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Issue 39, 2018
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Effect of positional isomerism on the spectroelectrochemical response of 3,6-bis(2-pyridyl)-diketopyrrolopyrrolate bridged bis(carbonylhydridoruthenium) compounds

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Abstract

Reaction of 3,6-bis(2-pyridyl)-diketopyrrolopyrrole (H2-BPDPP) with two equivalents of [Ru(H)(CO)(Cl)(PPh3)3] in EtOH produced two symmetrical dinuclear isomers, (μ-BPDPP)[Ru(CO)H(PPh3)2]2, green 1 and blue 2, which could be separated chromatographically and characterised spectroscopically (1H and 31P NMR, IR, and UV-VIS). Isomeric forms of 1 and 2 were authenticated using their single crystal X-ray structures. In addition to the essentially planar bis-chelating bridge BPDPP2− and the mutually trans positioned axial PPh3 ligands in both complexes, compound 1 was established with the CO groups trans to the pyrrolate–N atoms, whereas 2 has the π acceptors CO and pyridine–N situated trans to each other. While the reduction of 1 and 2 proceeds irreversibly at negative potentials, the reversible oxidations at rather low potentials could be monitored by EPR and UV-VIS-NIR absorption measurements. Together with TD-DFT calculations, these results reveal that the primary electron transfers are largely confined to the BPDPP ligand. Despite the bridge centred processes, small differences between the isomers 10/+ and 20/+ were found, affecting e.g. the near infrared absorption of the radical cation species.

Graphical abstract: Effect of positional isomerism on the spectroelectrochemical response of 3,6-bis(2-pyridyl)-diketopyrrolopyrrolate bridged bis(carbonylhydridoruthenium) compounds

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Publication details

The article was received on 09 Jul 2018, accepted on 13 Sep 2018 and first published on 17 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT02806K
Citation: Dalton Trans., 2018,47, 14078-14084
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    Effect of positional isomerism on the spectroelectrochemical response of 3,6-bis(2-pyridyl)-diketopyrrolopyrrolate bridged bis(carbonylhydridoruthenium) compounds

    A. S. Hazari, P. Ghosh, K. Beyer, B. Schwederski, W. Kaim and G. K. Lahiri, Dalton Trans., 2018, 47, 14078
    DOI: 10.1039/C8DT02806K

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