3 years ago

Coordination chemistry of the redox non-innocent bis(2-amino-3,5-di-tert-butylphenyl)amine with group 10 metal ions (Ni, Pd, Pt)

Jules Moutet, Fabrice Thomas, Florian Molton, Thibaut Constantin, Christian Philouze, Nicolas Leconte
The pincer ligand H3L3N was chelated to Ni(II), Pd(II) and Pt(II). Square planar complexes of stoichiometry (2:1) ligand:metal formed, wherein the ligand coordinates in a bidentate fashion. By X-Ray diffraction we establish that each ligand molecule coordinates under its diiminosemiquinone radical form in the neutral Ni(II), Pd(II) and Pt(II) complexes (1, 2 and 3, respectively). The resulting systems are singlet diradical species, with a predicted J in the range -1062 to -1764 cm-1. These diradicals display an intense LLCT transition involving the diiminosemiquinone moieties: 860 nm (1), 852 nm (2) and 760 nm (3). Complex 1, 2 and 3 exhibit reversible oxidation waves in their CV curve. The cations 1+, 2+ and 3+ are (S = ½) systems with g values close to 2. The intensity of the resonance, 1+ < 2+, 3+ is consistent with easy comproportionation of 1+. X-Ray diffraction analysis discloses that 3+ is a mixed-valent radical mononuclear complex. An intense IVCT is observed at low energy (1536, 1656 and 1256 nm for 1+, 2+ and 3+, respectively), confirming that this classification applies to all the cations. The dications 12+, 22+ and 32+ are closed-shell bis(diiminobenzoquinone) species. The crystal structure of 32+ shows that this complex exhibits the shortest mean C-N bond distances within the series.

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

DOI: 10.1002/ejic.201701448

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.