3 years ago

Ru(II) Complexes with a Chemical and Redox-Active S2N2 Ligand: Structures, Electrochemistry, and Metal–Ligand Cooperativity

Ru(II) Complexes with a Chemical and Redox-Active S2N2 Ligand: Structures, Electrochemistry, and Metal–Ligand Cooperativity
Christian Haas, Scott R. Daly, Kyle D. Spielvogel, Javier A. Luna, Scott K. Shaw, Gummadi Durgaprasad
Here we describe the synthesis, structures, and reactivity of Ru complexes containing a triaryl, redox-active S2N2 ligand derived from o-phenylenediamine and thioanisole subunits. The coordination chemistry of N,N′-bis[2-(methylthio)phenyl]-1,2-diaminobenzene [H2(MeSNNSMe)] was established by treating RuCl2(PPh3)3 with H2(MeSNNSMe) to yield {Ru[H2(MeSNNSMe)]Cl(PPh3)}Cl (1). Coordinated H2(MeSNNSMe) was sequentially deprotonated to form Ru[H(MeSNNSMe)]Cl(PPh3) (2) followed by the five-coordinate, square pyramidal complex Ru(MeSNNSMe)(PPh3) (3). Single-crystal X-ray diffraction (XRD) studies revealed that the ligand structurally rearranged around the metal at each deprotonation step to conjugate the adjacent aryl groups with the o-phenylenediamine backbone. Deprotonation of 2 with NaBH4 or treatment of 3 with BH3·tetrahydrofuran (THF) yielded Ru[(μ-H)BH2](MeSNNSMe)(PPh3) (5) with BH3 bound across a Ru–N bond in a metal–ligand cooperative fashion. The cyclic voltammogram of 3 in THF revealed three redox events consistent with one-electron oxidations and reductions of the o-phenylenediamine backbone and the metal (Ru3+/Ru2+). Reactions of 3 with CO, HBF4, and benzoic acid yielded the new complexes Ru(MeSNNSMe)(CO)(PPh3), {Ru[H(MeSNNSMe)](PPh3)(THF)}BF4, and Ru[H(MeSNNSMe)](PPh3)(PhCO2), indicating broader suitability for small molecule binding and reactivity studies. Subsequent nuclear magnetic resonance spectroscopy, infrared spectroscopy, and mass spectrometry data are reported in addition to molecular structures obtained from single-crystal XRD studies.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00623

DOI: 10.1021/acs.organomet.7b00623

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.