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Updated: May 23, 2026

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
9-Oxidophenalenone: a noninnocent β-diketonate ligand?
Amit Das1, Thomas Michael Scherer, Shaikh M Mobin
1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
Abstract:
The redox systems [Ru(L)(bpy)(2)](k), [Ru(L)(2)(bpy)](m), and [Ru(L)(3)](n) containing the potentially redox-active ligand 9-oxidophenalenone = L(-) were investigated by spectroelectrochemistry (UV-vis-near-IR and electron paramagnetic resonance) in conjunction with density functional theory (DFT) calculations. Compounds [Ru(L(-))(bpy)(2)]ClO(4) ([1]ClO(4)) and [Ru(L(-))(2)(bpy)]ClO(4) ([2]ClO(4)) were structurally characterized. In addition to establishing electron-transfer processes involving the Ru(II)/Ru(III)/Ru(IV) and bpy(0)/bpy(•-) couples, evidence for the noninnocent behavior of L(-) was obtained from [Ru(IV)(L(•))(L(-))(bpy)](3+), which exhibits strong near-IR absorption due to ligand-to-ligand charge transfer. In contrast, the lability of the electrogenerated anion [Ru(L)(2)(bpy)](-) is attributed to a resonance situation [Ru(II)(L(•2-))(L(-))(bpy)](-)/[Ru(II)(L(-))(2) (bpy(•-))](-), as suggested by DFT calculations.
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