Square-Planar Ruthenium(II) Complexes: Control of Spin State by Pincer Ligand Functionalization
2015 | journal article. A publication with affiliation to the University of Göttingen.
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Square-Planar Ruthenium(II) Complexes: Control of Spin State by Pincer Ligand Functionalization
Askevold, B.; Khusniyarov, M. M.; Kroener, W.; Gieb, K.; Mueller, P.; Herdtweck, E. & Heinemann, F. W. et al. (2015)
Chemistry - A European Journal, 21(2) pp. 579-589. DOI: https://doi.org/10.1002/chem.201404282
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Details
- Authors
- Askevold, Bjorn; Khusniyarov, Marat M.; Kroener, Wolfgang; Gieb, Klaus; Mueller, Paul; Herdtweck, Eberhardt; Heinemann, Frank W.; Diefenbach, Martin; Holthausen, Max C.; Vieru, Veacheslav; Chibotaru, Liviu F.; Schneider, Sven
- Abstract
- Functionalization of the PNP pincer ligand backbone allows for a comparison of the dialkyl amido, vinyl alkyl amido, and divinyl amido ruthenium(II) pincer complex series [RuCl{N(CH2CH2PtBu2)(2)}], [RuCl{N(CHCHPtBu2)(CH2CH2PtBu2)}], and [RuCl{N(CHCHPtBu2)(2)}], in which the ruthenium( II) ions are in the extremely rare square-planar coordination geometry. Whereas the dialkylamido complex adopts an electronic singlet (S=0) ground state and energetically low-lying triplet (S=1) state, the vinyl alkyl amido and the divinyl amido complexes exhibit unusual triplet (S=1) ground states as confirmed by experimental and computational examination. However, essentially non-magnetic ground states arise for the two intermediate-spin complexes owing to unusually large zero-field splitting (D> +200 cm(-1)). The change in ground state electronic configuration is attributed to tailored pincer ligand-to-metal pi-donation within the PNP ligand series.
- Issue Date
- 2015
- Status
- published
- Publisher
- Wiley-v C H Verlag Gmbh
- Journal
- Chemistry - A European Journal
- ISSN
- 1521-3765; 0947-6539
