Bonding and Substituent Effects in Electron-Rich Mononuclear Ruthenium σ-Arylacetylides of the Formula [(η<sup>2</sup>-dppe)(η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>)Ru(C⋮C)-1,4-(C<sub>6</sub>H<sub>4</sub>)X][PF<sub>6</sub>]<i><sub>n</sub></i> (<i>n</i> = 0, 1; X = NO<sub>2</sub>, CN, F, H, OMe, NH<sub>2</sub>)
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This study reports the isolation and the structural (X-ray), UV−vis, and NMR characterization of a series of electron-rich Ru(II) acetylide complexes of the formula (η2-dppe)(η5-C5Me5)Ru(C⋮C)-1,4-(C6H4)X (1a−f; X = NO2, CN, F, H, OMe, NH2) and (η2-dppe)(η5-C5Me5)Ru(C⋮C)-1,3-(C6H4)F (1c-m), as well as the spectroscopic (near-IR and ESR) in situ characterization of the corresponding elusive Ru(III) radical cations. The spectroscopic data are discussed in connection with DFT computations, and a consistent picture of the electronic structure of these Ru(II) and Ru(III) acetylide complexes is proposed. Notably, the strong reactivity of the Ru(III) radicals evidenced in this contribution constitutes a major difference with the relative stability of the known iron analogues.
