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

Abstract

The new complexes trans-[Ru^IIIL¹Cl₂]Cl, trans-[Ru^IVL¹(O)(NCO)]ClO₄, and trans-[Ru^VI-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-[Ru^VIL¹(O)₂]²⁺/trans-[Ru^IVL¹(O)(H₂O)]²⁺ couple occurs at 0.76 V vs. saturated calomel electrode. The complex cation trans-[Ru^IVL¹(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-K_α, 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-[Ru^VIL¹(O)₂]²⁺ is capable of oxidizing alcohols, styrene, and toluene at room temperature.