Multistep redox sequences of azopyridyl (L) bridged reaction centres in stable radical complex ions {(μ-L)[MCl(η⁵-C₅Me₅)]₂}˙⁺, M = Rh or Ir: spectroelectrochemistry and high-frequency EPR spectroscopy

Structures, Redox and Spectroscopic Properties of PdII and PtII Complexes Containing an Azo Functionality

“…The lability of metal-halide bonds on reduction is much more pronounced for 4d metals than for 5d metals. [27,28] Such lability can sometimes be desirable for certain kinds of catalytic activation. [29,30] The reduction potentials for both complexes are anodically shifted compared to that of the free ligand.…”

The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

“…The resulting compounds [IrCp*(E-E)] [11,6,21], mixed-valent intermediates [Cp*Ir(l-(E-E))IrCp*] + [16] and dinuclear complexes [Cp*Ir(l-(E-E))IrCp*] [15][16][17][18] were identified and investigated by various methods including EPR, UV-vis-NIR spectroelectrochemistry, resonance Raman spectroscopy, fast scan cyclovoltammetry, and DFT methodology [1,2,6,[22][23][24]. The catalysis potential of such complexes, mainly of the prototypical E-E = bpy = 2,2 0 -bipyridine system, has been studied with emphasis on hydride activation and photoreactivity [4,5,13,14,25].…”

“…The two-electron reductive elimination of chloride from complexes [IrCp*Cl(E-E)] + where E-E is a bidentate ligand has been described and analyzed [1][2][3] for mononuclear [4][5][6][7][8][9][10][11][12][13][14], for homodinuclear [15][16][17][18] and for heterodinuclear systems [19,20]. The resulting compounds [IrCp*(E-E)] [11,6,21], mixed-valent intermediates [Cp*Ir(l-(E-E))IrCp*] + [16] and dinuclear complexes [Cp*Ir(l-(E-E))IrCp*] [15][16][17][18] were identified and investigated by various methods including EPR, UV-vis-NIR spectroelectrochemistry, resonance Raman spectroscopy, fast scan cyclovoltammetry, and DFT methodology [1,2,6,[22][23][24].…”

Komplexe mit Stickstoffradikalliganden: Einteilung, spektroskopische Eigenschaften, Reaktivität und katalytische Anwendungen

“…Das Q-Band-EPR-Spektrum (15 K) von 4 zeigt eine ziemlich kleine Anisotropie des g-Tensors (g 1 = 2.0822, g 2 = 2.0467, g 3 = 2.0247), die darauf schließen lässt, dass die Spin-Bahn-Wechselwirkung in 4 viel schwächer ist als für ein Rh II -Zentrum erwartet. [14] Mit Puls-EPR-Methoden ( [15] Die Deprotonierung und Oxidation der 16e-trop-Komplexe 5 machte einige ähnliche offenschalige Spezies zugänglich (Schema 4). [16] Da diese gegenüber dem Solvens reaktiver sind als 4, konnten die vermuteten Radikalkomplexe 6 nicht durch Rçntgenstrukturanalyse charakterisiert werden.…”