Synthesis and characterization of oxoruthenium(IV) complexes that utilize a 2,2'-biquinoline ligand

Abstract

Novel oxoruthenium(IV) complexes of the form [(bpy)(biq)(O)(PR3)RuIV] (C104)2 (where bpy = 2,2'-bipyridine, biq = 2,2'biquinoline, and PR3 = a tertiary phosphine ligand) have been generated through the oxidation of the analogous aquoruthenium(II) species. Characterization of the oxoruthenium(IV), aquoruthenium(II), and chlororuthenium(II) complexes was accomplished through the following methods: IR spectroscopy, cyclic voltammetry, constant-potential coulometry, and UV-visible spectroscopy. The chlororuthenium(II) complex was also characterized by 13C NMR spectroscopy. Aqueous cyclic voltammetric measurements of the aquoruthenium(II) and oxoruthenium(IV) complexes are consistent with a mechanism involving two concomitant oneelectron, one-proton transfers: Rulv(0)/Rum(0H)/Run(OH2). The oxoruthenium(IV) complexes act as oxidants toward organic substrates, where the 2,2'-biquinoline ligand has a clear effect on the kinetics of substrate oxidation.

Synthesis and structure of FeCl(C.tplbond.CPh)(DMPE)2

“…13 The structure was solved by direct methods using shelxs-8614 and was refined by full-matrix least-squares analysis with shelx-76. 15 All non-hydrogen atoms were refined anisotropically; hydrogen atoms were included at calculated sites (C-H = 0.97 A) with individual isotropic thermal parameters. Scattering factors and anaomalous dispersion corrections used for Fe were taken from ref 16, and all others were those supplied in shelx-76.15 Non-hydrogen atom coordinates are listed in Table II.…”

Selective Photoinduced Ligand Exchange in a New Tris–Heteroleptic Ru(II) Complex

“…1 Ru(biq) 2 Cl 2 . Ru(biq) 2 Cl 2 was prepared using a modification of the synthesis reported by Kubow et al 44 RuCl 3 ·H 2 O (0.18 g, 0.67 mmol), 2,2′-biquinoline (0.37 g, 1.5 mmol), and LiCl (0.087 g, 2.1 mmol) were dissolved in 7 mL of N,Ndimethylformamide. The solution was stirred until all solids dissolved, was degassed with N 2 for 5 min, and was then refluxed for 6 h turning a dark green color.…”

“…A yellow solid precipitated, and the powder was collected by vacuum filtrations and washed with 20 mL of diethyl ether (0.053 g, 62% yield). 1 H NMR (400 MHz, (CD 3 ) 2 CO) δ 10.05 (dd, 2H, 3 J = 5.3 Hz, 4 J = 1.2 Hz), 9.05 (dd, 2H, 3 J = 8.3 Hz, 4 J = 1.3 Hz), 8.64 (dd, 2H, 3 J = 7.1 Hz, 4 44 RuCl 3 •H 2 O (0.18 g, 0.67 mmol), 2,2′-biquinoline (0.37 g, 1.5 mmol), and LiCl (0.087 g, 2.1 mmol) were dissolved in 7 mL of N,Ndimethylformamide. The solution was stirred until all solids dissolved, was degassed with N 2 for 5 min, and was then refluxed for 6 h turning a dark green color.…”

Steric and Electronic Factors Associated with the Photoinduced Ligand Exchange of Bidentate Ligands Coordinated to Ru(II)

“…All other solvents were purchased from commercial sources and used as received. The complex Ru(biq) 2 Cl 2 and the dpb ligand were synthesized according to literature procedures .…”