New diruthenium complexes formed via modification with 1,1′-ferrocene dicarboxylic acid

Carboxylate exchange reactions between Ru2(DArF)3(OAc)Cl (1) and 1,1′-ferrocene dicarboxylic acid resulted in the new compounds [Ru2(DArF)3Cl]2(μ-1,1′-(O2CFcCO2) (3), where DArF is either N,N′-di(3,5-dichlorophenyl)formamidinate (D(3,5-Cl2Ph)F, a), or N,N′-di(3-methoxyphenyl)formamidinate (DmAniF, b). The exchange reactions between Ru2(DArF)2(OAc)2Cl (2) and 1,1′-ferrocene dicarboxylic acid yielded the new compounds Ru2(DArF)2(O2CFcCO2)Cl (4a and 4b). The dimeric nature of compounds 3 was confirmed by both the MS data and an X-ray structural study of 3b. The monomeric nature of compounds 4a and 4b was confirmed by the MALDI-TOF MS data. Both compounds 3 and 4 were also characterized with cyclic (CV) and differential pulse voltammetry (DPV) and room temperature magnetic susceptibility measurements.

Carboxylate exchange reactions between Ru2(DArF)4-n(OAc)nCl type compounds and 1,1′ -ferrocene dicarboxylic acid resulted in either the O2CFcCO2-bridged dimers (n = 1) or the simple monomers with dicarboxylate in a tetradentate chelating mode (n = 2).Figure optionsDownload as PowerPoint slideResearch highlights
► We demonstrated the ability of 1,1′-ferrocene dicarboxylate to bridge two Ru2(DArF)3 units.
► We determined that 1,1′-ferrocene dicarboxylate prefer the tetra-dentate chelating coordination with the Ru2(DArF)2(OAc)2Cl type precursors.
► Voltammetric studies revealed insignificant intermetallic electronic couplings.