Isomeric Diruthenium Complexes Bridged by Deprotonated Indigo in cis and trans Configuration

0487713 - ÚFCH JH 2019 RIV DE eng J - Journal Article
Chatterjee, M. - Ghosh, P. - Beyer, K. - Paretzki, A. - Fiedler, Jan - Kaim, W. - Lahiri, G. K.
Isomeric Diruthenium Complexes Bridged by Deprotonated Indigo in cis and trans Configuration.
Chemistry-An Asian Journal. Roč. 13, č. 1 (2018), s. 118-125. ISSN 1861-4728. E-ISSN 1861-471X
Institutional support: RVO:61388955
Keywords : isomerism * ruthenium * spectroelectrochemistry * structure
OECD category: Physical chemistry
Impact factor: 3.698, year: 2018

The doubly deprotonated form L2- of indigo=H2L can bind two [Ru(acac)(2)] complex fragments in the cis (1) and trans configuration (2), as evidenced from crystal structure analysis. While the latter type of N,O. N',O' coordination has been observed earlier, for example, with [Ru(bpy)(2)](2+), leading to two equivalent six-membered ring chelates, the cis arrangement in 1 is observed here for the first time in a dinuclear complex, producing one five-membered ring chelate with N,N-' coordination and one seven-membered chelate with O,O-' coordination. The different structures of the isomers result in differing electrochemical and spectroelectrochemical (EPR, UV-Vis-NIR) responses for various accessible charge states 1(n) and 2(n), n=-, 0, +, 2+. The associated electronic structures were analyzed by DFT (structures, spin density) and TD-DFT calculations (electronic transitions), revealing mainly metal-based reduction but largely indigo ligand-based oxidation of both neutral precursors.
Permanent Link: http://hdl.handle.net/11104/0282353