New insights into progressive ligand replacement from [Ru 2 Cl(O 2 CCH 3 ) 4 ]: synthetic strategies and variation in redox potentials and paramagnetic shifts.

The complete series of [Ru 2 Cl(D p -FPhF) x (O 2 CCH 3 ) 4- x ] ( x = 1-4; D p -FPhF - = N , N '-bis(4-fluorophenyl)formamidinate) compounds, has been prepared and characterized by a multi-technique approach, including single crystal X-ray diffraction. A careful study of the different methodologies has allowed us to prepare four compounds with good yields and without an inert atmosphere or further purification. Specifically, [Ru 2 Cl(D p -FPhF)(O 2 CCH 3 ) 3 ] (1) was obtained using an ultrasound-assisted (USS) method, while [Ru 2 Cl(D p -FPhF) 4 ] (4) was prepared by microwave assisted solvothermal synthesis (MWS). The intermediate substitution products cis -[Ru 2 Cl(D p -FPhF) 2 (O 2 CCH 3 ) 2 ] (2) and [Ru 2 Cl(D p -FPhF) 3 (O 2 CCH 3 )] (3) have been prepared by conventional heating, controlling the molar ratio of the starting materials. ESI-MS and infrared spectroscopy were used to follow all the reactions and permitted a qualitative evaluation of the axial reactivity in this series. Magnetic and absorption measurements confirmed a high spin σ 2 π 4 δ 2 (π*δ*) 3 electronic configuration in all cases. However, the effect of the gradual modification of the electronic density in the diruthenium core markedly affects other properties. The cyclic voltammograms of the compounds show a strong decrease in the one electron oxidation potential and an increase in the reduction potential in the series from 1 to 4. Furthermore, despite their paramagnetic nature, 1 H- and 19 F-NMR spectra were recorded, and a correlation between the paramagnetic shift of the signals and the substitution degree of the diruthenium species was observed. These results provide a comprehensive guide to synthesise and understand the effects of equatorial ligand substitution on the properties of Ru 2 5+ compounds.