[RuIVL1(O)(H2O)]2+couple occurs at 0.76 V vs. saturated calomel electrode. The complex cation trans-[RuIVL1(O)(NCO)]+[space group P1, a = 7.765(1), b = 10.714(1), c = 14.076(1) Å, α = 80.49(1), β = 86.03(1), γ = 88.11(1)°, Z = 2, and R = 0.034 for 3 629 observed MO-Kα, data] has been determined by X-ray crystallography. The Ru=O distance is 1.777(2) Å. The N-Me groups all lie on the same side of the macrocyclic ring. The complex trans-[RuVIL1(O)2]2+is capable of oxidizing alcohols, styrene, and toluene at room temperature.
Original languageEnglish
Pages (from-to)2011-2016
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number10
DOIs
Publication statusPublished - 1 Dec 1989
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)

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