Diastereomerization Dynamics of a Bistridentate Ru^II Complex

Summary, in English

The unsymmetrical nature of a new tridentate ligand bis(quinolinyl)-1,3-pyrazole (DQPz) is exploited in a bistridentate Ru(II) complex [Ru(DQPz)₂]²⁺ to elucidate an unexpected dynamic diastereomerism. Structural characterization based on a combination of nuclear magnetic resonance spectroscopy and density functional theory calculations reveals the first quantifiable diastereomerization dynamics for Ru complexes with fully conjugated tridentate heteroaromatic ligands. A mechanism that involves a large-scale twisting motion of the ligands is proposed to explain the dynamic interconversion between the observed diastereomers, and the analysis of both experiments and calculations reveals a potential energy landscape with a transition barrier for the diastereomerization of ∼70 kJ mol^-1. The structural flexibility demonstrated around the central transition metal ion has implications for integration of complexes into catalytic and photochemical applications.

• Författare: Martin Jarenmark; Göran Carlström; Lisa A. Fredin; Joachim Hedberg Wallenstein; Isa Doverbratt; Maria Abrahamsson; Petter Persson
• Avdelning/ar: Centrum för analys och syntes; Beräkningskemi; eSSENCE: The e-Science Collaboration
• Publiceringsår: 2016-03-21
• Språk: Engelska
• Sidor: 3015-3022
• Publikation/Tidskrift/Serie: Inorganic Chemistry
• Volym: 55
• Issue: 6
• Länkar: http://dx.doi.org/10.1021/acs.inorgchem.5b02893
• Dokumenttyp: Artikel i tidskrift
• Förlag: The American Chemical Society (ACS)
• Ämne: Inorganic Chemistry
• Status: Published
• ISBN/ISSN/Övrigt: ISSN: 0020-1669