%0 Journal Article %1 Hazari.2018 %A Hazari, Arijit Singha %A Ghosh, Prabir %A Beyer, Katharina %A Schwederski, Brigitte %A Kaim, Wolfgang %A Lahiri, Goutam Kumar. %D 2018 %J Dalton Transactions %K carbonyl complex complex;isomer crystal diketopyrrolopyrrolate hydrido mol optimized prepn response ruthenium spectroelectrochem structure %N 39 %P 14078--14084 %R 10.1039/c8dt02806k %T Effect of positional isomerism on the spectroelectrochemical response of 3,6-bis(2-pyridyl)-diketopyrrolopyrrolate bridged bis(carbonylhydridoruthenium) compounds %V 47 %X Reaction of 3,6-bis(2-pyridyl)-diketopyrrolopyrrole (H2-BPDPP) with two equiv. of Ru(H)(CO)(Cl)(PPh3)3 in EtOH produced two sym. dinuclear isomers, (m-BPDPP)Ru(CO)H(PPh3)22, green 1 and blue 2, which could be sepd. chromatog. and characterized 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 addn. to the essentially planar bis-chelating bridge BPDPP2- and the mutually trans positioned axial PPh3 ligands in both complexes, compd. 1 was established with the CO groups trans to the pyrrolate-N atoms, whereas 2 has the p acceptors CO and pyridine-N situated trans to each other. While the redn. of 1 and 2 proceeds irreversibly at neg. potentials, the reversible oxidns. at rather low potentials could be monitored by EPR and UV-VIS-NIR absorption measurements. Together with TD-DFT calcns., these results reveal that the primary electron transfers are largely confined to the BPDPP ligand. Despite the bridge centered processes, small differences between the isomers 10/+ and 20/+ were found, affecting e.g. the near IR absorption of the radical cation species. on SciFinder(R)

@article{Hazari.2018, abstract = {Reaction of 3,6-bis(2-pyridyl)-diketopyrrolopyrrole (H2-BPDPP) with two equiv. of [Ru(H)(CO)(Cl)(PPh3)3] in EtOH produced two sym. dinuclear isomers, (\textgreek{m}-BPDPP)[Ru(CO)H(PPh3)2]2, green 1 and blue 2, which could be sepd. chromatog. and characterized 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 addn. to the essentially planar bis-chelating bridge BPDPP2- and the mutually trans positioned axial PPh3 ligands in both complexes, compd. 1 was established with the CO groups trans to the pyrrolate-N atoms, whereas 2 has the \textgreek{p} acceptors CO and pyridine-N situated trans to each other. While the redn. of 1 and 2 proceeds irreversibly at neg. potentials, the reversible oxidns. at rather low potentials could be monitored by EPR and UV-VIS-NIR absorption measurements. Together with TD-DFT calcns., these results reveal that the primary electron transfers are largely confined to the BPDPP ligand. Despite the bridge centered processes, small differences between the isomers 10/+ and 20/+ were found, affecting e.g. the near IR absorption of the radical cation species. [on SciFinder(R)]}, added-at = {2018-12-07T10:56:03.000+0100}, author = {Hazari, Arijit Singha and Ghosh, Prabir and Beyer, Katharina and Schwederski, Brigitte and Kaim, Wolfgang and Lahiri, Goutam Kumar.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2fc28486b28b9df01f1ec649d546b87bb/galaktoze}, doi = {10.1039/c8dt02806k}, interhash = {433c03a4b44b5be5821b0890fde99957}, intrahash = {fc28486b28b9df01f1ec649d546b87bb}, issn = {1477-9226}, journal = {Dalton Transactions}, keywords = {carbonyl complex complex;isomer crystal diketopyrrolopyrrolate hydrido mol optimized prepn response ruthenium spectroelectrochem structure}, number = 39, pages = {14078--14084}, timestamp = {2018-12-07T09:56:03.000+0100}, title = {Effect of positional isomerism on the spectroelectrochemical response of 3,6-bis(2-pyridyl)-diketopyrrolopyrrolate bridged bis(carbonylhydridoruthenium) compounds}, volume = 47, year = 2018 }