Bisaryl and Bisalkynyl Diruthenium (III,III) Compounds Based on an Electron-Deficient Building Block

Reported herein is a new series of diruthenium(III,III) bisalkynyl and bisaryl diruthenium(III,III) compounds supported with 2-amino-3-(trifluoromethyl)pyridinate (amtfmp). Using Ru₂(amtfmp)₄Cl₂ from a modified preparation, cis 2:2 Ru₂(amtfmp)₄(C≡CPh)₂ (1), cis 2:2 Ru₂(amtfmp)₄(Ph)₂ (2), and 3:1 Ru₂(amtfmp)₄(Ph)₂ (3) were synthesized via a lithium-halogen exchange reaction using LiC₂Ph and LiPh, respectively. Compounds 1-3 are all Ru₂(III,III) species with a ground-state configuration of π⁴δ²(π*)⁴ (S = 0) and were characterized via mass spectrometry, electron absorption and ¹H/¹⁹F NMR spectroscopies, and voltammetry. The molecular structures of 1-3 were established using single-crystal X-ray diffraction analysis, and preliminary density functional theory analysis was performed to elaborate the electronic structures of 1 and 2. Comparisons of the electrochemical properties of 1-3 against the Ru₂(amtfmp)₄Cl₂ starting material reveal cathodic shifts of the Ru₂^7+/6+ oxidation and the Ru₂^6+/5+ and Ru₂^5+/4+ reduction potentials. In comparison to related Ru₂(III,III) bisalkynyl and bisaryl compounds, the electrode potentials for 1-3 are anodically shifted up to ca. 0.95 V, highlighting the strong electron-withdrawing nature of the amtfmp ligand.