Square-Planar Ruthenium(II) Complexes: Control of Spin State by Pincer Ligand Functionalization

Askevold B, Khusniyarov M, Kroener W, Gieb K, Müller P, Herdtweck E, Heinemann FW, Diefenbach M, Holthausen MC, Vieru V, Chibotaru LF, Schneider S (2015)

Publication Language: English

Publication Status: Published

Publication Type: Journal article, Original article

Publication year: 2015

Journal

Publisher: Wiley-VCH Verlag

Book Volume: 21

Pages Range: 579-589

DOI: 10.1002/chem.201404282

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.

Authors with CRIS profile

Involved external institutions

Katholieke Universiteit Leuven (KUL) / Catholic University of Leuven Belgium (BE) Georg-August-Universität Göttingen Germany (DE) Technische Universität München (TUM) Germany (DE) Goethe-Universität Frankfurt am Main Germany (DE)

How to cite

APA:

Askevold, B., Khusniyarov, M., Kroener, W., Gieb, K., Müller, P., Herdtweck, E.,... Schneider, S. (2015). Square-Planar Ruthenium(II) Complexes: Control of Spin State by Pincer Ligand Functionalization. Chemistry - A European Journal, 21, 579-589. https://doi.org/10.1002/chem.201404282

MLA:

Askevold, Bjorn, et al. "Square-Planar Ruthenium(II) Complexes: Control of Spin State by Pincer Ligand Functionalization." Chemistry - A European Journal 21 (2015): 579-589.

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