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-[Ru IV L1(O)(NCO)]ClO4

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 P, 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 RuO 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.