Preparation and characterization of ruthenium(II), rhodium(III) and iridium(III) complexes of isocyanide bearing the azo group

Reactions of [(η6-arene)RuCl2]2 (1) (η6-arene=p-cymene (1a), 1,3,5-Me3C6H3 (1b), 1,2,3-Me3C6H3 (1c) 1,2,3,4-Me4C6H2(1d), 1,2,3,5-Me4C6H2 (1e) and C6Me6 (1f)) or [Cp*MCl2]2 (M=Rh (2), Ir (3); Cp*=C5Me5) with 4-isocyanoazobenzene (RNC) and 4,4′-diisocyanoazobenzene (CN–R–NC) gave mononuclear and dinuclear complexes, [(η6-arene)Ru(CNC6H4NNC6H5)Cl2] (4a–f), [Cp*M(CNC6H4NNC6H5)Cl2] (5: M=Rh; 6: M=Ir), [{(η6-arene)RuCl2}2{μ-CNC6H4NNC6H4NC}] (8a–f) and [(Cp*MCl2)2(μ-CNC6H4NNC6H4NC)}] (9: M=Rh; 10: M=Ir), respectively. It was confirmed by X-ray analyses of 4a and 5 that these complexes have trans-forms for the NN moieties. Reaction of [Cp*Rh(dppf)(MeCN)](PF6)2 (dppf=1,1′-bis (diphenylphosphino)ferrocene) with 4-isocyanoazobenzene gave [Cp*Rh(dppf)(CNC6H4NNC6H5)](PF6)2 (7), confirmed by X-ray analysis. Complex 8b reacted with Ag(CF3SO3), giving a rectangular tetranuclear complex 11b, [{(η6-1,3,5-Me3C6H3)Ru(μ-Cl}4(μ-CNC6H4NNC6H4NC)2](CF3SO3)4 bridged by four Cl atoms and two μ-diisocyanoazobenzene ligands. Photochemical reactions of the ruthenium complexes (4 and 8) led to the decomposition of the complexes, whereas those of 5, 7, 9 and 10 underwent a trans-to-cis isomerization. In the electrochemical reactions the reductive waves about −1.50 V for 4 and −1.44 V for 8 are due to the reduction of azo group, [NN]→[NN]2−. The irreversible oxidative waves at ca. 0.87 V for the 4 and at ca. 0.85 V for 8 came from the oxidation of Ru(II)→Ru(III).