Reaction of Tris(β-diketonato)ruthenium(III) Complexes with Strong Acids in Acetonitrile. Formation of Bis(acetonitrile)bis(β-diketonato)ruthenium(III) Complexes

Abstract

Bis(acetonitrile)bis(β-diketonato)ruthenium(III) was readily formed through the reaction of the corresponding tris(β-diketonato)ruthenium(III) with perchloric, sulfuric, or hydrochloric acid in acetonitrile. The reaction was quantitative; the stoichiometry was 1:1 for each strong acid studied here. This reaction was employed to prepare several bis(acetonitrile)bis(β-diketonato)ruthenium(III) complexes, which proved to be convenient intermediates for the synthesis of mixed-ligand β-diketonato ruthenium(III) complexes of the [RuIIIL2L′] type.

Invariant Oxidation State of Copper but not of Ruthenium in Complexes with Noninnocent N‐(2‐Methyl‐5,8‐dioxo‐5,8‐dihydroquinolin‐7‐yl)acetamide: A Combined Structural, Electrochemical and Spectroelectrochemical Investigation

“…General Considerations: The complexes cis-Ru(acac) 2 (CH 3 CN) 2 , [38] [(dppf)Cu(CH 3 CN) 2 ](BF 4 ) [39] and the ligand (L) [40] were synthesized according to reported procedures. RuCl 3 ·nH 2 O was purchased from Merck, CuCl from Strem, and 1,1Ј-bis(diphenylphosphanyl)ferrocene from Alfa Aesar.…”

Synthesis and Characterization of a Series of Ruthenium Tris(β‐diketonato) Complexes by an UHV‐STM Investigation and Numerical Calculations

“…Complex 2 can also be obtained from another method (see Scheme 2), but with lower yield, by the preparation of the bis(MeCN)bis(β-diketonato)ruthenium(III) species through a ligand displacement reaction of tris(β-diketonato)ruthenium(III) complexes, induced by strong acid. [49,50] The iodination or bromination selectively occurred at the γ-position of the acac ligand and led to compounds 5 and 6 in good yield (77 and 89 %, respectively); this was adapted from literature procedures. [51][52][53] Scheme 1.…”

Syntheses, Crystal Structures and Electrochemical Properties of Acetylacetonato-Ruthenium Complexes Containing Substituted Pyridine Ligands

“…Treatment of Ru(acac) 3 with an excess of the substituted pyridines in the presence of Br 2 in refluxing THF afforded the neutral paramagnetic ruthenium(III) complexes [Ru III Each of the cyclic voltammograms of complexes 1 and 2 shows one oxidation peak (E 1/2 = 0.82 V for 1, E 1/2 = − 0.42 V for 2) and one reduction peak (E 1/2 = 0.23 V for 1, E 1/2 = 0.47 V for 2), which are assigned to the Ru III -Ru II couple and ligandcentered oxidation, respectively. It is also noted that each of the cyclic voltammograms of complexes 3 and 4 reveals two reversible couples (E 1/2 = − 0.59 V and − 1.23 V for 3, E 1/2 = − 0.42 V and − 1.27 V for 4) assigned to the metal-centered oxidation of Ru IV -Ru III and the metal-centered Ru III -Ru II couple, respectively, which are shifted to negative potential compared with that of Ru(acac) 3 (oxidation: 0.60 V, reduction: − 1.16 V) [24]. All peaks are corresponding to reversible one-electron transfer processes [25].…”