Synthesis, structures, and properties of lantern-type dinuclear ruthenium(II,III) complexes cis-[Ru2{3,5-(CF3)2-pf}2(O2CMe)2Cl] and [Ru2{3,5-(CF3)2-pf}3(O2CMe)Cl], 3,5-(CF3)2-pf−=N,N′-bis[3,5-bis(trifluoromethyl)phenyl]formamidinate anion

New insights into progressive ligand replacement from [Ru2Cl(O2CCH3)4]: synthetic strategies and variation in redox potentials and paramagnetic shifts

“…This is in good accordance with other tri-substituted complexes containing other formamidinate ligands, whose syntheses give final products after long reaction times. 39,45,47,49…”

“…The synthesis of di-substituted complexes with a cis-configuration has been carried out using THF as the solvent, excess of LiCl and Et 3 N, and [Ru 2 Cl (O 2 CCH 3 ) 4 ] : formamidine in an approximate ratio of 1 : 2. 38,45,46 However, chromatographic column purification [45][46][47] or recrystallization 38 is needed in order to obtain the pure product. As above mentioned, a mixture of all the compounds of the series [Ru 2 Cl(DArF) x (O 2 CCH 3 ) 4-x ] (x = 1-4) is found when HDp-FPhF is used.…”

“…This is in good accordance with other tri-substituted complexes containing other formamidinate ligands, whose syntheses give final products after long reaction times. 39,45,47,49 Lastly, it is well known that to obtain tetra-substituted compounds, a reaction in molten ligand 56,57 or a large ligand excess under reflux conditions 56 is needed. In this regard, synthesis under reflux was not used to obtain compound [Ru 2 Cl (Dp-FPhF) 4 ] (4).…”

“…7 For [Ru 2 Cl(DArF) x (O 2 CCH 3 ) 4-x ]-type compounds, only a few species have been described. 38,39,[43][44][45][46][47][48][49] To the best of our knowledge, only one full series with x = 1-4 with the same formamidinate ligand has been published, 38,39,44 although no structural characterization for all the intermediates has been reported, nor a systematic evaluation of the substitution effect on their properties. In this work, a combination of conventional synthesis under reflux and non-conventional methods, such as ultrasonic irradiation and microwave heating, has allowed the obtention of tailored substitutions of acetate bridging ligands in [Ru 2 Cl(O 2 CCH 3 ) 4 ] by N,N′-bis(4-fluorophenyl)formamidinate (Dp-FPhF − ).…”