Disproportionation of a ruthenium(III) nitro complex of a macrocyclic tertiary amine in an aqueous medium

Abstract

The reaction of trans-[RuLCl₂]⁺(L = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane) with NO₂^– in water at 60 °C leads to the formation of trans-[RuL(O)Cl]⁺ and trans-[RuL(OH)(NO)]²⁺. The formation of the products can be rationalized by the disproportionation of trans-[RuL(Cl)(NO₂)]⁺. The structures of the products have been determined by X-ray crystallography: trans-[RuL(O)Cl]ClO₄, space group Pna2₁(no. 33), a= 12.616(1), b= 15.421(3), c= 11.292(3)Å; RuO and Ru–Cl 1.75(1) and 2.435(6)Å; trans-[RuL(OH)(NO)][ClO₄]₂, space group Pbca(no. 61), a= 20.459(3), b= 29.16(1), c= 25.13(1)Å; average Ru–OH and Ru–NO 1.906(9) and 1.74(1)Å.