5 years ago

The Femtochemistry of a Ferracyclobutadiene

The Femtochemistry of a Ferracyclobutadiene
Alexander C. Filippou, Ujjal Das, Peter Vöhringer, Boris Wezisla, Jörg Lindner
The eminent role of metallacyclobutadienes as catalytic intermediates in organic synthesis and polymer chemistry is widely acknowledged. In contrast, their photochemistry is as yet entirely unexplored. Herein, the photo-induced primary processes of a ferracyclobutadiene tricarbonyl complex in solution are revealed by femtosecond mid-infrared spectroscopy. The time-resolved vibrational spectra expose an ultrafast substitution of a basal CO ligand by a solvent molecule in a consecutive dissociation–association mechanism. Following optical excitation, the system relaxes non-radiatively to the triplet ground state from which a CO is expelled. Since the triplet state is bound with respect to Fe−CO cleavage, the dissociation can only occur from vibrationally excited states. The excitation energy, vibrational relaxation, and intersystem crossing to the singlet ground state control the primary quantum yield for formation of the ferracyclic dicarbonyl–solvent product complex. Blink and you'll miss it: Femtosecond infrared spectroscopy was used to monitor the photochemical dynamics of an electron-rich, puckered ferracyclobutadiene in liquid solution. The results show an ultrafast substitution of a CO ligand by a solvent molecule.

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

DOI: 10.1002/anie.201702987

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.