3 years ago

Noninnocent β-Diiminate Ligands: Redox Activity of a Bis(alkylimidazole)methane Ligand in Cobalt and Zinc Complexes

Noninnocent β-Diiminate Ligands: Redox Activity of a Bis(alkylimidazole)methane Ligand in Cobalt and Zinc Complexes
Robertus J. M. Klein Gebbink, Marc-Etienne Moret, Charl F. Riemersma, Martin Lutz, Richard Naastepad, Pradip Ghosh
A new β-diiminate ligand (the bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane anion, BMIMPh2−) is introduced, in which the ligand framework bears an extended imidazole-based π-system in conjugation with a formal β-diketiminates (NacNac) backbone. Bis-ligated transition metal complexes (Co, Zn) featuring this anionic ligand undergo a series of four consecutive single-electron oxidations that are all ligand-based. The singly and doubly oxidized complexes can be synthesized on a preparative scale and have been fully characterized by various spectroscopic techniques. This is in sharp contrast to the corresponding NacNac-based complexes in which only singly oxidized complexes were isolated and characterized. Single crystal X-ray structure determination revealed a correlation between the intra-ligand metrical parameters and the oxidation state of BMIMPh2−. These structural changes in the ligand framework make BMIMPh2− as a perceptible non-innocent ligand in contrast to NacNac type ligands. Guilty as charged! Homoleptic transition metal complexes of a new class of β-diiminate ligand can undergo four ligand-based single-electron oxidations in total. The redox non-innocence of the ligand is perceptible by means of single crystal structural analysis.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701215

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.