title: Noninnocence of Indigo: Dehydroindigo Anions as Bridging Electron-Donor Ligands in Diruthenium Complexes.
abstract: Complexes of singly or doubly deprotonated indigo (H2Ind) with one or two [Ru(pap)2](2+) fragments (pap = 2-phenylazopyridine) have been characterized experimentally [molecular structure, voltammetry, electron paramagnetic resonance (EPR), and UV-vis-near-IR spectroelectrochemistry] and by time-dependent density functional theory calculations. The compound [Ru(pap)2(HInd(-))]ClO4 ([1]ClO4) was found to contain an intramolecular NH---O hydrogen bond, whereas [{Ru(pap)2}2(μ-Ind(2-))](ClO4)2 ([2](ClO4)2), isolated as the meso diastereoisomer with near-IR absorptions at 1162 and 991 nm, contains two metals bridged at 6.354 Å distance by the bischelating indigo dianion. The spectroelectrochemical study of multiple reversible reduction and oxidation processes of 2(n) (n = 4+, 3+, 2+, 1+, 0, 1-, 2-, 3-, 4-) reveals the stepwise addition of electrons to the terminal π-accepting pap ligands, whereas the oxidations occur predominantly at the anionic indigo ligand, producing an EPR-identified indigo radical intermediate and revealing the suitability of deprotonated indigo as a σ- and π-donating bischelating bridge.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India.
authors.forename: Prasenjit
authors.initials: P
authors.lastname: Mondal
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India.
authors.forename: Madhumita
authors.initials: M
authors.lastname: Chatterjee
authors.affiliation: Institut für Anorganische Chemie, Universität Stuttgart , Pfaffenwaldring 55, D-70550 Stuttgart, Germany.
authors.forename: Alexa
authors.initials: A
authors.lastname: Paretzki
authors.affiliation: Institut für Anorganische Chemie, Universität Stuttgart , Pfaffenwaldring 55, D-70550 Stuttgart, Germany.
authors.forename: Katharina
authors.initials: K
authors.lastname: Beyer
authors.affiliation: Institut für Anorganische Chemie, Universität Stuttgart , Pfaffenwaldring 55, D-70550 Stuttgart, Germany.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Kaim
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay , Powai, Mumbai 400076, India.
authors.forename: Goutam Kumar
authors.initials: GK
authors.lastname: Lahiri