129873-57-0Relevant academic research and scientific papers
Synthesis and characterization of (nitro)ruthenium complexes that utilize identical trans-positioned tertiary phosphine ligands
Leising, Randolph A.,Kubow, Stephen A.,Takeuchi, Kenneth J.
, p. 4569 - 4574 (2008/10/08)
We report the synthesis and characterization of a variety of complexes with the form [Ru(NO2)(PR3)2(trpy)](ClO4) (trpy = 2,2′:6′,2″-terpyridine and PR3 = tertiary phosphine ligand, where R = ethyl, n-propyl, n-butyl, phenyl, and benzyl) and [Ru-(NO)(PR3)2(trpy)](ClO4)3. Two routes toward the syntheses of the [Ru(NO2)(PR3)2(trpy)](ClO4) complexes, starting from Ru(Cl)3·3H2O, will be discussed. One method involves a five-step synthesis, with the stepwise addition of the phosphine ligands. The other route, a three-step synthesis, involves a novel one-pot incorporation of two phosphine ligands into the trans positions of a ruthenium coordination center. Characterization of the [Ru(NO2)(PR3)2(trpy)](ClO4) complexes was accomplished through elemental analysis, IR, UV-visible, 1H NMR, and 13C NMR spectroscopies, and cyclic voltammetry. Notably, variations in the phosphine ligands resulted in cyclic voltammograms that ranged from reversible to irreversible, where the utilization of trimethylphosphine resulted in the greatest reversibility. The irreversible voltammograms indicated that the electrochemically generated [Ru(NO2)(PR3)2(trpy)]2+ complexes were unstable and that the analogous [Ru(NO)(PR3)2(trpy)]3+ complexes were the decomposition products. In this regard, we also report the synthesis and characterization of [Ru(NO)(PR3)2(trpy)](ClO4)3 complexes, where the complexes were characterized by elemental analysis, IR and UV-visible spectroscopies, and cyclic voltammetry.
