RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground stateGrupp, A., Bubrin, M., Ehret, F., Zeng, Q., Hartl, F., Kvapilová, H., Zálisˇ, S. and Kaim, W. (2013) RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state. European Journal of Inorganic Chemistry, 2014 (1). pp. 110-119. ISSN 1434-1948 Full text not archived in this repository. It is advisable to refer to the publisher's version if you intend to cite from this work. See Guidance on citing. To link to this item DOI: 10.1002/ejic.201301206 Abstract/SummaryThe new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297<d(CN)<1.344 Å and 1.382<d(CC)<1.425 Å, which suggest a RuIII(R-DAB·–) oxidation state formulation. This notion is confirmed by the negligible solvatochromism of the intense (ε ≈ 104 M–1cm–1) charge-transfer absorption band in the visible region and by DFT calculations. Oxidation of the compounds occurs mainly at the R-DAB·– radical ligand to produce UV/Vis/NIR and electron paramagnetic resonance (EPR) spectroelectrochemically detectable RuIII species, whereas the reduction proceeds less reversibly and yields predominantly (R-DAB)-ligand-based spin for the 4-methoxyphenyl derivative, measured at low temperature. The results are discussed with respect to metal-to-ligand chargetransfer (MLCT) excited states of conventional (α-diimine)- ruthenium(II) complexes and in view of other (α-diimine)- metal complexes with ambiguous oxidation-state assignments.
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