Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/xmlui/handle/123456789/19687
Title: Noninnocence of Indigo: Dehydroindigo Anions as Bridging Electron-Donor Ligands in Diruthenium Complexes
Authors: MONDAL, P
CHATTERJEE, M
PARETZKI, A
BEYER, K
KAIM, W
LAHIRI, GK
Keywords: Density-Functional Theory
Beta-Diketonate Ligand
Ruthenium Complexes
Triangular Metalloprism
Dinuclear Ruthenium
Excitation-Energies
Nindigo Complexes
Chelate Ligands
Metal-Complexes
Non-Innocence
Issue Date: 2016
Publisher: AMER CHEMICAL SOC
Citation: INORGANIC CHEMISTRY,55(6)3105-3116
Abstract: Complexes of singly or doubly deprotonated indigo (H(2)Ind) with one or two [Ru(pap)(2)](2+) fragments (pap = 2-phenyl-azopyridine) 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)(mu-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 angstrom 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, 17, 2, 3, 4) reveals the stepwise addition of electrons to the terminal pi-accepting pap ligands, whereas the oxidations occur predominantly at the. anionic indigo ligand, producing an EPA-identified indigo radical intermediate and revealing the suitability of deprotonated indigo as a sigma and pi-donating biSchelating bridge.
URI: http://dx.doi.org/10.1021/acs.inorgchem.6b00038
http://localhost:8080/xmlui/handle/123456789/19687
ISSN: 0020-1669
1520-510X
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