Synthesis and Crystal Structure of Metal Complexes of N‐phenyl‐o‐benzoquinonediimine (M = Ru²⁺, Co³⁺, Ni²⁺)

Abstract

Abstract Electron‐delocalized quinoid‐like complexes — [Ru II (bipy) 2 (N‐ph‐bqdi)] 2+ , cw‐[Co III (N‐ph‐s‐bqdi) 2 (py)] + and trans ‐[Ni II (N‐ph‐s‐bqdi) 2 ] (N‐ph‐bqdi = N‐phenyl‐ o ‐benzoquinonediimine, N‐ph‐s‐bqdi = N‐phenyl‐ o ‐semi‐benzoquinonediimine) were synthesized that display reversible multi‐electron redox couples. The respective cis ‐ and trans ‐ conformation of the Co and Ni complexes are controlled by the steric effect of the substituent phenyl group. The Ni complex forms one‐dimensional stacks in crystals. The crystal and molecular structures of three compounds are reported. [Ru(bipy) 2 (N‐ph‐bqdi)](PF 6 ) 2 : space group P2 l /c, a = 13.292(2), b = 18.785(4), c = 13.959(2) Å; β = 97.42(1)°, V = 3456(1) Å 3 , Z = 4, Rf = 0.047, Rw = 0.044; cis ‐[Co(N‐ph‐s‐bqdi) 2 (py)](OAc)(H 2 O): space group P2 1 /n, a = 12.752(4), b = 13.303(2), c = 16.683(3) Å; β = 102.27(2)°, V = 2765(1)Å 3 Z = 4, Rf = 0.035, Rw = 0.035; and trans ‐[Ni(N‐ph‐s‐bqdi) 2 ]: space group P‐1, a = 9.771(2), b = 10.417(1), c = 11.541(2) Å; α = 92.24(1), β = 104.04(1), γ = 117.94(1)°, V = 990.6(3) Å 3 , Z = 2, Rf = 0.030, Rw = 0.031. Infrared, 1 H NMR, 15 N NMR and electronic absorption spectra, elemental analyses, magnetic and cyclic voltammetric data are presented.